RU2260022C2 - Epoxy binding agent for reinforced plastics (variants) and method for its preparing - Google Patents

Abstract

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to hybrid binding agents based on epoxy triphenolic resin designated for reinforced plastics with enhanced corrosion resistance and thermal stability and to methods for their preparing. A binding agent comprises epoxy triphenolic resin, plasticizing agent as a diluting agent representing resin DEG-1, resol-phenolformaldehyde resin SF-340A as a hardening agent and mixture of acetone, ethyl alcohol and petroleum and/or coal toluene as a solvent. Anti-static additive, antipyrene additive, crystalline sodium alumosilicate and a filling agent can be added to the binding agent composition additionally. A filling agent can be in forms of monolith or hollow thread-like crystals, finely divided powder-like filling of monolith, hollow, scaly and fibrous particles. The combination of components taken in the definite ratios and carrying out a method for preparing a binding agent at enhanced temperatures and in the definite sequence of addition of components into reactor and assigned temperature-temporal regimens of their stirring and dissolving provides the improvement of properties of the binding agent. Monolith composites as product of hardening binding agents elicit improved physical-mechanical, heat-physical, electric and anti-static properties with the density value 0.96-1.1 g/cm³, the mass content of nonvolatile substances 55-63% and the gelatinizing time 4-8 min at temperature 160-200°C. The claimed invention can be used in preparing prepregs by impregnation method of glass-organo-coal-filled filling agents, among them caproamide, basalt, polyphene and fibers with different lubricants, dressings and other coatings.

EFFECT: improved and valuable properties of binding agent.

50 cl, 3 dwg, 67 tbl, 20 ex

Description

The invention relates to heat-erosion-resistant binder based on epoxy resins intended for the manufacture of glass-carbon-boron-organoplastic products with increased corrosion resistance, thermal stability, as well as products from composite fibrous materials that are operated under conditions of exposure to highly enthalpy high-speed gas flows and / or in long-term exposure to aggressive environments of flue gases and can be used in the rocket and space industry, aircraft manufacturing, and also in a number of other sectors of the national economy - mechanical engineering, railway transport, nuclear, oil and gas and chemical industries, in the fields of large and small energy, medicine, construction, agriculture and other industries.

In particular, it can be widely used in the creation and repair of pipelines of various classes and purposes, containers and tanks for the transport of goods, aerospace products, for example, when creating power and / or protective linings for ships and aircraft, pipes and pipelines for large and small energy, containers of various classes and purposes, launch tubes, mine and / or smoke shafts, etc.

Known binder for fiberglass based on epoxytriphenol (ETF), anilinophenol formaldehyde (AFP) resins and an organic solvent (ed. Certificate. SU No. 226146, class C 08 L 63/04, 1968). The disadvantage of this binder is the low viability of the "prepregs" based on it, as well as the low interlayer transverse and shear strength of plastic structural products based on these "prepregs", which leads to cracking and delamination of them as in the manufacturing process (during winding, heat treatment, removal with mandrels, machining), and during operation.

A modified hybrid binder is known, formed from an epoxytriphenol resin and a mixture of aniline-formaldehyde and novolac phenol-formaldehyde resins, in plastics, on the basis of which reduction of cracking is achieved by the introduction of phenol-formaldehyde novolac resin according to ed. testimonial. SU No. 726137, class C 08 L 63/04, 1977. The disadvantage of the binder is the low shear, bending, and transverse strength of tubular plastic shells made by winding methods.

During winding, heat treatment, removal from mandrels and machining of tubular plastic products based on this binder, high internal stresses are formed, leading to cracking of the material. Both types of binders have disadvantages - increased fluidity, porosity and low shear and tear strength, which prevent their use for the manufacture of wound plastic products.

In the production of sheet PCBs, these shortcomings can largely be compensated for by selecting the mode of binder polymerization. In the production of tubular products manufactured by continuous layer-by-layer winding, it is necessary to reduce the temperatures of the support shafts of the winding machine to temperatures of 50-70 ° C.

In turn, the low temperatures of the support shafts of the winding machine do not allow completely to remove volatile products from each layer of material wound on the mandrel of the tubular product and this leads to a sharp deterioration in the physicomechanical, thermophysical and electrical properties of the product material, in particular, transversal strength, bending strength, dielectric loss tangent and other characteristics.

To obtain tubular products with high physicomechanical properties, in particular, with high transverse strength, it is necessary to apply higher temperatures (100-130 ° C) of the support shafts of the winding machine, which when using these binders leads to a sharp increase in the flow of the binder and / or uneven distribution of the binder along the length and thickness of the tubular product. And this, in turn, causes a decrease in the corresponding characteristics of plastic.

The closest analogue, the prototype of the invention, is a binder according to ed. testimonial. SU No. 1036730A, cl. C 08 L 63/00; B 32 B 17/04 of 05/19/82 (bull. No. 31 of 08/23/83). This binder also contains epoxytriphenol ETF and phenolaniline formaldehyde resins and an organic solvent - a mixture of isopropyl alcohol and toluene.

To improve the physico-mechanical and electrical characteristics of the material of the tubular cylinders and improve the technology of their manufacture in a binder-prototype according to ed. testimonial. SU No. 1036730A additionally introduced a thixotropic additive - linear oligoesterurethane (OEU) with terminal phenylcabamate groups in an amount of 21-37%.

The introduction of oligoesterurethane sharply reduces the fluidity of the binder during winding of the fabric soaked and brought to the “prepreg” state under conditions of roll temperatures of 100-130 ° C and, at the same time, does not affect the viability of the “prepreg” semi-finished product.

The main disadvantages of the binder for ed. testimonial. No. 1036730A:

- the binder has a fairly high viscosity (more than 1Pa · s.), since it contains components such as aniline, which binds free formaldehyde in the resin, and oligoester urethane (OEU), which in the presence of 3.5-9.0 wt.h. in resin sharply reduces the viscosity of the binder;

- the binder is not optimal from the point of view of impregnation of tissue fillers, in most cases resins with low dynamic viscosity are more technologically advanced, such resins easily penetrate into thin pores of complex structure; the optimal viscosity values of the binders used to obtain “prepreg” tissue fillers and / or for “wet” winding are in the range from 0.1 to 1 Pa · s (this is 15-85 s when controlling viscosity with a B3-4 viscometer) ; a binder with such a viscosity easily fills pores with a diameter of 5-6 microns;

- the binder does not have a sufficiently high viability, especially at elevated temperatures; for a binder testimonial. No. 1036730A, this dependence of viability on temperature is presented in table 1.

Table 1
Hybrid Binder Viability by Auth. testimonial. No. 1036730A Temperature, K 293 313 353 393 413 Temperature ° C twenty 40 80 120 140 Viability of the binder according to ed. testimonial. No. 1036730A 4-5 days 2-3 days 90-110 minutes 10-15 minutes 4-8 minutes

The above data show that this binder cannot be used when forming large-sized large-tonnage products from composite fibrous materials, since their manufacturing cycles are more than 6 days.

It should be noted that the viscosity of the binder according to ed. testimonial. No. 1036730 A can vary significantly both during the preparation of the binder and during its processing into “prepreg” fillers and during their winding on a mandrel in connection with the structuring process, that is, the initial viscosity value of this binder depends on the age of its preparation and storage conditions. Therefore, careful control of the temperature of the binder is one of the ways to maintain its optimal viscosity, and therefore the quality of the impregnation.

Heating the binder within its operating temperature significantly improves the impregnation even with lower amounts of the binder applied to the reinforcement, which allows some control of the volume content of the fibrous filler in the polymer composite.

From the point of view of optimum strength and stiffness of power composites, the volume content of the fibrous filler and binder should be in the ratio of 2.3: 1, that is, filler - 70 parts by weight, binder - 30 parts by weight

However, the limits of the working zone of this binder are sharply limited both in temperature (20-70 ° С) and in heating time (120 min). These factors sharply limit the technological regulations of the binder, its manufacturability.

The disadvantage of the prototype binder should be attributed to the fact that during processing it emits a large number of volatile products - more than 7%, including phenol and aniline. The amount and dynamics of the release of volatiles of this binder has a significant effect on the porosity of plastics based on it and, as a consequence, on the physical, mechanical and other properties thereof.

The main disadvantages of the binder according to ed. testimonial. No. 1036730 A are: large shrinkage and low degree of cure; for a binder of this type, the degree of cure is usually in the range of 94-97%, while for high-quality binders it should reach 97-99%.

Binder shrinkage is a consequence of the formation of a three-dimensional polymer structure during its curing, when during the chemical interaction the distances between the monomer molecules and other components of the binder change. Shrinkage is estimated by the relative size change of the product after winding and after curing on a technological mandrel. The presence of a reinforcing filler in the composition prevents the free shrinkage of the binder, leads to the formation of internal stresses, the most significant at the boundary of the two phases.

Introduction to the composition of the binder by ed. testimonial. No. 1036730 A oligoesterurethane reduces the negative effects of shrinkage, but does not completely eliminate it. In addition, with the introduction of oligoester in a binder, there is a significant decrease in heat resistance and deterioration of the physicomechanical and thermophysical properties of plastics based on it at elevated temperatures (above 160 ° C), and when oligoetherurethane in a binder (below 4%) decreases, cracking of cylindrical pipes generally occurs and leakage of the binder in the process of winding and heat treatment of products based on it.

Binder by author testimonial. No. 1036730 A has other disadvantages:

- in composites based on it, protection against the accumulation of charges of static electricity is not provided;

- Composites based on it have low interlayer tear-off (transverse) and shear characteristics;

- products based on this binder have low bending strength, separation and shear, low impact strength, and therefore products made of composite fibrous materials based on it do not work satisfactorily in conditions of vibration and shock loads;

- the binder has a low adhesive strength (table 2);

- the binder is not universal, it is suitable for the impregnation of only fiberglass structures of aluminosilicate fibers with plain weaving; for other structures (twill, satin, knitting-stitching, cord) it is not effective; its use is also irrational for the impregnation of tissue structures formed from organic, coal, polyphene, caproamide, carbon, basalt fibers and their modifications, since this binder has a very low adhesive strength with respect to them. In order to be able to use this binder to impregnate the aforementioned fibrous tissue structures, these fibers should be coated on the outside with special formulations - finishes and sizing agents that increase the adhesion of glass fibers to the binder. At the same time, even for the impregnation of woven fillers from aluminosilicate fibers, sizing additives must also be introduced into this binder to increase adhesion to fiberglass, which significantly increases the cost of the finished product and reduces its competitiveness.

table 2
The adhesion strength of the most famous binders to alumino-silicate glass fibers (Table 3) in comparison with the prototype binder according to ed. testimonial. No. 1036730 A Binder Stamps Adhesive Strength, MPa Paraffin Sizing Fibers Fibers finished with AGM-3 and / or AGM-9 Binder-prototype by ed. certificate No. 1036730 A 27.1-28.3 35.2-36.1 Epoxy - EDT-10, ED-16, ED-20, EP 5122 28.6-29.9 36.3-40.4 Epoxytriphenol - ETF 30.2-31.1 41.2-42.3 Phenol formaldehyde:
SF-010
SF-341A
SF-340A
Hybrid binder according to claim 1 16.1-17.2 19,4-20,1 17.1-18.2 19.8-21.5 18.4-18.5 20.1-21.9 32.1-33.4 42.1-43.2 Note
AGM-3, AGM-9 formulations are used only for epoxy and / or phenol-formaldehyde resins

The disadvantages of the binder by ed. testimonial. No. 1036730A should also include such as:

- large shrinkage during curing,% - 0.5-3.6;

- low elongation at break,% - 0.4-3.0;

- low impact strength, kJ / m ² - 2.5-12.5.

The prototype binder has low thermophysical characteristics, for example, plastics made of T-13 fiberglass and this binder with a ratio of components of 2.3: 1 have the following characteristics:

- operating temperature for continuous operation, ° C - 120-160;

- heat resistance according to Martens, K - 383-438;

- temperature of the beginning of intense destruction, K - 520-533;

- coefficient of thermal expansion · 10 ³ , K ^-1 - 3-11.5;

- oxygen index (CI) - 35-38;

- burning time after removal of the flame of a gas burner - ≈5 sec;

- the average linear ablation from the high-enthalpy heat flow of gases 3.5 · 10 ⁶ W / m ² - 1.2-1.5 mm / sec (for plastics based on T-13 fabric and this binder);

- the average speed of ablation by weight loss from a highly enthalpy gas flow of 3.5 · 10 ⁶ W / m ² - 1.0-1.2 mm / sec (for plastics based on fabrics TEMS-k (p) and this binder);

- effective enthalpy · 10 ⁶ , J / kg - ≈2.3-2.5;

- sublimation temperature, ° С - 160-250.

The objective of the invention is to improve the manufacturability of the manufacture of plastic products based on the new hybrid binder and at the same time increase the physico-mechanical, heat-physical, electrostatic (antistatic), antifriction and anticorrosion properties of plastics and products based on it and fillers made by winding, as well as increasing their thermo-fire resistance and thermal stability.

The technical result is achieved by the fact that a binder containing a mixture of epoxytriphenol ETF and epoxyaliphatic DEG-1 resins in an organic solvent contains resole phenol-formaldehyde resin SF-340A as a hardener resin, in the following ratio, in parts by weight:

- epoxytriphenol resin ETF - 97-103;

- epoxyaliphatic resin DEG-1 - 9-15;

- resol phenol-formaldehyde resin SF-340A - 31-37;

- acetone - 87-93;

- ethyl alcohol - 43-49;

- toluene oil and / or coal - 7-13.

The technical result is achieved by the fact that the binder containing a mixture of epoxytriphenol ETF, epoxyaliphatic DEG-1 and phenol-formaldehyde SF-340A resins and an organic solvent additionally contains a flame retardant additive - 7-18 parts by weight, selected from the group consisting of trichloroethyl phosphate, carbon tetrachloride , hexachlorobenzene, antimony trioxide and freon.

The technical result is achieved by the fact that the binder containing a mixture of epoxytriphenol ETF, epoxyaliphatic DEG-1 and resol phenol-formaldehyde SF-340A resins and an organic solvent additionally contains a group of flame retardants - 2-13 wt.h. freon, 2-13 parts by weight hexachlorobenzene, 2-13 parts by weight antimony trioxide, in the following ratio of components, in parts by weight:

- epoxytriphenol resin ETF - 97-103;

- epoxyaliphatic resin DEG-1 - 9-15;

- resol phenol-formaldehyde resin SF-340A - 31-37;

- acetone - 87-93;

- ethyl alcohol - 43-49;

- toluene oil and / or coal - 7-13;

- Freon - 2-13;

- hexachlorobenzene - 2-13;

- antimony trioxide - 2-13.

The technical result is achieved by the fact that the binder containing a mixture of epoxytriphenol ETF, epoxyaliphatic DEG-1 and resol phenol-formaldehyde SF-340A resins and an organic solvent additionally contains flame retardants - 12-23 wt.h. trichloroethyl phosphate and 12-23 parts by weight hexachlorobenzene and / or carbon tetrachloride, in the following ratio, in parts by weight:

- epoxytriphenol resin ETF - 97-103;

- epoxyaliphatic resin DEG-1 - 9-15;

- resol phenol-formaldehyde resin SF-340A - 31-37;

- acetone - 87-93;

- ethyl alcohol - 43-49;

- toluene oil and / or coal - 7-13;

- trichloroethyl phosphate - 12-23;

- hexachlorobenzene and / or carbon tetrachloride - 12-23.

The technical result is achieved by the fact that the binder containing a mixture of epoxytriphenol ETF, epoxyaliphatic DEG-1 and resol phenol-formaldehyde SF-340A resins and an organic solvent additionally contains flame retardants - 12-23 wt.h. trichloroethyl phosphate, 12-23 parts by weight hexachlorobenzene, 12-23 parts by weight carbon tetrachloride, 12-23 wt.h. antimony trioxide and 12-23 wt.h. freon, in the following ratio of components, in parts by weight:

- epoxytriphenol resin ETF - 97-103;

- epoxyaliphatic resin DEG-1 - 9-15;

- resol phenol-formaldehyde resin SF-340A - 31-37;

- acetone - 87-93;

- ethyl alcohol - 43-49;

- toluene oil and / or coal - 7-13;

- trichloroethyl phosphate - 12-23;

- hexachlorobenzene - 12-23;

- carbon tetrachloride - 12-23;

- antimony trioxide - 12-23;

- Freon - 12-23.

The technical result is achieved by the fact that the binder containing a mixture of epoxytriphenol ETF, epoxyaliphatic DEG-1 and resole phenol-formaldehyde SF-340A resins and an organic solvent additionally contains an additive - 1-1.5 wt.h. copper phthalcyanine, in the following ratio of components, in parts by weight:

- epoxytriphenol resin ETF - 97-103;

- epoxyaliphatic resin DEG-1 - 9-15;

- resol phenol-formaldehyde resin SF-340A - 31-37;

- acetone - 87-93;

- ethyl alcohol - 43-49;

- toluene oil and / or coal - 7-13;

- copper phthalcyanine - 1-1.5.

The technical result is achieved by the fact that the binder containing a mixture of epoxytriphenol ETF, epoxyaliphatic DEG-1 and resole phenol-formaldehyde SF-340A resins and an organic solvent additionally contains an additive - 1-6 wt.h. chlorine-containing compounds of Nickel, in the following ratio, in parts by weight:

- epoxytriphenol resin ETF - 97-103;

- epoxyaliphatic resin DEG-1 - 9-15;

- resol phenol-formaldehyde resin SF-340A - 31-37;

- acetone - 87-93;

- ethyl alcohol - 43-49;

- toluene oil and / or coal - 7-13;

- chlorine-containing compound of Nickel - 1-6.

The technical result is achieved by the fact that the binder containing a mixture of epoxytriphenol ETF, epoxyaliphatic DEG-1 and rezol phenol-formaldehyde SF-340A resins and an organic solvent additionally contains 0.001-0.003 wt.h. antistatic additives in the form of additives like "Sigbol" containing a conductive solution of metal compounds of organic acids and a polymer component in toluene, in the following ratio, in parts by weight:

- epoxytriphenol resin ETF - 97-103;

- epoxyaliphatic resin DEG-1 - 9-15;

- resol phenol-formaldehyde resin SF-340A - 31-37;

- acetone - 87-93;

- ethyl alcohol - 43-49;

- toluene oil and / or coal - 7-13;

- a solution of metal compounds of organic acids and a polymer component in toluene - 0.001-0.003.

The technical result is achieved by the fact that the binder containing a mixture of epoxytriphenol ETF, epoxyaliphatic DEG-1 and resole phenol-formaldehyde SF-340A resins and an organic solvent additionally contains 0.001-0.005 wt.h. antistatic additives in the form of additives such as ASP-1, containing a solution of chromium salts in synthetic fatty acids, in the following ratio of components, in parts by weight:

- epoxytriphenol resin ETF - 97-103;

- epoxyaliphatic resin DEG-1 - 9-15;

- resol phenol-formaldehyde resin SF-340A - 31-37;

- acetone - 87-93;

- ethyl alcohol - 43-49;

- toluene oil and / or coal - 7-13;

- a solution of chromium salts in synthetic fatty acids - 0.001-0.005.

The technical result is achieved by the fact that the binder containing a mixture of epoxytriphenol ETF, epoxyaliphatic DEG-1 and rezol phenol-formaldehyde SF-340A resins and an organic solvent additionally contains 7-13 wt.h. crystalline sodium aluminosilicate, in the following ratio, in parts by weight:

- epoxytriphenol resin ETF - 97-103;

- epoxyaliphatic resin DEG-1 - 9-15;

- resol phenol-formaldehyde resin SF-340A - 31-37;

- acetone - 87-93;

- ethyl alcohol - 43-49;

- toluene oil and / or coal - 7-13;

- crystalline sodium aluminosilicate - 7-13.

The technical result is achieved by the fact that the binder containing a mixture of epoxytriphenol ETF, epoxyaliphatic DEG-1 and resole phenol-formaldehyde SF-340A resins, an organic solvent and crystalline sodium aluminosilicate, additionally contains a flame-retardant additive - 7-23 wt.h. antimony trioxide, in the following ratio of components, in parts by weight:

- epoxytriphenol resin ETF - 97-103;

- epoxyaliphatic resin DEG-1 - 9-15;

- resol phenol-formaldehyde resin SF-340A - 31-37;

- acetone - 87-93;

- ethyl alcohol - 43-49;

- toluene oil and / or coal - 7-13;

- crystalline sodium aluminosilicate - 7-13;

- antimony trioxide - 7-23.

The technical result is achieved by the fact that the binder containing a mixture of epoxytriphenol ETF, epoxyaliphatic DEG-1 and resole phenol-formaldehyde SF-340A resins, an organic solvent, crystalline sodium aluminosilicate, additionally contains a flame-retardant additive - 7-23 wt.h. hexachlorobenzene, in the following ratio, in parts by weight:

- epoxytriphenol resin ETF - 97-103;

- epoxyaliphatic resin DEG-1 - 9-15;

- resol phenol-formaldehyde resin SF-340A - 31-37;

- acetone - 87-93;

- ethyl alcohol - 43-49;

- toluene oil and / or coal - 7-13;

- crystalline sodium aluminosilicate - 7-13;

- hexachlorobenzene - 7-23.

The technical result is achieved by the fact that the binder containing a mixture of epoxytriphenol ETF, epoxyaliphatic DEG-1 and resole phenol-formaldehyde SF-340A resins, an organic solvent and crystalline sodium aluminosilicate, additionally contains flame retardants - 7-23 wt.h. carbon tetrachloride and / or freon, in the following ratio of components, in parts by weight:

- epoxytriphenol resin ETF - 97-103;

- epoxyaliphatic resin DEG-1 - 9-15;

- resol phenol-formaldehyde resin SF-340A - 31-37;

- acetone - 87-93;

- ethyl alcohol - 43-49;

- toluene oil and / or coal - 7-13;

- crystalline sodium aluminosilicate - 7-13;

- carbon tetrachloride and / or freon - 7-23.

The technical result is achieved by the fact that the binder containing a mixture of epoxytriphenol ETF, epoxyaliphatic DEG-1 and resole phenol-formaldehyde SF-340A resins, an organic solvent and crystalline sodium aluminosilicate, additionally contains a flame-retardant additive - 7-23 wt.h. trichloroethyl phosphate, in the following ratio of components, in parts by weight:

- epoxytriphenol resin ETF - 97-103;

- epoxyaliphatic resin DEG-1 - 9-15;

- resol phenol-formaldehyde resin SF-340A - 31-37;

- acetone - 87-93;

- ethyl alcohol - 43-49;

- toluene oil and / or coal - 7-13;

- crystalline sodium aluminosilicate - 7-13;

- trichloroethyl phosphate - 7-23.

The technical result is achieved by the fact that the binder containing a mixture of epoxytriphenol ETF, epoxyaliphatic DEG-1 and resole phenol-formaldehyde SF-340A resins, an organic solvent and crystalline sodium aluminosilicate, additionally contains flame retardants - 2-13 wt.h. trichloroethyl phosphate, 2-13 parts by weight hexachlorobenzene, 2-13 parts by weight carbon tetrachloride, 2-13 parts by weight antimony trioxide and 2-13 parts by weight freon, in the following ratio of components, in parts by weight:

- epoxytriphenol resin ETF - 97-103;

- epoxyaliphatic resin DEG-1 - 9-15;

- resol phenol-formaldehyde resin SF-340A - 31-37;

- acetone - 87-93;

- ethyl alcohol - 43-49;

- toluene oil and / or coal - 7-13;

- crystalline sodium aluminosilicate - 7-13;

- trichloroethyl phosphate - 2-13;

- hexachlorobenzene - 2-13;

- carbon tetrachloride - 2-13;

- antimony trioxide - 2-13;

- Freon - 2-13.

The technical result is achieved by the fact that the binder containing a mixture of epoxytriphenol ETF, epoxyaliphatic DEG-1 and resole phenol-formaldehyde SF-340A resins and an organic solvent additionally contains an antistatic additive - 7-18 wt.h. carbon black and / or carbon-graphite mixture with a ratio of carbon to graphite from 1: 1 to 1: 0.1, with the following ratio of components, in parts by weight:

- epoxytriphenol resin ETF - 97-103;

- epoxyaliphatic resin DEG-1 - 9-15;

- resol phenol-formaldehyde resin SF-340A - 31-37;

- acetone - 87-93;

- ethyl alcohol - 43-49;

- toluene oil and / or coal - 7-13;

- carbon black and / or carbon-graphite mixture - 7-18.

The technical result is achieved by the fact that a binder containing a mixture of epoxytriphenol ETF, epoxyaliphatic DEG-1 and resole phenol-formaldehyde SF-340A resins, an organic solvent and soot and / or carbon-graphite mixture with a carbon to graphite ratio of from 1: 1 to 1: 0.1 additionally contains a flame retardant additive - 7-18 wt.h. hexachlorobenzene and / or antimony trioxide, in the following ratio of components, in parts by weight:

- epoxytriphenol resin ETF - 97-103;

- epoxyaliphatic resin DEG-1 - 9-15;

- resol phenol-formaldehyde resin SF-340A - 31-37;

- acetone - 87-93;

- ethyl alcohol - 43-49;

- toluene oil and / or coal - 7-13;

- carbon black and / or carbon-graphite mixture - 7-18;

- hexachlorobenzene and / or antimony trioxide - 7-18.

The technical result is achieved by the fact that a binder containing a mixture of epoxytriphenol ETF, epoxyaliphatic DEG-1 and resole phenol-formaldehyde SF-340A resins, an organic solvent and soot and / or carbon-graphite mixture with a carbon to graphite ratio of from 1: 1 to 1: 0.1 additionally contains a flame retardant additive - 7-18 wt.h. trichloroethyl phosphate, in the following ratio of components, in parts by weight:

- epoxytriphenol resin ETF - 97-103;

- epoxyaliphatic resin DEG-1 - 9-15;

- resol phenol-formaldehyde resin SF-340A - 31-37;

- acetone - 87-93;

- ethyl alcohol - 43-49;

- toluene oil and / or coal - 7-13;

- carbon black and / or carbon-graphite mixture - 7-18;

- trichloroethyl phosphate - 7-18.

The technical result is achieved by the fact that a binder containing a mixture of epoxytriphenol ETF, epoxyaliphatic DEG-1 and resole phenol-formaldehyde SF-340A resins, an organic solvent and soot and / or carbon-graphite mixture with a carbon to graphite ratio of from 1: 1 to 1: 0.1 additionally contains a flame retardant additive - 7-18 wt.h. carbon tetrachloride and / or freon, in the following ratio of components, in parts by weight:

- epoxytriphenol resin ETF - 97-103;

- epoxyaliphatic resin DEG-1 - 9-15;

- resol phenol-formaldehyde resin SF-340A - 31-37;

- acetone - 87-93;

- ethyl alcohol - 43-49;

- toluene oil and / or coal - 7-13;

- carbon black and / or carbon-graphite mixture - 7-18;

- carbon tetrachloride and / or cool it is 7-18.

The technical result is achieved by the fact that a binder containing a mixture of epoxytriphenol ETF, epoxyaliphatic DEG-1 and resole phenol-formaldehyde SF-340A resins, an organic solvent and soot and / or carbon-graphite mixture with a carbon to graphite ratio of from 1: 1 to 1: 0.1 additionally contains flame retardants - 2-13 parts by weight trichloroethyl phosphate, 2-13 parts by weight carbon tetrachloride and 2-13 parts by weight freon, in the following ratio of components, in parts by weight:

- epoxytriphenol resin ETF - 97-103;

- epoxyaliphatic resin DEG-1 - 9-15;

- resol phenol-formaldehyde resin SF-340A - 31-37;

- acetone - 87-93;

- ethyl alcohol - 43-49;

- toluene oil and / or coal - 7-13;

- carbon black and / or carbon-graphite mixture - 7-18;

- trichloroethyl phosphate - 2-13;

- carbon tetrachloride - 2-13;

- Freon - 2-13.

The technical result is achieved by the fact that a binder containing a mixture of epoxytriphenol ETF, epoxyaliphatic DEG-1 and resole phenol-formaldehyde SF-340A resins, an organic solvent and soot and / or carbon-graphite mixture with a carbon to graphite ratio of from 1: 1 to 1: 0.1 additionally contains flame retardants - 2-13 wt.h. hexachlorobenzene, 2-13 parts by weight antimony trioxide, 2-13 parts by weight trichloroethyl phosphate, 2-13 parts by weight carbon tetrachloride and 2-13 parts by weight freon, in the following ratio of components, in parts by weight:

- epoxytriphenol resin ETF - 97-103;

- epoxyaliphatic resin DEG-1 - 9-15;

- resol phenol-formaldehyde resin SF-340A - 31-37;

- acetone - 87-93;

- ethyl alcohol - 43-49;

- toluene oil and / or coal - 7-13;

- carbon black and / or carbon-graphite mixture - 7-18;

- hexachlorobenzene - 2-13;

- antimony trioxide - 2-13;

- trichloroethyl phosphate - 2-13;

- carbon tetrachloride - 2-13;

- Freon - 2-13.

The technical result is achieved by the fact that the binder containing a mixture of epoxytriphenol ETF, epoxyaliphatic DEG-1 and resol phenol-formaldehyde SF-340A resins and an organic solvent additionally contains flame retardants - 12-23 wt.h. antimony trioxide and hexachlorobenzene in a ratio of 1: 1 to 1: 0.1, in the following ratio of components, in parts by weight:

- epoxytriphenol resin ETF - 97-103;

- epoxyaliphatic resin DEG-1 - 9-15;

- resol phenol-formaldehyde resin SF-340A - 31-37;

- acetone - 87-93;

- ethyl alcohol - 43-49;

- toluene oil and / or coal - 7-13;

- antimony trioxide and hexachlorobenzene - 12-23.

The technical result is achieved by the fact that a binder containing a mixture of epoxytriphenol ETF, epoxyaliphatic DEG-1 and resole phenol-formaldehyde SF-340A resins, an organic solvent and flame retardants - antimony trioxide and hexachlorobenzene in a ratio of 1: 1 to 1: 0.1, additionally contains 12-23 parts by weight powdered additives in the form of monolithic, hollow, scaly and fibrous particles from metal oxides and / or nitrides, and / or from silicon oxides, in the following ratio, in parts by weight:

- epoxytriphenol resin ETF - 97-103;

- epoxyaliphatic resin DEG-1 - 9-15;

- resol phenol-formaldehyde resin SF-340A - 31-37;

- acetone - 87-93;

- ethyl alcohol - 43-49;

- toluene oil and / or coal - 7-13;

- antimony trioxide and hexachlorobenzene - 12-23;

- monolithic, hollow, scaly and fibrous particles from metal oxides and / or nitrides, and / or from silicon oxides - 12-23.

The technical result is achieved by the fact that a binder containing a mixture of epoxytriphenol ETF, epoxyaliphatic DEG-1 and resole phenol-formaldehyde SF-340A resins, an organic solvent and flame retardants - antimony trioxide and hexachlorobenzene in a ratio of 1: 1 to 1: 0.1, additionally contains 2-13 parts by weight discrete fillers in the form of whiskers, for example, from oxides of aluminum, chromium and iron and carbon silicon, in the following ratio of components, in parts by weight:

- epoxytriphenol resin ETF - 97-103;

- epoxyaliphatic resin DEG-1 - 9-15;

- resol phenol-formaldehyde resin SF-340A - 31-37;

- acetone - 87-93;

- ethyl alcohol - 43-49;

- toluene oil and / or coal - 7-13;

- antimony trioxide and hexachlorobenzene - 12-23;

- whiskers from oxides of aluminum, chromium and iron and carbon silicon - 2-13.

The technical result is achieved by the fact that the binder containing a mixture of epoxytriphenol ETF, epoxyaliphatic DEG-1 and rezol phenol-formaldehyde SF-340A resins and an organic solvent additionally contains a finely divided filler - 7-18 parts by weight, containing nitrides and / or metal oxides and silicon selected from the group: magnesium oxide (burnt magnesia), aluminum oxide (alumina), titanium oxide (rutile), silicon oxide (silica), boron nitride BN, borazon, borazole in the following ratio, in parts by weight:

- epoxytriphenol resin ETF - 97-103;

- epoxyaliphatic resin DEG-1 - 9-15;

- resol phenol-formaldehyde resin SF-340A - 31-37;

- acetone - 87-93;

- ethyl alcohol - 43-49;

- toluene oil and / or coal - 7-13;

- filler - 7-18.

The technical result is achieved by the fact that the binder containing a mixture of epoxytriphenol ETF, epoxyaliphatic DEG-1 and resole phenol-formaldehyde SF-340A resins and an organic solvent additionally contains whiskers - 2-18 wt.h. from oxides of aluminum and / or chromium and / or iron and / or carbon silicon in the following ratio of components, in parts by weight:

- epoxytriphenol resin ETF - 97-103;

- epoxyaliphatic resin DEG-1 - 9-15;

- resol phenol-formaldehyde resin SF-340A - 31-37;

- acetone - 87-93;

- ethyl alcohol - 43-49;

- toluene oil and / or coal - 7-13;

- antimony trioxide and hexachlorobenzene - 12-23;

- whiskers from oxides of aluminum, and / or chromium, and / or iron, and / or carbon silicon - 2-18.

Analogs of the claimed methods for producing a hybrid binder for plastics are: a method for producing a binder for fiberglass based on epoxy and phenol-formaldehyde resins according to ed. testimonial. SU No. 730756 dated 06/05/78, Mcl ² C 08 L 63/04, B 32 V 17/10, bull. No. 16 dated April 30, 1980 and a method for producing an epoxy powder composition according to ed. testimonial. SU No. 702050 of 08.28.77, MKI 5 09 D 5/03, C 09 D 163/00, C 08 J 3/20, bull. No 45 on December 05, 79

In the invention by ed. testimonial. SU No. 730756 (analogue 1) describes a method for producing a binder for fiberglass based on epoxy and phenol-formaldehyde resins by pre-dissolving dicyandiamide in ethyl cellosolve and mixing it with an epoxy resin.

The method is aimed at improving the manufacturability of the binder and physico-mechanical properties of fiberglass based on it.

A distinctive feature of this method is that as a phenol-formaldehyde resin, novolac phenol-formaldehyde resin with a free phenol content of 10-12% is used, dissolution of dicyandiamide (DCDA) is carried out in the presence of this resin, taken in an amount of 3.8-19 wt.h. by 3.5-6.3 parts by weight dicyandiamide.

In the invention by ed. testimonial. SU No. 702050 (analog 2) describes a method for producing an epoxy powder coating composition. In the invention by ed. testimonial. SU No. 702050 describes the technology for producing an epoxy powder composition for coatings by combining an epoxy melt, a hardener - dicyandiamide and a filler consisting of aerosil and pigments - titanium dioxide (TiO ₂ ) and ultramarine.

The invention is aimed at reducing the duration of the curing of the epoxy powder composition and increasing the physico-mechanical properties of the coatings.

The main distinguishing feature of the method according to ed. testimonial. SU No. 702050 - before the introduction of the hardener DTSDA it is pre-crushed in the presence of aerosil in the ratio dicyandiamide - aerosil from 3: 1 to 1: 3 by weight.

The disadvantage of the plastic coatings of the above analogues: the binders obtained on the basis of the above methods have weak adhesive strength for fibers on a paraffin sizing - 4-5 MPa, for sizing fibers with AGM-3 and / or AGM-9 resins - 6-9 MPa, and plastics on them based on low impact strength (40-150 kJ / m ² ) and very low strength at interlayer separation (59-245 MPa) and low strength at interlayer shear (5.9-78.5 MPa). At the same time, lower values are characteristic for wound structures, and higher values - for pressed ones.

In addition, plastics obtained on the basis of the above methods have low heat resistance - only 185-200 ° C according to Martens and almost unsatisfactorily work under conditions of exposure to high-enthalpy high-speed gas flows. In addition, plastics based on binders made in accordance with the above methods have low corrosion resistance, are not waterproof, and do not have the ability to remove static electricity charges from their surfaces.

The prototype of the claimed methods for producing epoxy binders is a method for producing an epoxy composition according to ed. testimonial. SU No. 1445163 of 05/13/86, bull. No47 on 12/23/90

This invention relates to methods for producing epoxy compositions for the preparation of long-lived "prepregs" by impregnating a tissue filler with a binder solution. Epoxy compositions and “prepregs” made in accordance with the proposed method are used to obtain composite fibrous materials and structural products based on them.

This method aims to create a binder with improved technological properties, namely: to increase the viability of the binder and improve the physico-mechanical properties of composite fibrous materials created on the basis of this binder.

In the method of producing an epoxy composition according to ed. testimonial. SU No. 1445163, class C 08 L 63/00, including mechanical mixing of an epoxy resin and a latent hardener of the class of alkyl substituted ureas in the presence of an organic solvent at elevated temperature, a mixture of epoxy diane resin (ED 20, ETF, ECD, etc.) and epoxyaliphatic resin DEG -1, bis-N, N-dimethylcarbamide (diphenylmethane) as the hardener, and an alcohol-acetone mixture as the solvent, and the mass ratio of the epoxyaliphatic resin DEG-1 and hardener is (0.3-1.5): 1 the ratio of alcohol to acetone (1 -2): 1, and mixing is carried out at a temperature of 60-70 ° C for 60-90 minutes.

The disadvantage of a method of obtaining a binder according to ed. testimonial. SU No. 1445163: the method allows to obtain plastics based on it with low physical, mechanical and thermophysical characteristics, low water corrosion resistance, as well as low interlayer characteristics: shear and transverse (tear-off) strength.

In addition, the fact that the plastics obtained on the basis of a binder prepared in accordance with the method of ed. testimonial. SU No. 1445163, have low antifriction properties and vibration resistance, do not have protection against the accumulation of charges of static electricity and do not work satisfactorily on the erosion of the mass under the influence of high-speed and high-enthalpy high-speed gas flows.

SUMMARY OF THE INVENTION

The main objective of the invention is the creation of universal hybrid binders and methods for their preparation, which would make it possible to obtain plastics from any fibrous fillers (glass, organic - CBM fiber, carbon, carbon, basalt, etc.) by winding or pressing products with any degree of anisotropy, with the degree of curing of the binder up to 97-99% and at the same time would have high adaptability, vibration-heat resistance, fire-corrosion resistance, resistance to aggressive environments, including ag gas fumes, high-speed and high-enthalpy flows, and at the same time would have high operational reliability (antistatic, anti-vibration, anti-friction, anti-corrosion, anti-vandal, etc.) and reasonable cost, that is, they would meet all the requirements of a market economy.

The developed new types of binders and methods for their preparation are intended for the manufacture of structural products from composite fibrous materials formed from woven and / or tape "prepregs" based on aluminum-borosilicate (ABS) alkali-free and aluminum-magnesian alkaline fibers, titanium-containing alkali-free fibers of the T273 brand, as well as acid-resistant boron-containing and heat-resistant silica and quartz fibers (table 3). At the same time, the developed binder compositions can be effectively used for the impregnation of fabrics and tapes from organic (CBM), carbon, Kevlar, basalt and other fibers, as well as polyphene and caproamide fibers and heat-protective fabrics of the type TEMS-k (p) based on them .

From the above it follows that the fibrous reinforcing fillers used in conjunction with the developed hybrid binders for the manufacture of products from various plastics and various methods, including winding or pressing methods, are very diverse both in appearance and chemical composition, as well as for their intended purpose.

In appearance, fibrous fillers intended for impregnation with hybrid binders are divided into two main groups:

- the first main group should include primary threads (untwisted and twisted), which are a set of 100-200 elementary fibers simultaneously pulled in a fiber-spinning unit, as well as bundles obtained by combining primary threads (untwisted and twisted bundles, unidirectional tape);

- the second main group should include all the fillers of the roll type, that is, various woven and non-woven materials used in the winding process only for molding products, the surface of which unfolds in a plane.

One of the most important conditions for the effective use of a fibrous filler and a binder in power structures is the simultaneous operation of elementary fibers and their good compatibility with the binder.

Untwisted yarns and bundles more fully retain the initial strength of the elementary fiber and are more acceptable in the technology of winding high-strength structures. In particular, untwisted yarns and tows allow to realize 75-81% of the strength of elementary fibers in finished products, while twisted ones - only 68-71%. When using fabric and / or tape fillers, this figure decreases even lower - up to 60-65%.

However, twisted yarns are more convenient in the weaving process and more technologically advanced in the production of pre-impregnated composite materials - semi-finished products - "prepregs".

In terms of chemical composition, the fibers used in domestic and foreign industries also differ significantly from each other; the Russian and American formulations of the main glasses for producing fibers are quite similar in chemical composition (Table 3). That is why, when developing the hybrid binder formulations described in the invention, it was necessary to take into account the effectiveness of their application, taking into account the structure and chemical composition of the fillers. At the same time, their physicomechanical, thermophysical and other properties were taken into account: strength, chemical resistance, resistance at elevated temperatures, manufacturability and manufacturing cost.

Table 3
The chemical compositions of the main glasses to obtain fibers, the use of which is possible to obtain woven "prepregs" and products from them on the basis of binders presented in this invention Glass SiO ₂ B ₂ O ₃ Al ₂ O ₃ + Fe ₂ O ₃ CaO MgO Na ₂ O Fe Other oxides Alkaline borosilicate alkaline (ABS) (acid-resistant),% 54 10 14.5 16.5 4 0.5 0.5 - Alumagnesial alkaline,% 71 - 3 8.5 2,5 fifteen - - Alkaline-free titanium-containing T-273,% 52,5 - eighteen fifteen 4 0.5 - TiO ₂ (9), BaO (1) US formulations Glass type E,% 55.2 7.3 14.8 17.7 4.3 0.3 0.4 ZrO ₂ (4) Glass type S,% 63 - 23 - 10 - - TiO ₂ (8), ZrO ₂ (2), CeO ₂ (3) Glass type M,% 53.7 - 0.5 12.8 nine - - BeO (8), Li ₂ O (3)

Alkaline glass fibers are cheaper (30-40%) and more technologically advanced, however, in terms of strength properties, chemical resistance, and especially at elevated temperatures, they are significantly inferior to alkaline. In the serial production of large-sized structures that are not subject to high mechanical loads and are operated in the absence of aggressive environments, fiberglass fillers obtained from cheap alkaline glass are used.

Aluminoborosilicate alkali-free glass (Table 3), as well as compositions with increased strength and rigidity, are used in the manufacture of fibers and fabrics intended for the manufacture of critical structural elements.

Increased corrosion resistance of fiberglass structures is achieved by using acid-resistant boron-containing glass. The heat resistance of structures can be increased if silica and quartz fibers are used as filler.

Therefore, alkali-free fibers are more widely used in industry. Work on the selection of fiber compositions and hybrid binders for them, as well as methods for their preparation, is ongoing and, in particular, they are carried out at the FSUE PO Avangard enterprise.

Typically, when developing fiber compositions and binders for them, the alkali metal oxides in their compositions are replaced with metal oxides and / or nitrides. This is done in order to improve the quality and operational reliability of plastics based on them. Therefore, studies were conducted to reduce the content of alkali metal oxides in both fibers and hybrid binders.

Reducing the content of alkali metal oxides in the fibers can be achieved by various methods, for example, by treating the fibers with specially selected solutions.

Silica and quartz fibers in which the content of silicon oxide is from 53.7 to 71% are obtained in a similar way (Table 3).

Due to the high viscosity of the melt, quartz fibers, which are almost silica, are made in two stages: first, piles (rods) with a diameter of about 1 mm were obtained by extraction from the melt, and then, under local heating conditions, the fibers were drawn from them. Table 4 below shows the properties of fiberglass.

Table 4
The main properties of fiberglass Name of indicator Indicator value Density, g / cm ³ 2.2-2.9 Tensile stress, GPa 2.1-6.1 Elongation at break,% 2.1-5.5 Modulus of elasticity, GPa 65-125 Shear modulus, GPa 3.83-32 Impact strength, kJ / m ² 0.2-10 Poisson's ratio 0.13-0.3 Hardness, MPa 390-785 The coefficient of thermal expansion, K ^-1 (0.5-6) ^10-6 Specific heat, kJ / (kg · K) 0.5-0.95 The coefficient of thermal conductivity, W / (m · K) 0.08-0.95 Volume resistivity, Ohm · m (2-20) · 10 ¹⁴ Dielectric constant at 10 ⁶ Hz 6.2-9.8 Dielectric loss tangent at 10 ⁶ Hz 0.001-0.013 Note - Table 4 shows data for fiberglass with round sections.

The use of fibers with hexagonal and rectangular sections also makes it possible to increase the density of their packaging in fiberglass, and therefore to increase the strength and stiffness of the composite material. Replacing monolithic fibers with hollow fibers can not only reduce the density of fiberglass, but also significantly increase the strength and stiffness of composites during compression and bending.

As can be seen from table 4, the range of properties of glass fibers is wide enough to meet various industry requirements.

In this case, both the diameter of the fibers and the coefficient of capillarity, that is, the ratio of the inner diameter to the outer, are significant. For fibers with a diameter of 9-15 microns (the most effective fiber sizes from the point of view of impregnating them with a binder and processing them into products from composite fibrous materials by winding methods), the capillarity coefficient is usually in the range 0.6-0.85. It should also be noted that the use of hollow fibers expands the possibilities of the dielectric and thermophysical properties of polymer composite materials.

Superthin fibers with a diameter of less than 1 micron are very effective in tensile structures. However, their preparation and processing, especially in relation to high-modulus compositions, have significant design and technological limitations due to high sensitivity to defects, brittleness, low shear strength, etc. Therefore, the use of superthin fibers is more justified in structures used for sound and heat insulation, and therefore, they will not be considered in the claimed materials, since this is a different class of polymer composites.

Fibers with a diameter of more than 15 microns are effective in compression structures. These designs also belong to another class of products from polymer composite materials and will not be further considered in the description of this invention.

In general, the relationship between the strength characteristics of composites and glass fiber diameter is quite complex and the choice of the optimal fiber diameter is due to many factors, among which the most important are: the nature of loading, the adhesive strength of the hybrid binder, the ratio of elongations at break of the fiber and hybrid binder, the ratio of elastic moduli fiber and hybrid binder, the presence of alkali metal oxides in the glass and hybrid binder, etc.

At the same time, along with the search for ways to increase the strength and stiffness of composites, special attention was paid to increasing their crack resistance, as well as interlayer shear and transverse (tear) strength, since these indicators practically determine the loading boundaries of fiberglass structures and other organic-based plastics. caproamide, polyphene, boric, basalt and carbon fibers.

In the modern large-tonnage production of plastic products, which is the Avangard FSUE, mainly fibers with a diameter of 9-15 microns are used, which is technically and economically justified. The most common technological recommendations are as follows: it is advisable to use fibers with a diameter of 9-11 microns with phenol-formaldehyde resin, with a diameter of 11-15 microns with epoxy.

Such recommendations are based on the assessment of the cohesive and adhesive properties of binders, and the adhesive characteristics were given the greatest importance when choosing the composition of the binder (Table 2).

New compositions of hybrid binders and technologies for producing new polymers based on them were developed taking into account this factor. It should also be noted that the surface of elementary fibers in the process of their production is coated with a sizing to protect against external influences, increase elasticity and improve technological properties.

At the enterprise FSUE PO Avangard, fibers most often used are coated with various types of emulsions. They are made from mineral oils or fatty acids with the addition of paraffin or polyvinyl alcohol.

A variety of requirements are imposed on sizing agents. They must prevent the abrasion of the fibers during processing, protect them from various external influences, have good adhesion to the surface of both the fiber and the binder, not have a harmful effect on the properties of the finished plastic, and also be non-toxic, heat-resistant and, finally, high-tech. However, lubricants significantly worsen the adhesion ability of the fibers and reduce the physicomechanical and thermophysical properties of reinforced plastics. So, with a typical paraffin lubricant content of 1.5-2%, a decrease in the strength of epoxyphenolic compositions is 12-15%.

Before molding products, and most often before obtaining semi-finished products - “prepregs” for them, lubricants of tissue fillers are removed chemically or thermally. Chemical washing is carried out with aqueous (less often in organic solvents) solutions of detergents, such as sulfones of fatty acids, urea, chromium mixtures, etc. Chemical treatment reduces the lubricant content to 0.3-0.6%.

More effective is the heat treatment of the fabric filler coated with a sizing for 4-6 hours at temperatures of 570-575 K. With this heat treatment, the residual content of the sizing is brought to 0.05%, however, there is a significant (25-35%) decrease the strength of the fibrous filler.

To increase the adhesion of the hybrid binder to the fiber and to improve the manufacturability of the fibrous fillers after removing the lubricant, the surface of the fibers is treated with special substances - resins, which are special multifunctional compounds that can interact with both the fiber materials and the hybrid binder.

Their effect on adhesive strength is shown in Table 2. The same table shows the effectiveness of the use of direct sizing agents (such as AGM-3, AGM-9) based on organosilicon compounds (diethylaminomethyltriethoxysilane, epoxypropyltriethoxysilane, etc.), which include substances with adhesive and hydrophobic properties and contribute to increased bond strength on phase boundary; they are not removed from the surface of the fibers before forming the products (with "wet" impregnation) or before receiving "prepregs" for forming the products with "dry" winding and are therefore called straight.

Direct lubricants increase not only the adhesive strength by 15-20%, but also the weather resistance of the fibers and composite as a whole. However, direct sizing agents based on organosilicon compounds can reduce the viability of the hybrid binder in pre-impregnated materials and its manufacturability. An increase in the adhesive strength of composites can be achieved by introducing into the composition of the hybrid binder up to 3-10% chemically active additives capable of interacting with both the fiber material and the hybrid binder.

The analysis of the reinforced materials carried out above showed that for creating responsible structural products from composite fibrous materials, as well as individual components and elements, alkali-free glass with a fiber diameter of 9-15 microns is most effective. The reason for the high strength of glass fiber lies in the technology for its production and is associated with a high speed of mechanical extraction of the molten glass mass coming from the dies of the melting chamber, and intensive cooling in air of a fiber with a diameter of several microns. The effect of the fiber diameter on its strength, due to the dependence of the cooling rate on the temperature gradient along the radius of the fiber, of course, takes place.

However, in most cases, this dependence is determined by the fact that the probability of mechanical damage to the surface of the fiber increases with an increase in its diameter.

The theoretical strength of fiberglass, calculated by various methods, is 10–20 GPa: the practically achieved values of the strength of fiberglass at the enterprise FSUE PO Avangard do not exceed 5–6 GPa.

The desire to increase the bearing capacity of fiberglass structures led to the development of high-modulus fibers, the stiffness of which is 1.5-2 times higher than fibers of conventional composition.

However, a further increase in the elastic modulus, achieved by varying the chemical composition of the glass, causes increasing technological difficulties (associated with applying a sizing agent, sizing, as well as brittle fibers, etc.) and therefore is hardly economically justified.

The various types of fiberglass fillers used in the manufacture of products from reinforced plastics are characterized by the packing density of the fibers and their relative position.

The linear density of the threads is expressed in tex (tex is the mass in grams of thread 1000 m long). Most often at the enterprise FSUE PO Avangard, when winding products, yarns with a linear density of 50-100 tex are used.

For the production (production) of fiberglass and / or fabric tapes, yarns with a linear density of 50-100 tex are also used, obtained from fibers with a diameter of 3-15 microns.

In the manufacture of fiberglass products, linen, satin, twill and cord weaving have been used. In designs subject to significant interlayer shear loads, VPR-10 type weave fabrics, consisting of several layers sequentially joined by common threads, have proven themselves well. Such fabrics reach thicknesses of the order of 1 mm and are characterized by a weight of 1 m ² from 1800 to 8600 g.

Note - Multilayer and bulk fiberglass fabrics are mainly intended for the production of fiberglass by pressing and impregnation methods under pressure or in vacuum in a closed form; since the possibilities of their use for winding are very limited due to the difficulty of selecting binders for them and the modes (methods) of their impregnation, the development of binders for this type of tissue structure was not carried out; The development of hybrid binder formulations was carried out mainly for fiberglass fiberglass structures of linen, satin and twill weaving, as well as for fibrous polyphene and caproamide tissue structures of the type TEMS-k (p).

Hybrid Binder Specifications

As a binder for fiberglass (and plastics based on organic, caproamide, polyphene, basalt, boron and carbon), a thermoset hybrid binder was used that meets the following requirements:

- good ability to wet glass, carbon, organic, boric, caproamide, polyphene and basalt fibers;

- high adhesive and cohesive strength and high modulus of elasticity with a viscous nature of the fracture;

- sufficient deformability, that is, elongation, up to fracture, must be not less than the corresponding values for reinforcement - threads (strands) and / or bundles;

- slight shrinkage during curing and the value of the coefficient of thermal expansion, close to the value of this indicator for reinforcement (glass, organic, carbon, boric, polyphene, caproamide, etc.);

- the absence of curing by-product emissions (the so-called volatile components removed during the manufacture of "prepregs" and products from them) that violate the monolithicity of plastics;

- sufficient heat resistance, thermal stability and stability of physico-chemical characteristics during storage and operation, including long-term operation at elevated temperatures;

- hydrophobicity and high water resistance, including corrosion resistance to aggressive environments;

- low corrosion activity in relation to metals, chemical neutrality of the cured binder in relation to reinforcement (fibers of various types);

- high (and in some cases - even acceptable) technological properties - viscosity, viability, curing temperature, release of volatile substances, shrinkage, etc .;

- high (or at least acceptable) economic indicators of the polymer (cost, scarcity of raw materials, energy consumption for its production, etc.);

- high specific physical and mechanical characteristics;

- high erosion resistance to high-enthalpy high-speed gas flows (laminar and / or turbulent);

- high shear strength (at least not lower than the adhesion strength of the binder to fiberglass);

- high impact strength;

- high antifriction, electrical, electrostatic, thermophysical and other properties.

This section of this description provides data on the properties of the main types of binders in a generalized form; The aim was to draw the attention of developers of the technology of winding plastic products from composite fibrous materials to the possibilities of one or another type of binder, as well as to their comparative assessment. Table 5 shows the specific properties of polymer binders, and Table 6 shows the main properties of binders for fiberglass.

Table 5
Indicators of some specific properties of polymer binders Indicator Name Indicator value Shear modulus, GPa 0.15-1.9 Impact strength, kJ / m ² 2.5-24.5 Poisson's ratio 0.15-0.28 Hardness, MPa 2,5-200 Thermal diffusivity, · 10 ³ , m ² / hour 0.1-5 Specific heat, kJ / (kg · K) 0.5-2.95 The coefficient of thermal conductivity, W / (m · K) 0.16-0.95 The specific volume resistance, · 10 ¹² , Ohm · m 1-320 Dielectric constant at 10 ⁶ Hz 2.4-6.9 Dielectric loss tangent at 10 ⁶ Hz 0.0002-0.05

Table 6
The main properties of binders for fiberglass Name of indicator Type of binder polyester epoxy phenolic organosilicon Density, g / cm ³ 1.1-1.46 1.1-1.4 1.2-1.36 1.15-1.36 Breaking stress, MPa: tensile 24-69 27-97 23-79 6.8-34 under compression 79-250 85-275 69-205 50-105 when bending 10-130 59-158 45-120 7-96 Tensile modulus, GPa 1,5-4,5 2-5 2.1-6.8 1,5-3,8 Elongation at break,% 3,5-6 1.2-6.5 0.5-3 0.3-1.5 Impact strength, kJ / m ² 6-11 3-25 2,5-11 2,3-5,5 The coefficient of thermal expansion, · 10 ³ , K ^-1 7-15 3-12 2-12 2-18 Heat resistance according to Martens, K 360-385 385-440 405-455 525-560 Operating temperature for continuous operation, K 395 475 535 725 The temperature of the beginning of intense destruction, ° K 475 535 575 875 Water absorption,% 0.15-0.6 0.03-0.3 0.15-0.6 0.15-0.2 Shrinkage during curing,% 4-15 0.5-3.6 0.9-7 2.1-4.5

From the data given in Tables 5, 6, it can be seen that the range of properties of polymer binders is quite wide and allows you to choose the necessary combination of them to obtain composite materials for various purposes.

The most widely used in the manufacture of plastic products are polyester, epoxy, phenol-formaldehyde and organosilicon binders (Table 6).

The disadvantages and advantages of the binders listed in table 5, 6

Due to their high manufacturability and low cost, polyester binders are used in the production of large-sized large-tonnage structures that do not experience significant loads. Limitations in their use are mainly associated with low transverse, shear and vibration strength, high shrinkage during curing, low heat resistance and thermal stability, as well as low atmospheric corrosion resistance.

Organosilicon binders also, due to their low adhesive strength, find application in lightly loaded structures. Their advantages are fully manifested when defining requirements for products are presented: high heat resistance, radio transparency and chemical resistance.

The disadvantages of this type of binder include low adhesive strength, brittleness, high shrinkage, low technology, and, as a consequence of these disadvantages, a significant cost.

In the manufacture of critical plastic constructions, epoxy and phenol-formaldehyde binders are mainly used, the latter, along with a sufficiently high strength, give the composite material increased heat resistance and thermal stability.

The advantages of epoxy binders include: slight shrinkage during curing and the highest adhesion to almost all fibrous materials - glass, organic, carbon, polyphene, caproamide, metals, as well as their oxides and nitrides. In addition, epoxy resins (in comparison with others) have higher physical and mechanical characteristics.

However, these binders are toxic and expensive. The price of phenol-formaldehyde resins is relatively low, however, their processing is usually associated with fairly high pressures and temperatures. In addition, they are also toxic. The use of hybrid binders, for example, epoxyphenol, and / or epoxyphenol formaldehyde, and / or organosilicon, allows to maximize the advantages of their constituent resins and to avoid their disadvantages.

Of particular importance for the production of wound plastics are the epoxy resin brands ED-16, ED-20, EHD, EHD-U and ETF.

ETF resin, for example, having a low molecular weight (350-700), at ordinary temperature is a viscous liquid, which is especially important in the technology of forming large-sized products.

Possessing a high content of epoxy groups (13-29%) (Table 7), this resin is very reactive and can be cured with amine hardeners without heating, practically without emitting volatile products (up to 2.5%).

Characteristics of the resins used to produce hybrid binders according to claims 1-38 of the claims are presented in table 7.

Table 7
Characteristics of the resins used to produce hybrid binders according to claims 1-38 of the claims Performance Indicators ETF resin Resin DEG-1 Resin SF-340A The hybrid binder of claim 1 Density, g / cm ³ 1.25-1.35 - - 0.95-1.1 Mass fraction of the epoxy group,% 13-29 26 - - Dynamic viscosity, not more than, MPa · s 0.1-1 0,07 10-20 0.1-0.2 Mass fraction of volatile substances, not more than,% 1 1,5 1,5 3,5-5,5 Mass fraction of chlorine ions,% 0.018 0.04 - 0.013 Mass fraction of washed chlorine,% 1 1.4 - 0.8 Mass fraction of free phenol,% - - <4 1.5-2.5 Mass fraction of free aniline,% - - <4 1,5-2 Gelatinization time, sec - - 60-110 - Drop temperature, ° С - - 90-100 - Cher softening temperature, ° С 40-65 - - - Molecular mass 350-700 240-320 - -

Lateral hydroxyl groups in the ETF epoxytriphenol resin molecule allow another curing mechanism to be realized, for example, when phenol-formaldehyde resin is used as a hardener and is carried out at elevated temperatures (180-200 ° С).

Hot curing of this binder allows to obtain plastics with higher physical and mechanical characteristics, especially strength and stiffness.

Table 8 below shows some characteristics of cold and hot cured ETF epoxy resin.

Table 8
Characteristics of cold and hot cured ETF epoxy resin Name of indicator ETF Resin Cold Cured ETF Hot Cure Resin Density, g / cm ³ 1.1-1.25 1.2-1.27 Breaking stress, MPa: tensile
when bending
under compression 35-75 75-100 60-100 90-130 110-130 100-160 Strength at separation from fiberglass, MPa 9.5-12 15-18 Elongation at break,% 3-7 1,2-4 Impact strength, kJ / m ² 3-11 4-25 Heat resistance according to Vika, K 660-695 770-820 The viability of the prepared binder at 298 K less than a day up to 6 months

ETF epoxytriphenol uncured resin can be converted into a non-melting and insoluble state by the action of curing agents of various classes: di- and polycarbamide acid anhydrides, primary amines, etc.

A number of diminishing activities of some amines can be represented as PEPA - THETA - HMDA - TEA - TEAT, where:

PEPA - polyethylene polyamine,

TETA - triethylenetetramine,

HMDA - hexamethylenediamine,

TEA - triethanolamine,

TEAT - triethanolamine titanate.

The above primary amines allow the curing of the ETF epoxy resin without heating, that is, in the cold state.

A decrease in the activity of amines is also observed during the transition from aliphatic to aromatic compounds, as a result of which the use of the latter requires hot curing. This series of activity reflects a decrease in the toxicity of hardeners under normal temperature conditions, as well as a decrease in water resistance, an increase in heat resistance, strength and stiffness of the compositions cured with these hardeners. The aggregate state of the hardener changes from liquid to solid in the same sequence. The use of solid curing agents of ETF epoxytriphenol resin for its hot curing causes significant technological difficulties.

With the heating of the ETF epoxytriphenol resin, it can be cured using anhydrides of certain organic acids (usually carboxylic acids), most often maleic anhydride (MA) or phthalic anhydride (FA).

Maleic anhydride in comparison with phthalic has a lower melting point, however, it is characterized by great volatility and a strong irritating effect on the mucous membranes of the eyes. Compositions with it have a relatively low heat resistance and limited viability. But at the same time they are slightly porous and have a low level of residual stresses.

In addition to the indicated ones, some phenolic, urea-melamine and amino formaldehyde and aniline-phenol formaldehyde resins, as well as low molecular weight polyamides, isopropylbenzene hydroperoxide, methyl perketone, cobalt naphthenate, and other alcoholates can be used as hardeners for ETF epoxytriphenol resin. The resulting composites are characterized by elasticity, ductility and other properties that expand their application.

However, all of the above hardeners, except phenol-formaldehyde resins, allow to obtain composites based on ETF resin with a very low interlayer tear (transverse) and shear strength.

The use of rezol phenol-formaldehyde resins as hardeners of ETF epoxy resin requires the use of hot curing. Hot curing, especially at elevated temperatures (180-200 ° C), is characterized by a higher labor intensity of the process, high energy consumption and the need to use additional expensive tooling and equipment: impregnation machines, winding machines with heating and prepress shafts, heat chambers with automatic adjustment of cured temperatures blanks, special mandrels, etc.

Nevertheless, hot curing provides higher reproducibility of properties (for example, tensile strength of hot curing plastics increases by 2–3 times) and is used in the manufacture of critical structures, although there is a tendency to lower the curing temperatures of the binders used.

Note - The benefits of cold curing ETF epoxy resin are fully realized in the manufacture of products of especially large dimensions, when it is almost impossible to provide the temperature regime required for hot curing.

ETF epoxytriphenol resin, TU 2225-316-09201208-94, is intended for technical use as part of other resins for reinforced plastics, impregnating and casting compounds, adhesives in the electrical industry, power structures made of composite fiber materials of rocket and space, aircraft building and energy industries with increased heat resistance , thermal stability and corrosion resistance. The resin is processed at temperatures of 180-200 ° C. Its main disadvantage is high viscosity (more than 1 Pa · s).

The optimal viscosity values of resins from the point of view of their processing by winding methods are in the range of 0.1-1 Pa · s (when controlling viscosity with a viscometer B 3-4 this corresponds to 15-85 s). Resins with this viscosity easily fill pores (cells, voids) with sizes of 5-6 microns. Partially required optimal viscosity of ETF resin (especially hot curing) can be ensured by concomitant winding or impregnation with heating, the temperature of which is 323-353 K (50-80 ° C) and is supported by the temperature control system of the impregnating bath with an accuracy of ± 5 K.

The viscosity of the epoxytriphenol resin ETF mixed with rezol phenol-formaldehyde resin SF-340A (taken into the mixture as a hardener) composition, in parts by weight:

- epoxytriphenol resin ETF - 97-103;

- resol phenol-formaldehyde resin SF-340A - 31-37;

- acetone - 87-93;

- ethyl alcohol - 43-49;

- toluene oil and / or coal - 7-13,

at normal temperature, 20 ± 1 ° С is 2-5 MPa · s.

With the concomitant heating of these ETF + SF-340A resins in the bath of the impregnation machine to temperatures of 323-353 K (50-80 ° C) upon receipt of the “prepreg” woven filler for “dry” winding of products on them or with direct impregnation of the filler with these resins in the tub of the winding machine for the "wet" winding of products can bring the viscosity of these resins to 1-3 MPa · s. The temperature of these resins should be automatically maintained by the temperature control system of the impregnation bath with an accuracy of ± 5 K.

It should be noted that the viscosity of the binder may change during the impregnation of the “prepreg” or winding upward due to the structuring process, and its initial value depends on the age of preparation and storage conditions.

These factors should be taken into account by developers when developing technological regulations for the preparation of binders and products formed from composite fibrous materials by winding methods. Particularly strongly affects the viability of the binder temperature. For the binding ETF (≈60%) + SF-340A (≈40%), the temperature dependence of its viability is given in Table 9.

Table 9
The vitality of the hybrid binder ETF + SF-340A Temperature, K 293 313 353 393 413 Temperature ° C twenty 40 80 120 140 The viability of the hybrid binder ETF + DEG-1 6.6-7 days 3.3-3.5 days 135 minutes 17 minutes 9 minutes

It should be noted that the viability of this binder in comparison with the prototype is 10-13% higher (table 1).

Thus, careful control of the temperature of the binder is one of the ways to maintain its optimal viscosity, and therefore the quality of the impregnation.

Heating the binder within its operating temperature significantly improves the impregnation of the filler even with lower amounts of the binder applied to the fiber reinforcement, which allows some control of the volumetric content of the fibrous filler in the composition; the optimal volumetric content of the fibrous filler and ETF + SF-340A binder from the point of view of obtaining composite strength: filler - 70%, binder - 30%.

It should be noted that the SF-340A phenol-formaldehyde resin used above for curing the ETF resin was taken to improve the heat resistance and thermal stability of the plastics obtained on its basis.

However, the ETF + SF-340A binder has non-optimal viscosity values; The optimal viscosity values for wet winding and / or impregnation of the tissue filler are in the range of 0.1-1 Pa · s (when controlling viscosity with a B3-4 viscometer, this corresponds to 15-85 s). Binders with this viscosity easily fill pores with a diameter of 3-6 microns.

When the viscosity of the binder ETF + SF-340A is 1-3 MPa · s, this leads to a deterioration in the impregnation and quality of products: firstly, it leads to a large deposit of resin, which degrades the strength and stiffness of plastics, overspending resin and increasing the cost of the finished product, and secondly, this leads to a lack of impregnation of the spaces (pores) between the fibers - composites, and, as a result of this, the formation of significant shrinkage, large internal stresses, pores, warping, cracking, etc.

The developers have three fallback options for achieving optimal binder viscosity during winding or impregnation:

Option 1 - more accurate dosing of the hardener - resin SF-340A in a binder ETF and its uniform distribution.

Option 2 - introducing a diluent-plasticizer into the complex binder resin with a low viscosity, as the epoxyaliphatic resin DEG-1 with a molecular weight of 240-320, a mass fraction of epoxy groups of 26% and a dynamic viscosity of not more than 0.07 MPa in the proposed binder recipe S (at t = 20 ± 1 ° С) (Table 7).

Option 3 - programming the speed and intensity of thermal effects during curing, optimizing the composition and doses of the introduced hardener and binder activators - zeolites (alkali and alkaline earth metal aluminosilicates used as catalysts, etc.).

It must be borne in mind that:

- excess hardener does not lead to a more complete or faster cure, but can cause corrosion of metal and fibers, reduce adhesion to them, deteriorate mechanical properties, reduce water and corrosion resistance, heat resistance and other characteristics of materials;

- the lack of a hardener slows down the curing process of the hybrid binder or completely stops it.

It is already almost impossible to introduce additionally or remove excess hardener from the binder. The dosage accuracy of the hardener ingredients, many of which are volatile, must be very high, since they have a stronger effect on the characteristics of the polymer.

The efficiency of the curing process of the binder, its viability and other properties are significantly increased when, along with the hardener ingredients, other chemically active substances are introduced that act as a catalyst (reaction accelerator), complexly affect the speed and depth of the curing process and prevent the formation of thermal explosions that distort the properties of the cured hybrid binder. To prevent thermal explosions, it is necessary to program the speed and intensity of thermal effects during curing, to optimize the composition and doses of activators introduced into the hardener: chalk or calcium sulfate (up to 20%), and also to moisten the hardener granules and aluminosilicates introduced into it with water (up to 25%).

Another technological solution is proposed - introducing into the ETF + SF-340A composite binder a diluent-plasticizer resin of a low-viscosity epoxyaliphatic resin DEG-1 with the properties shown in Table 7.

The highly viscous ETF and SF-340A resins can be used to impregnate fibrous materials due to their good compatibility with the active diluent, which is the DEG-1 resin, which is a product of the condensation of diethylene glycol with epichlorohydrin.

Resin DEG-1 due to approximately the same composition with epoxy resin ETF is well compatible with it and various types of fibrous fillers. The temperature of its processing is in the range of 180-200 ° C and is in the temperature range used in the processing of ETF resin.

By introducing the epoxyaliphatic resin DEG-1 into the ETF + SF-340A complex binder, the optimum viscosity of the hybrid binder is obtained in the range of 0.1-1.0 Pa · s.

The introduction of DEG-1 resin reduces the shrinkage of the material and reduces the internal stresses in the composites based on a hybrid binder, their warping, cracking, pore formation and other defects, and, as a result of the foregoing, increases the productivity of winding equipment, improves the quality of products from composite fibrous materials and reduces their cost.

On the basis of epoxytriphenol ETF, epoxyaliphatic DEG-1 and phenol-formaldehyde SF-340A resins, in accordance with the methods described below, new hybrid binders are formed according to claims 1-38 of the claims.

These hybrid binders in comparison with the prototype have higher manufacturability and vitality, higher physical and mechanical (by 5-10%) and thermophysical (by 10-20%) properties, and in terms of interlayer tear-off (transverse) and shear strength of plastic on it based superior plastic based on a binder-prototype several times.

Hybrid binders according to claims 1-38 of the claims are well compatible with acetone-alcohol-toluene solvents, have a sufficiently high adhesive strength (Table 2), are compatible with almost all fibrous fillers, including flame retardants introduced into them, antistatic additives, metal oxides and nitrides, silicon oxides and discrete whiskers.

The developed hybrid binders are well compatible with the powdered fillers introduced into them, formed from metal oxides and / or nitrides, and with soot, and with carbon-graphite mixtures, and with discrete fibrous fillers, and with molecular sieves such as zeolites, introduced in order to improve one or another physicomechanical, thermophysical, antistatic and other properties of composites formed on their basis by winding and / or pressing methods.

So, for example, molecular sieves of the type Na-zeolite (or sodium aluminosilicates - pp 13-18, 50) introduced into the hybrid binder increase its viability during the hot curing method by 2-3.5 times in comparison with the prototype.

The introduction of finely divided fillers in the form of whiskers into the composition of glass-carbon-boron-organoplastics, as well as some powder fillers from metal oxides and / or nitrides and / or silicon oxide (silica) allows to reduce the exothermic effect during curing, improve mechanical and some thermophysical characteristics, as well as a number of special properties (resistance to fire, radiation and aging, electrical, magnetic properties, etc.) and reduce the cost of plastics.

As fillers for hybrid binders, powdered (monolithic and hollow), scaly and fibrous particles from metal oxides and / or nitrides and / or silicon oxide with the properties shown in Table 10 and whiskers with the properties shown in Table 1 can be used. .eleven.

Table 10
Properties of powder fillers introduced into hybrid binders according to claims 26-27, 29-33 of the claims Filler Molecular mass Density, g / cm ³ Melting point, K Boiling point, K Specific heat, kJ / (kg · K) The coefficient of thermal conductivity, W / (m · K) Magnesium Oxide (Burnt Magnesia), MgO 40.3 3,58 3073 3098 2.09 34.2 Alumina (Alumina), Al ₂ O ₃ 101.9 3.97 2288 3253 1.09 30,2 Titanium oxide (rutile), TiO ₂ 79.9 4.24 2113 2500 0.84 6.3 Silica (silica), SiO ₂ , SiO ₄ 60.1 2,32 2011 3223 0.75 1.7 Boron Nitride, BN 24.8 2.27 3023 3273 0.92 14.3 Table 11
Properties of whiskers introduced into hybrid binders according to claims 28, 34-38 of the claims Whiskers Density, g / cm ³ Melting point, K Tensile stress, GPa Modulus of elasticity, GPa Al ₂ About ₃ 3.94-3.96 2313 20.6-276 413.6-507.6 SiC 3.16-3.2 2963 11.0-20.6 480.2-483.1 Cr, Cr ₂ O ₃ , CrO ₃ 7.2 2163 8.85 240 Fe, FeO, Fe ₃ O ₄ , Fe ₂ O ₃ 7.85 1813 13.03 199

The amount of introduced powder and discrete fibrous fillers (NK) can reach 30-50% and 5-15%, respectively, while powder fillers (Table 10) mainly increase the toughness of plastics based on hybrid binders according to items 26-27 , 29-33 of the claims, and whiskers (Table 11) - mainly increase interlayer characteristics: tear-off (transverse) and shear strength.

Some of the powder fillers, such as aluminum oxides AlO ₄ , Al ₂ O ₃ (alumina), silicon oxides SiO ₂ , SiO ₄ , iron oxides FeO, Fe ₃ O ₄ , Fe ₂ O ₃ can additionally play a role even in small doses catalytically active structure-forming agents in the polymer binder, adjusting the size and number of formed elements of the supramolecular structure, and therefore the physicomechanical and thermophysical characteristics of the composites based on it.

Some powder fillers introduced into hybrid binders, for example, carbon black, carbon-graphite mixtures (claims 19-24), can give the composites good antistatic properties, as well as improve their electrical and corrosion properties, resistance to high-enthalpy high-speed gas flows and also give the composites the desired color and some specific properties - magnetic, resistance to fire, heat resistance and thermal stability, resistance to various radiation, including magnetic, thermal, light and radiation.

However, powder fillers and whiskers can cause some undesirable effects, such as:

- reduction of hygroscopicity and gas permeability of reinforced plastic;

- significant slowdown or, conversely, acceleration of the curing of the binder;

- reduction of adhesive and cohesive strength with fibers, including fibers coated with lubricants and finishes.

The introduction of finely divided powder fillers and whiskers into hybrid binders leads to an increase in the viscosity of hybrid binders and thereby causes technological difficulties in their processing into “prepregs” and further into structural products.

To increase fire resistance, heat resistance, thermal stability and resistance to the effects of high-speed and high-enthalpy gas flows at the stages of preparation of the hybrid binder, it is proposed to introduce flame retardant additives - trichloroethyl phosphate, carbon tetrachloride, hexachlorobenzene, antimony trioxide and chladone, which slow down the combustion of plastics decomposition (claims 2-8, 14-18 of the claims).

The principle of operation of flame retardants is as follows: flame retardants in plastic slow down, and in many cases prevent their burning due to endothermic effects during their thermal decomposition, the gases emitted in this case (ammonia, carbon dioxide, chloride, bromide and phosphoric anhydrides, water vapor, etc. ) also interfere with combustion. One of the best flame retardants is boric acid H ₃ BO ₃ . However, it has a significant drawback, which is that it gives a precipitate when introduced into a hybrid binder.

Among the flame retardants introduced into hybrid binders, the most effective are chlorine-containing flame retardants:

- trichloroethyl phosphate (C ₂ Cl ₃ H ₄ PO ₄ ) of the structural formula:

- carbon tetrachloride (CCl ₄ ) structural formula:

- hexachlorobenzene (C ₆ Cl ₆ ) of the structural formula:

- Freon (freon) brand F-114B ₁ (C ₂ Br ₂ F ₄ ) or freon brand F-114B ₂ (C ₄ Cl ₄ F ₄ ) structural formulas:

and antimony trioxide SbO ₃ .

All of the above flame retardants are introduced into hybrid binders according to claims 2-8, 14-18 of the claims to increase the fire resistance of plastics based on them and to reduce the explosion and fire hazard of processing hybrid binders into “prepregs” and further into structural products.

The above flame retardants slow down the burning of plastics due to endothermic effects during their thermal decomposition. The gases released during this (ammonia, carbon dioxide, phosphoric and chlorine anhydrides, water vapor, etc.) also prevent combustion. Antimony trioxide is also a good flame retardant, which simultaneously increases both heat resistance, and fire resistance, and antifriction properties of plastics.

Its use as a flame retardant is known together with boric acid H ₃ BO ₂ (see fire-resistant binder for fiberglass according to author certificate No. 670593 of 03/01/78, bull. No. 24, 1979, class C 08 L 67 / 08, 32 V 27/03).

In this binder, in order to increase fire resistance while maintaining the high physical and mechanical properties of the binder and fiberglass based on it, antimony trioxide (SbO ₃ ) is used in a mixture with chloroendic anhydride and boric acid (H ₃ BO ₃ ), taken in the ratio (3-4) : (1-1,4) in the form of a 60-65% suspension in glycerol in the following ratio of the components of the binder, in parts by weight:

- polyester resin - 65-70;

- 60-65% glycerin suspension of chloroendic anhydride of boric acid and antimony trioxide - 30-35.

This hybrid binder can be used in the manufacture of large structures that do not experience significant loads. Restrictions on the use of a binder according to ed. testimonial. No. 670593 are mainly associated with its low technology, high shrinkage during curing, low viability (1-2 days at temperatures of 20-25 ° C), the ability to precipitate (the main disadvantage of using boric acid), as well as the following low characteristics of plastics on its basis: atmospheric corrosion resistance, heat resistance (less than 120 ° C) and resistance to high-enthalpy high-speed gas flows.

In the claimed variants of the hybrid binders, antimony trioxide (SbO ₃ ) is used in combination with rezol phenol-formaldehyde resin SF-340A and epoxy-epoxytriphenol ETF and epoxyaliphatic DEG-1 resins.

In their compositions, hybrid binders according to claims 1-38 of the claims contain up to 4% of free phenol C ₆ H ₅ OH and aniline C ₆ H ₅ NH ₂ (Table 7). The use of phenol-formaldehyde resin SF-340A in a hybrid binder according to claim 1 allows to increase the heat resistance and thermal stability of plastics based on it to 210-250 ° C. At the same time, the introduction of the SF-340A phenol-formaldehyde resin into the hybrid binder allows maintaining the fire resistance of the plastics based on it at a sufficiently high level (the burning time of the plastic after removal of the gas burner flame is no more than 5 seconds, and the plastic oxygen index is 38-42%).

Apparently, this is due both to the influence of phenol, which enhances the fire extinguishing characteristics of the plastic during combustion due to the release of coal, and due to the influence of aniline, which rigidly binds free formaldehyde in a hybrid binder.

The influence on the fire resistance of plastics and another flame retardant, freon, introduced into hybrid binders according to items 4-6, 14, 16, 18 of the claims in the form of two modifications is very significant: Ф114B ₁ or Ф114В ₂ . Both modifications contain unsaturated fluorocarbons containing bromine Br ₂ or chlorine Cl ₂ related to extinguishing components.

The first modification of the freon C ₂ Br ₂ F ₄ has the structural formula:

The second modification of the freon C ₂ Cl ₂ F ₄ has the structural formula:

In the first embodiment, the introduction of C ₂ Br ₂ F ₄ freon into the plastic increases its fire resistance by 10-15% (with the bromine content in the plastic up to 2-15%) and the temperature resistance of the plastic up to 200 ° C with a flame spread of 3-4 seconds (bromine enhances the extinguishing characteristics of plastic during combustion due to the release of coal). The oxygen index of such plastics is in the range of 42-45%, the heat resistance of plastics is up to 350 ° C.

In the second embodiment, the introduction of C ₂ Cl ₂ F ₄ in plastics also increases its fire resistance - by 15-20% (with a chlorine content of 5-20%) and the heat resistance of plastic - up to 300 ° C.

Note - When burning plastic containing C ₂ Cl ₂ F ₄ freon, chlorine anhydride is formed, which also prevents burning. The oxygen index of such plastics is in the range of 45-50%.

Hexachlorobenzene (C ₆ H ₅ Cl ₄ ) ₆ - aromatically halogenated hydrocarbon, water insoluble liquid; Hexachlorobenzene in the manufacture of hybrid binders according to claims 5 to 8 is used both as a solvent, well soluble in acetone-alcohol-toluene mixture, reducing its dynamic viscosity to 0.1-1.0 Pa · s, and as a flame retardant, due to hydrocarbon and chlorine, it increases the fire resistance of plastics by 5-10% and their heat resistance at temperatures of 300-350 ° C.

Trichloroethyl phosphate C ₂ Cl ₃ H ₄ PO ₄ (claim 2) and carbon tetrachloride CCl ₄ (claim 3) are also highly effective flame retardants that increase the fire resistance of plastics. Trichloroethyl phosphate - due to the release of flame-extinguishing phosphoric and chloride anhydrides during combustion, carbon tetrachloride - due to the allocation of carbon chloride anhydrides.

Due to the introduction of trichloroethyl phosphate into plastics, their fire resistance increases to 15-25% (the oxygen index of plastics is 50-52%). Due to the introduction of carbon tetrachloride into plastics, their fire resistance increases to 10-20% (the oxygen index of plastics is 45-50%).

The most effective is the introduction into hybrid binders according to claims 2-8 of the claims of fire retardants in microencapsulated form, that is, when they are introduced into hybrid binders in the form of finely dispersed capsules with a dispersion of up to 300 microns. Microencapsulation of these substances is carried out in order to preserve their fire-extinguishing properties in plastic by enclosing their small particles in a thin shell of a solid film-forming material.

As shells for microencapsulation of flame retardant particles, a material based on resorcinol-formaldehyde-urea resins modified with polyvinyl alcohol is used.

Table 12 below shows the plastics data on the tensile strength of the hybrid binder (σ _growth , kgf / cm ² ), as well as the values of their oxygen index (KI,%), average linear ablation (V _y , mm / s) and average the rate of entrainment due to weight loss (m _y , mg / s) of the plastic from highly enthalpy gas flows, depending on the dispersion of the flame retardant microcapsules entered into the hybrid binder according to claims 2-8.

Table 12
Properties of plastics based on hybrid binders according to claims 2 to 8 of the claims containing microencapsulated and non-microencapsulated flame retardants Plastic with additives Dispersion, microns Tensile strength, σ _rast , kgf / cm ² Oxygen Index, CI,% Average linear ablation by temperature sensor V _у , mm / s The average speed of ablation by weight loss, m _y , mm / s Plastic on the basis of TEMS-k (p) fabrics and hybrid. communication according to claim 1 with flame-retardant microencapsulated additives (7-18 parts by weight): trichloroethyl phosphate 10-80 175 49.5 0.7 0.69 carbon tetrachloride 80-200 136 53 0.8 0.78 hexachlorobenzene 200-230 90 52 1,0 0.9 freon 230-250 <4 - 1,2 - antimony trioxide 350 0 - - - Plastic on the basis of TEMS-k (p) fabrics and hybrid. communication according to claim 1 with flame-retardant non-microcalculated additives (7-18 parts by weight): trichloroethyl phosphate carbon tetrachloride hexachlorobenzene chladone antimony trioxide - 130-150 49-55 0.85 0.8 Note - Microencapsulated flame retardants were introduced into hybrid binders according to claims 2-8 in the form of microcapsules, the shells of which were formed from a copolymer based on resercin-urea resins modified with polyvinyl alcohol

The data in table 12 show that plastics based on TEMC-k (p) tissue and a hybrid binder according to claim 1 with the flame retardant microcapsules introduced into them have:

- maximum tensile strength ≈175 kgf / cm ² (with a dispersion of microcapsules of 10-80 μm), 130-150 kgf / cm ² - for flame retardants introduced in liquid and / or powder form;

- maximum oxygen index ≈53% (with a dispersion of microcapsules of 80-200 microns), 49-55% - for flame retardants administered in liquid and / or powder form;

- average linear ablation by a temperature sensor ≈0.7 mm / s - for plastics with a filler made of TEMS-k (p) fabrics with microcapsules of flame retardants with a dispersion of 10-80 microns; 0.85 mm / s - for flame retardants administered in liquid and / or powder form;

- the average rate of ablation by weight loss is 0.69 mm / s (with a dispersion of microcapsules of 10-80 microns), 0.8 - for flame retardants administered in liquid and / or powder form. The data in Table 12 show that plastics based on TEMC-k (p) tissue and a hybrid binder according to claim 1 with the flame retardant microcapsules inserted into it have:

- increased strength ≈175 kgf / cm ² ;

- high oxygen index ≈49-55%;

- average linear ablation by a temperature sensor of 0.7 mm / s - for plastics with fillers from TEMS-k fabrics (p);

- the average rate of ablation by weight loss of 0.69 mm / s for plastics with microencapsulated flame retardants introduced, 0.8 mm / s for plastics with powdered and / or liquid flame retardants added.

The data in Table 12 show that the introduction of flame retardants into a hybrid binder according to claim 1 significantly increases the oxygen index (CI) of plastics based on it - 49-55%, instead of CI - 38-48% - for plastics based on a hybrid binder according to claim 1 of the claims, and the average linear ablation of the temperature sensor for plastics based on it is 0.7 mm / s, instead of 1.0-1.2 mm / s - for plastics based on a hybrid binder according to claim 1.

The tensile strength of hybrid binders, depending on the amount and dispersion of the flame retardants introduced into them, decreases, and for microcapsules with a dispersion of 350 microns it becomes close to zero, that is, it is impractical to use such binders to create plastics with both high heat and flame retardant and strength properties.

It should be noted that the hybrid binder with the introduced flame retardants has a slightly lower viability (1-3 days at a temperature of 20 ± 1 ° C) and higher dynamic viscosity (> 1 Pa · s for plastics with powdered and microencapsulated flame retardants), which is somewhat degrades the processability of processing hybrid binders. The viscosity of hybrid binders can also vary both in the direction of decreasing (depending on the amount and composition of the flame retardants introduced into them), and in the direction of increasing (depending on the age of preparation and storage conditions). And all of the above factors should also be taken into account by technologists when developing technological regulations for their processing into “prepregs” and further into structural products based on them.

The viability of the hybrid binder according to claim 13 can be increased by introducing into it the so-called molecular sieve in the form of sodium aluminosilicate and / or zeolites (aluminosilicates), which can adsorb its various components, including the components of the phenol-formaldehyde resin hardener SF-340A (table 7).

As the molecular sieve, crystalline aluminosilicates are used in the present invention. Their introduction can be carried out both by mixing with a hybrid binder, and with their direct preliminary mixing with resin-hardener SF-340A. The hybrid binder may be saturated with aluminosilicates and pairs of adsorbable hardener (item 50 of the claims).

Molecular sieves such as Na zeolite (or sodium aluminosilicates), as well as alkali and alkaline earth metal aluminosilicates, can be used both in the purification and separation of mixtures of a hybrid binder, as well as agents that slow down the rate of chemical reactions that occur in a hybrid binder.

Aluminosilicates are used as inhibitors of the curing of the hybrid binder; these are heterogeneous porous granular inhibitors based on silicon oxides SiO ₂ , SiO ₄ and aluminum oxides Al ₂ O ₃ , AlO ₄ .

Introduction to the hybrid binders of inhibitors based on silicon oxides SiO ₂ and aluminum oxides Al ₂ O ₃ , as well as crystalline sodium aluminosilicates in an amount of 7-13 parts by weight allows to increase the viability of hybrid binders by 2-3.5 times, ≈15-20 days at temperatures of 293-303 K and 7-10 days at temperatures of 313-353 K.

Therefore, in order to maintain the optimal viscosity (0.1-1.0 MPa) of the hybrid binders, and therefore the quality of the impregnation, it is recommended that they be heated with an impregnation of 40-70 ° C.

In this case, the impregnation improves even with lower doses of a binder applied to the fabric reinforcement, which, in turn, allows some control of the volume content of the fibrous filler in the composition.

The developed variants of hybrid binders (according to items 26, 28-32 of the claims) allow the introduction of other finely divided fillers in their compositions.

The introduction of finely dispersed fillers, for example, metal oxides or nitrides and silicon oxides, into the composition of the hybrid binder allows to reduce the exothermic effect during curing, reduce shrinkage, lower the level of residual stresses (several times), as well as improve their mechanical characteristics: transverse and shear strength, some thermophysical characteristics and a number of specific properties - resistance to radiation, aging, as well as electrical, magnetic, antistatic properties ustv and reduce the cost of plastics.

Powdered (monolithic, hollow and scaly) fillers and discrete fibrous fillers - whiskers were used as dispersed fillers for the hybrid binder.

The amount of introduced powder and discrete fibrous fillers should be, respectively, 30-40% and 5-10%, while powder fillers increase mainly the impact strength of plastics to 50%, and discrete fillers (whiskers) increase mainly transverse strength and stiffness plastics and their interlayer shear and tear strength up to 20-40%.

Some types of powder fillers, such as silicon oxide SiO ₂ (silica) and alumina Al ₂ O ₃ (alumina), introduced into the binder even in small doses, play the role of catalytically active builders in the hybrid binder and control the size and amount of the formed elements of the supramolecular structure hybrid binder, and therefore, improve the physicomechanical characteristics of composites based on it.

Powder fillers from metal oxides and nitrides, introduced into hybrid binders, can also play the role of pigments, allowing to obtain the desired color of products.

However, the finely dispersed fillers introduced can cause some undesirable effects in plastics, such as a change in the hygroscopicity and gas tightness of reinforced plastics, a significant slowdown or, on the contrary, acceleration of the curing of the hybrid binder, an increase in the viscosity of the binder and the resulting technological difficulties in processing the hybrid binder into “prepregs” and further into structural products based on them.

The properties of composites and products made from them depend both on the properties of powder, discrete and flame retardant fillers, and on the methods for their preparation, as well as on methods for producing hybrid binders and fabric "prepregs" based on them, as well as on the properties of fabric fillers and their modes processing.

Analyzing table 3, 10, 11, we come to the conclusions:

- powdered alumina Al ₂ O ₃ and Al ₂ O ₃ whiskers are most efficiently used in composites with filler from aluminum-borosilicate alkali-free glass fibers of the ABS type (Table 3);

- powdered magnesium oxide MgO is most efficiently used in composites formed on the basis of aluminum-magnesium alkaline glass fiber fillers;

- powdered titanium oxide TiO _{2 is more} rational to use in composites formed on the basis of titanium-containing alkali-free glass fibers of type T273 brand (Table 3);

- powdered silicon oxide SiO ₂ and whiskers of carbon silicon SiC can be effectively used in composites containing all of the above fibrous fillers;

- powdered boron nitride BN is more appropriate to use in composites filled with alumina-borosilicate alkali-free glass fibers of the ABS type and glass fibers of type E of the US formulation (Table 3);

- whiskers of chromium Cr and iron Fe and their oxides can be effectively introduced into hybrid binders according to claims 34-38 of the claims, which can be used to impregnate any compositions of fiberglass fillers listed in table 3.

Below the description of the text presents the most preferred methods for producing hybrid binders and their effectiveness.

The effectiveness of the hybrid binder according to claim 1 of the claims and method for its preparation

The method involves the sequential dissolution of epoxytriphenol ETF, epoxyaliphatic DEG-1 and rezol phenol-formaldehyde SF-340A resins with each other at elevated temperatures. Obtaining a hybrid binder according to claim 1 of the claims is carried out in several sequentially interconnected operations.

First, a mixture of two epoxy resins is prepared - epoxytriphenol ETF (TU 2225-316-09201-208-94) - the base resin of the hybrid binder and epoxyaliphatic resin DEG-1 (TU 2225-027-002033-97) - the plasticizer resin. Both resins are dissolved among themselves in a mixing reactor by means of an acetone-alcohol-toluene mixture first fed to the reactor with a ratio of ingredients of 1: (0.5-0.6) :( 0.1-0.2), and then for bringing the hybrid binder to the calculated density and viscosity - alcohol-acetone mixture with a ratio of ingredients 1: 2.

Both resins (ETF and DEG-1), before being loaded into the reactor-mixer, are separately heated and at different heating rates to a temperature of 180-200 ° C in the melting chambers.

ETF epoxy resin is heated to temperatures of 180-200 ° C with heating rates of 20-30 ° C / hour.

The epoxyaliphatic resin DEG-1 is heated to temperatures of 180-200 ° C with heating rates of 90-100 ° C / h, then both resins heated to temperatures of 180-200 ° C are fed to the reactor-mixer, they are pre-mixed for 30-60 minutes, and then they are completely dissolved by mixing at a mixture temperature of 40-70 ° C for 3-6 hours based on one ton of the obtained product in the presence of a solvent: a mixture of acetone, ethyl alcohol and toluene oil and / or coal.

The dissolution of the ETF and DEG-1 resins is carried out by means of an acetone-alcohol-toluene mixture, which is loaded into the reactor-mixer with the following components, in parts by weight:

- epoxytriphenol resin ETF - 97-103;

- epoxyaliphatic resin DEG-1 - 9-15;

- acetone - 87-93;

- ethyl alcohol - 43-49;

- toluene oil and / or coal - 7-13.

At the next stage, ETF and DEG-1 resins, dissolved between themselves, are introduced into the mixer-resin phenol-formaldehyde resin SF-340A (GOST 18694-80) previously crushed and crushed into a powder mass with a particle size of not more than 3 mm

Resol phenol-formaldehyde resin SF-340A introduced into the reactor-mixer must comply with the following parameters:

- the content of free phenol is not more than 4%;

- the content of free aniline is not more than 4%;

- volatile matter and moisture content - not more than 1.5%;

- dynamic viscosity of the resin - 10-20 MPa · s.

After introducing SF-340A phenol-formaldehyde resin into the mixer, it is dissolved with ETF and DEG-1 resins there by stirring at mixture temperatures of 40-70 ° C for 3-6 hours per ton of product obtained, filtered and cooled to temperatures 20 ± 1 ° C. Thus, a hybrid binder according to claim 1 is obtained with a product density of 0.95-1.1 g / cm ³ .

In the next additional step, in cases of over density of the product, an alcohol-acetone solvent with an ingredient ratio of 1: 2 is additionally introduced into the mixture of ETF + DEG-1 + SF-340A resins obtained and located in the reactor-mixer and the newly obtained consistency of the prepared product is mixed at temperatures of 40-70 ° C for 30-60 minutes based on one ton of the product, bringing its density to 0.95-1.1 g / cm ³ (due to the alcohol-acetone mixture portionwise introduced into the reactor mixer with the ratio of ingredients 1: 2). The weight amount of the additional alcohol-acetone solvent introduced into the reactor-mixer is 20-30 kg per ton of the prepared hybrid binder.

After carrying out the above technological operations, mixing and dissolving the ETF, DEG-1 and SF-340A resins filter the hybrid binder by removing all insoluble components of the finished product by passing it through a special filter and / or filtering it through a special "Excelsior" fabric with mesh sizes 1-3 mm.

After filtering the finished product (hybrid binder), it is cooled to temperatures of 20 ± 1 ° С and packaged in a special container with sealing means or poured into the baths of impregnation machines, through which the binder is impregnated and further processed (together with a woven or unidirectional filler) with transferring the binder to the “prepreg” state.

The industrial method of obtaining a hybrid binder according to claim 1 of the claims (the method presents technological operations for producing a hybrid binder per ton of finished product):

1. Heated epoxytriphenol resin ETF in the amount of 365.6 kg (97-103 parts by weight) to temperatures of 180-200 ° C with a uniform heating rate of 20-30 ° C / hour.

2. The epoxytriphenol resin DEG-1 is heated in an amount of 43.8 kg (9-15 parts by weight) to temperatures of 180-200 ° C with a uniform heating rate of 90-100 ° C / hour.

3. An acetone-alcohol-toluene solvent is prepared in a quantitative ratio of 301.6: 168.2: 36.5 (1: (0.5-0.6) :( 0.1-0.2) (acetone - 87- 93 parts by weight, ethyl alcohol - 43-49 parts by weight, oil and / or coal toluene - 7-13 parts by weight).

4. Heated epoxy resins ETF, DEG-1 and acetone-alcohol-toluene solvent are poured into the reactor-mixer.

5. The mixture of the above components is brought to a temperature of 40-70 ° C in a mixing reactor and mixed with a stirrer for 3-6 hours based on one ton of the product being prepared.

6. The resol phenol-formaldehyde resin SF-340A is ground in an amount of 124.5 kg into particles (pieces) with sizes of 1-3 mm (31-37 parts by weight) and added to the reactor-mixer into acetone-alcohol already dissolved between each other -toluene solvent epoxy resins ETF and DEG-1.

7. The newly obtained consistency of resins (ETF + DEG-1 + SF-340A) is heated to temperatures of 40-70 ° C and mixed at these temperatures in the reactor-mixer for 3-6 hours based on one ton of the product being prepared.

8. The consistency of the binder is adjusted to a density of 0.95-1.1 g / cm ³ by additionally introducing into it an alcohol-acetone solvent with a component ratio of 1: 2 in an amount of 20 kg (≈1.64 parts by weight) and mix with the prepared product at temperatures of 40-70 ° C for 30-60 minutes.

9. The finished consistency of the hybrid binder is filtered through a special filter or sparse Excelsior fabric with mesh sizes from 0.1-0.1 to 3-3 mm in order to remove all insoluble resin particles SF-340A in the mixing reactor to obtain a hybrid binder according to claim 1 of the claims.

10. The hybrid binder according to claim 1, ready for impregnation, must meet the following requirements:

a) appearance - a homogeneous solution from brown to dark brown in color, not containing foreign inclusions and insoluble particles;

b) mass fraction of non-volatile substances - 50-63%;

c) the density of the hybrid binder at temperatures of 20 ± 1 ° C is 0.95-1.1 g / cm ³ ;

g) indicator "gelatinization time" of the binder - 3-6 minutes

The characteristics of the hybrid binder according to claim 10b, 10c, 10 g are checked in the Central Laboratory of Federal State Unitary Enterprise Avangard by special methods and, in case of deviation of the values of the characteristics from the above, the resin SF-340A is additionally portioned into the binder (in cases of low density) or components of an alcohol-acetone solvent with an ingredient ratio of 1: 2 (in cases of high density) and all introduced components are again mixed in a mixing reactor at temperatures of 40-70 ° C for 30-60 minutes.

11. Next, a tissue filler heated to temperatures of 40-70 ° C is filled into the impregnation machine.

12. The temperature regime is set in the shaft of the impregnation machine 90-130 ° C (at the inlet and outlet of its drying chamber) and 130-200 ° C in its main working areas.

13. Then the hybrid binder is poured into the bath of the impregnation machine and it is heated in the bath to temperatures of 40-70 ° C.

14. At the next processing stage, a continuously moving woven filler is impregnated with a hybrid binder at a speed of 1-3 m / min and a tension of 0.5-2 kg per centimeter of web width, followed by removal of excess binder on the squeeze rolls of the impregnation machine.

15. Then, upon reaching the tissue filler of the “prepreg” state, the movement of the “prepreg” stops for 2-3 minutes, samples are cut from it and checked for compliance with the following requirements:

a) mass fraction of the hybrid binder,% - 35-55;

b) mass fraction of volatile substances and moisture,% - 0.8-4.5;

c) mass fraction of soluble hybrid binder,% - 88-92.

16. Next, the manufacture of full-scale products or samples is carried out by winding or pressing on the basis of a “prepreg” from a hybrid binder according to claim 1 and fabric fillers, for example, plain weave, formed from aluminoborosilicate alkali-free filaments (Table 3) used in production responsible power structural products with increased strength and rigidity, and fabrics: caproamide (kapron) grade TEMS-k and polyphene grade TEMS-p (TU 6-06-31-I82-85), formed from multicomponent complex of electroconductive threads MKEN-k (p) (TU 6-06-31-120-76) used in the production of heat-protective plastics with high sublimation and antistatic properties.

17. Next, samples are cut from the allowances of wound products and / or from pressed plates and tested according to standard methods to obtain the following characteristics of plastics (Table 13).

Table 13
The properties of plastics based on a hybrid binder according to claim 1 and tissue fillers: from glass (based on T-13 plain glass fabric), caproamide (based on TEMS-k fabric) and polyphene (based on TEMS-p fabric) fabrics two manufacturing methods - winding (table 14) and pressing (table 15) (testing of samples of plastic material was carried out at temperatures of 20 ± 1 ° C) Specifications Winding Pressing Fiberglass T-13 + hybrid. communication according to claim 1 TEMC-K fabric + hybrid. communication according to claim 1 TEMS-p fabric + hybrid. communication according to claim 1 Fiberglass T-13 + hybrid. communication according to claim 1 TEMC-K fabric + hybrid. communication according to claim 1 TEMS-p fabric + hybrid. communication according to claim 1 Density, g / cm ³ 1.65-1.9 1,2 1.18 1.6-1.8 1.25 1.26 Destructive stress, MPa: tensile

when bending

Tensile modulus, GPa

2,8 2.6 Impact strength, kJ / m ²

The coefficient of thermal resistance, · 10 ⁶ , K

- -

- - Specific heat, kJ / (kg · K) 0.6-1.3 0.9-1.35 0.9-1.35 0.7-1.7 1-1,42 0.98-1.36 The coefficient of thermal conductivity, W / (m · K) 0.16-0.4 0.19-0.23 0.19-0.22 0.14-0.39 0.19-0.22 0.2-0.22 Water absorption,% 0.2-1.5 0.4 0.4 0.05-0.6 0.35 0.34 Poisson's ratio

- -

Heat resistance according to Martens, K 350-600 650 700 400-650 670 750 Temperature, K: long, hour
480-510
650
700
400-520
670
750 short time, sec 600-800 850 850 610-830 900 950 The temperature of the beginning of intense destruction, K 590 650 650 600 700 720 The coefficient of thermal diffusivity, · 10 ⁶ , m ² / s - 0.9-1.2 0.9-1.3 - 0.85-1.15 0.85-1.2 Notes:
1 The values given in the numerator correspond to the direction of the base of the plastic, in the denominator - to the direction of the weft of plastic.
2 For fiberglass based on T-13 fabric and a hybrid binder according to claim 1: the mass fraction of glass filler T-13 is 70%, the hybrid binder is 30% (structural plastic); for plastics based on caproamide and polyphene filaments: mass fraction of filler - 50-60%, hybrid binder - 40-50% (heat-resistant plastic).

Table 14
Modes of manufacturing structural plastics based on "prepreg" glass-carbon-boron-organoplastic fabric fillers and heat-shielding plastics based on fabrics TEMS-k (p), carbon fabrics such as UT-900-2.5 and a hybrid binder according to claim 1 obtained by winding Name of characteristic Characteristic Value The temperature of the heating shaft during its short-term contact with the heated "prepreg" for no more than 3 minutes, ° С 180 Recommended rolling pressure, n / m from 10,000 to 15,000 Heat treatment temperature, ° С from 130 to 200 Recommended value of the nominal tension "prepreg" when impregnated and wound on the mandrel for one centimeter of the width of the "prepreg", kgf from 0.1 (when refueling or without tension) to 1-1.5 (when impregnating and winding) Recommended winding speed "prepreg" on a rotating mandrel, m / min, no more from 1 to 3 Recommended rate of temperature change in polymerization heat chambers, ° С / g ² , no more twenty Heat treatment temperature, ° С from 130 to 200 Recommended holding time of plastic winding products with wall thicknesses, hour:
from 0.5 to 2 mm
from 2 to 5 mm
from 5 to 15 mm


2-3 (at temperatures 130-200 ° C)
3-4 (at temperatures 150-200 ° C)
14-16 (at temperatures 160-200 ° C)

Table 15
Modes of manufacturing structural plastics based on "prepreg" glass-carbon-boron-organoplastic fabric fillers and heat-shielding plastics based on fabrics TEMS-k (p), carbon fabrics such as UT-900-2.5 and a hybrid binder according to claim 1 obtained by pressing

Name of characteristic Characteristic Value Recommended pressing pressure, MPa 3 to 3.5 Recommended starting temperature, ° С the initial pressure should be created when the press plates reach temperatures from 80 to 130 Speed of temperature rise from 20 ° С to the temperature of the beginning of pressing (80-130 ° С), min, no more from 5 to 15 (depending on the thickness of the products or parts) The rate of temperature rise from 130 to 200 ° C, min, no more 3-5 (depending on the thickness of the products or parts) Press temperature, ° С from 150 to 200 The exposure time of the pressed bag at pressing temperatures of 150-200 ° C for products with a thickness, min: up to 2 mm not less than 30 min from 1 to 5 mm 15-20 (per 1 mm of the thickness of the pressed product) from 5 to 15 mm 20-25 (per 1 mm of the thickness of the pressed product) The possibility of machining plastics allow turning, milling and grinding processing, as well as drilling and cutting with a tool equipped with a hard alloy type VK, or a diamond tool

The obtained characteristics of plastics made on the basis of a hybrid binder according to claim 1 are compared with the characteristics of plastics based on a binder - a prototype according to ed. testimonial. No. 1036730A and T-13 fiberglass.

A comparative analysis shows that plastics based on a hybrid binder according to claim 1 in comparison with plastics based on a binder according to ed. testimonial. No. 1036730A have significant advantages:

- by tensile tensile stresses - by 2-5%, and by thermal stability at a temperature of 200 ° С - by 10-15%;

- by destructive stresses during bending - by 5-10%, and by thermal stability at a temperature of 200 ° С - by 20-30%;

- by heat resistance - by 10-15%;

- fire resistance - by 20-50%;

- at the beginning of the distraction from the heat flux of 3.6 · 10 ⁶ W / m ² and the gas flow velocity of 500 m / s - by 5-10%;

- for transverse stresses - by 30-40% (plastics based on a binder - prototype according to author certificate No. 1036730A begin to delaminate even at the milling stage when making samples from them);

- impact strength - by 15-30%.

In addition, there was a significant decrease in the performance of plastics on a binder prototype (in comparison with a hybrid binder according to claim 1) during long-term storage (imitation of storage for 10 years in a heated warehouse and 1.5 years in an unheated warehouse):

- by physical and mechanical characteristics - by 2-3%;

- according to thermophysical characteristics - by 5%;

- according to heat-shielding characteristics - by 10%;

- by electrical characteristics - by 20%;

- according to destructive stresses at separation from structural fiberglass SKN-24 (satin fiberglass T-10 + EP-5122) - by 10%, SKN-21 (linen fiberglass T-13 + EP-5122) - by 30%.

Note: The decrease in the above characteristics of plastics was determined only on plastics based on polyphenic and caproamide fabrics of the brands TEMS-k (p) (TU 6-06-31-I82-85) and binders (hybrid binder according to claim 1 of the invention and prototype) with the ratio of the compositions of the material, in parts by weight:

- fabric TEMS-k (p) - 50-60;

- binder - 40-50,

belonging to the class of TASM (heat-shielding antistatic sublimating materials).

Glass-carbon-boron-organoplastics, for example, based on fiberglass T-13, carbon fabric UT-900-2.5, etc. and a hybrid binder according to claim 1 of the claims relate to the class of structural. In such plastics, the optimum ratio of filler to binder is within, in parts by weight:

- fiberglass T-13, etc. - 70 ± 5,

- hybrid binder - 30 ± 5,

that is, they are structurally related to structural power plastics, which significantly differ in their properties from heat-protective plastics such as TASM.

The main strength and heat-shielding properties of plastics made on the basis of a hybrid binder according to claim 1 and various types of glass-carbon-boron-organo-fillers in comparison with the prototype plastic based on a hybrid binder according to ed. testimonial. No. 1036730A and linen fiberglass brand T-13 (GOST 19170-73).

Table 16
The main strength and heat-shielding properties of structural plastics, which contain filler - 70 ± 5%, hybrid binder - 30 ± 5%; thermoplastic-based plastics based on TEMS-k (p) fabrics, they contain a filler - 50-60%, a hybrid binder - 40-50% Name of indicator Hybrid binder based plastics according to claim 1 with different types of fillers in comparison with the prototype - plastic based on a hybrid binder according to ed. testimonial. No. 1036730A and T-13 fiberglass fiberglass organoplasty boro plastics coal plastics plastics based on fabric TEMS-p plastics based on fabric TEMS-k Prototype Density, g / cm ³ 1.6-2.2 1.2-1.35 1.6-1.9 1.3-1.9 1.78-1.8 1.27-1.3 1.6-2.2 Heat flux, · 10 ⁶ , W / m ² 3.6 3.6 3.6 3.6 3.6 3.6 3.6 Gas flow rate, m / s 500 500 500 500 500 500 500 Average linear ablation by temperature sensor, mm / s 0.9-1.3 0.9-1.1 0.9-0.95 0.5-0.8 0.85 0.8 > 1.5 The average linear loss of weight loss, g / s 0.85-0.9 0.86-1.09 0.95-0.92 0.5-0.8 0.8-0.9 0.7-0.8 > 1.5 Thermal resistance, sec / (kg / m ² ) ² 2.1 2.0 3-4.5 4,5-5 4.1 2,3 1.9 Effective enthalpy, · 10 ⁶ , J / kg 1.8 2.2 3,5-4 4.2 2,5 3,5 1.7 Sublimation temperature, ° С 280-300 270-280 290-320 350-800 700-750 300-350 <160 Specific Strength, km 30-100 66-110 21-38 33-82 70-80 75-85 30-80 Specific Stiffness, km 1100-3340 5000-5900 12500-14500 10800-12500 700-750 850-900 1000-3000 Elongation at break,% 1.5-2.8 2-7 0.3-0.7 0.4-1 0.3-0.7 0.4-0.8 1.4-2.5 Shear modulus, GPa 1,2-19,5 2.4-14.7 9.8-12.7 9.8-14.7 0.8 2,8 1.2-1.8 Tensile modulus, GPa 12.7-69 58-76 175-265

- - 15-20 Tensile stress, MPa 343-1264 784-1470 885-1375 1300-1900 126 115 350 Shear breaking stress, MPa 5.88-60

shear 79-137 tear-off

- - 6-10 Impact strength, kJ / m ² 19.6-68.6 156-191 44.1-88.2 25.5-82.3 - - 21-25 Poisson's ratio 0.13-0.25 0.35 0.22-0.24 0.05-0.17 - - 0.14-0.2 Water absorption within 24 hours,%, no more 0.05-6 3-18 0.06-2.5 0.12-2.5 0.4 0.35 2-3 The coefficient of thermal expansion, 10 ⁶ , K ^-1 3,5-30 0.6-5.3 4-5

- - 3,5-5 Specific heat, kJ / (kg · K) 1.7-4.2 1.4-2.3 1,1

0.9-1.35 0.9-1.35 - The coefficient of thermal conductivity, W / (m · K) 0.14-0.65 0.11-0.37 0.5-0.7

0.19-0.23 0.19-0.23 0.21-0.35 Thermal diffusivity, · 10 ³ , m ² / hour 0.3-1 0.2-4.55 0.24-0.58

- - 0.85-1.29 Note - The numerator shows values of the indicator along the direction of reinforcement, and in the denominator - across the direction of reinforcement

Fiberglass based on a hybrid binder according to claim 1 of the claims have higher performance in comparison with the prototype in terms of heat resistance (table 17).

Table 17
The heat resistance of fiberglass based on T-13 fiberglass and a hybrid binder according to claim 1 in comparison with the prototype

Test mode for plastics heating Fiberglass-based plastic T-13 + hybrid binder according to claim 1 Plastic based on fiberglass T-13 + hybrid binder according to ed. testimonial. No. 1036730A sample holding temperature, ° С sample exposure time at test temperature, hour tensile stress of samples under tension along the basis, kgf / cm ² modulus of elasticity of the samples under tension along the base, · 10 ⁵ , kgf / cm ² tensile stress of samples under tension along the basis, kgf / cm ² modulus of elasticity of the samples under tension along the base, · 10 ⁵ , kgf / cm ² twenty 3 5308 2,3 4200 2,3 3824 2,3 4250 2,3 4859 2,5 4350 2,4 5565 2,3 4200 2,3 5525 2,4 4100 2.2 average: 5,016.2 average: 2.36 average: 4200 average: 2.3 150 3 5162 2,3 3900 2.2 5318 2,4 4100 2,3 5518 2,3 3800 2.2 4779 2,4 4000 2.2 5453 2,4 4200 2.1 average: 5246 average: 2.36 average: 4000 average: 2.2 200 3 5330 2,38 3750 2.1 5726 2,58 3500 2.0 4733 2,51 3630 2.1 5219 2.61 4000 2.1 6272 2.67 4120 2.2 average: 5456 average: 2.55 average: 3800 average: 2.1

The table 18 below shows the physicomechanical properties of fiberglass based on fiberglass satin, linen and twill weave fiberglass with a diameter of 8-15 microns and a hybrid binder according to claim 1 in comparison with fiberglass prototype (fiberglass T-13 + binder by car certificate No. 1036730A).

Table 18
Physico-mechanical properties of fiberglass Indicator Name Glass fiber of VMPS 6-7.2 × 4 × 2-78 KPPN with a ratio of annular layers to axial 2: 1 Satin fiberglass T-10-80 + hybrid binder according to claim 1 Cloth fiberglass T-13 + hybrid binder according to claim 1 TSU-8/3 VM Twill Fiberglass + Hybrid Binder according to claim 1 Plastic - prototype: linen fiberglass T-13 + hybrid binder according to ed. testimonial. No. 1036730A 1 Tensile strength, MPa 848.1 650 470 450 420 after 10 years of storage in an unheated room 659 450 420 400 380 2 tensile strength in weft, MPa 825 380 290 550 230 after 10 years of storage in an unheated room 653 300 230 510 210 3 The tensile modulus of the base, GPa 27.6 26.2 24.2 23.1 23.3 after 10 years of storage in an unheated room 34.1 25.1 23.3 22.15 22.4 4 Density modulus of tensile weft, GPa 33.3 22.5 24.1 30.1 18.35 after 10 years of storage in an unheated room 27.7 24.1 24.8 31,2 17.21 5 The ultimate tensile strength in bending, MPa 801 584 540 570 550 after 10 years of storage in an unheated room 681 338 510 490 470 6 Breaking strength in a duck, MPa 735 390 310 590 250 after 10 years of storage in an unheated room 725 310 290 510 210 7 Tensile strength when shearing in layers (axial), MPa 35 40 41 39.1 38 after 10 years of storage in an unheated room 34 32,4 32.8 38,2 31 8 Tensile strength when shearing in layers (annular), MPa 34 41.2 39.5 39.5 37,2 after 10 years of storage in an unheated room 31 32,4 38.1 38.3 36.1 9 Specific gravity, g / cm ³ 1.9 1.87 1.86 1.88 1.85

Thus, the data given in tables 13, 16-18 show that all plastics based on a hybrid binder according to claim 1 of the invention significantly exceed plastic - a prototype based on fiberglass T-13 and a hybrid binder according to ed. testimonial. No. 1036730A.

The effectiveness of the use of hybrid binders according to claims 2-5 of the claims, methods for their preparation

In the prepared hybrid binder according to claim 1, add 7-18 parts by weight flame retardant: trichloroethyl phosphate, and / or carbon tetrachloride, and / or chladone, and / or hexachlorobenzene (45-90 kg of each of the flame retardants per ton of hybrid binder), mix at temperatures of 40-70 ° C for 30-60 minutes ( when loading these flame retardants, the reactor-mixer must be grounded).

The resulting hybrid binder must meet the following requirements:

a) appearance - a homogeneous solution from brown to dark brown in color, not containing inclusions and insoluble particles;

b) mass fraction of non-volatile substances,% - 57-70;

c) the density of the hybrid binder at a temperature of 20 ± 1 ° C, g / cm ³ - 0.95-1.1;

g) indicator "gelatinization time", min - 3-6.

We impregnate the tissue filler with a hybrid binder according to claims 2-5 and check for compliance with the following requirements:

a) mass fraction of binder,% - 35-57;

b) mass fraction of volatile substances and moisture,% - 1-6;

c) mass fraction of soluble binder,% - 86-92.

We produce, in accordance with the modes given in Table 14 or 15, structural products by winding or pressing from "prepregs" based on hybrid binders according to claims 2-5: hybrid binder (according to claim 1, + trichloroethyl phosphate - 7-18 parts by weight (claim 2 of the claims), a hybrid binder according to claim 1 + carbon tetrachloride CCl ₄ - 7-18 parts by weight (claim 3 of the claims), hybrid binder (according to claim .1 claims) + HFC - 7-18 parts by weight (claim 4), the hybrid binder according to claim 1 of the formula from brethenia + hexachlorobenzene - 7-18 parts by weight (claim 5 of the claims) and tissue fillers, we cut out samples from them, test them at temperatures of 20 ± 1 ° C and obtain plastic characteristics similar to those given in Tables 13, 16- 18, with the exception of:

- thermophysical properties improve - by 20-40%;

- electrostatic characteristics improve - by 10-30% (for plastics based on TEMS-k fabrics (p);

- combustibility decreases and fire resistance of plastics increases - by 10-40%;

- the rate of heat resistance according to Martenson increases - up to 850 K;

- the antistatic properties of heat-protective plastics based on hybrid binders according to items 2-5 of the claims and TEMS-k (p) fabrics are improved, these plastics practically do not accumulate static electricity charges on their surfaces;

- the thermophysical properties of plastics are improved: by thermal conductivity - by 10%, by thermal diffusivity - by 25%, by heat capacity - by 20%.

The effectiveness of the hybrid binder according to claim 6, the method for its preparation

In the prepared hybrid binder according to claim 1 of the claims, add flame retardant additives - 2-13 wt.h. freon (chlorine-containing or bromine-containing), 2-13 parts by weight hexachlorobenzene, 2-13 parts by weight antimony trioxide (for one ton of the prepared hybrid binder according to claim 1 we introduce 40-50 kg of each component), heat the mixture to temperatures of 40-70 ° C and mix at these temperatures for 30-60 minutes, then cool the mixture to temperatures of 20 ± 1 ° C.

The resulting hybrid binder must meet the following requirements:

a) appearance - a homogeneous solution from dark brown to black, not containing inclusions and insoluble particles;

b) mass fraction of non-volatile substances,% - 56-72;

c) the density of the hybrid binder at a temperature of 20 ± 1 ° C, g / cm ³ - 0.95-1.1;

g) indicator "gelatinization time", min - 3-6.

We impregnate the tissue filler with a hybrid binder according to claim 6 and check for compliance with the following requirements:

a) the mass fraction of the binder,% - 35-56;

c) mass fraction of soluble binder,% - 80-88.

According to the modes presented in table 14 or 15, we manufacture the product by winding or pressing from “prepreg” based on the hybrid binder according to claim 6 with flame retardant additives and fabric fillers by winding the “prepreg” filler onto a mandrel and curing it on a mandrel according to the mode of curing the binder, removal of the finished product and cutting samples from it with their subsequent testing. We obtain plastic characteristics similar to those presented in Tables 13, 16-18, with the exception of:

- increased fire resistance and reduced combustibility of plastic - by 10-40%;

- increases the heat resistance and thermal stability of plastic - by 5-10%;

- the physical and mechanical characteristics of plastics are reduced - by 2-5% (in comparison with Table 18);

- increased water absorption of plastic - by 1.5-2%;

- the adhesive characteristics of the binder are reduced - by 10-15%;

- the plastic shear strength is reduced by 10-15% and the gap is 15-20%;

- increases the viscosity of the binder - by 10-20%;

- increases the wear resistance and corrosion resistance;

- the manufacturability of its processing is deteriorating.

The effectiveness of the hybrid binder according to claim 7 of the claims, the method for its preparation

In the hybrid binder according to claim 1, add flame retardant additives - 12-23 wt.h. trichloroethyl phosphate and 12-23 parts by weight hexachlorobenzene and / or carbon tetrachloride (for one ton of the prepared hybrid binder according to claim 1, we introduce 40-50 kg of each of the components), heat the mixture to temperatures of 40-70 ° C and mix at this temperature for 30-60 minutes , then the mixture is cooled to a temperature of 20 ± 1 ° C.

The resulting hybrid binder must meet the following requirements:

a) appearance - a homogeneous solution from dark brown to black, not containing inclusions and insoluble particles;

b) mass fraction of non-volatile substances,% - 55-73;

c) the density of the hybrid binder at a temperature of 20 ± 1 ° C, g / cm ³ - 0.95-1.1;

g) indicator "gelatinization time" at a temperature of 180 ± 1 ° C, min - 3-6.

We impregnate the tissue filler with a hybrid binder according to claim 7 of the claims and check for compliance with the following requirements:

a) mass fraction of resin,% - 35-56;

c) mass fraction of soluble resin,% - 80-88.

According to the modes presented in table 14 or 15, we manufacture the product by winding or pressing from “prepreg” based on the hybrid binder according to claim 7 of the invention with flame retardant additives and fabric fillers by winding the “prepreg” filler onto a mandrel and curing it on a mandrel according to the mode of curing the binder, removal of the finished product and cutting samples from it with their subsequent testing. The obtained characteristics of plastics are similar to the characteristics of plastics, set forth in table 13, 16-18, with the exception of:

- increased fire resistance and reduced combustibility of plastic - by 10-40%;

- increases the heat resistance and thermal stability of plastic - by 5-10%;

- increases the wear resistance and corrosion resistance of plastics;

- the physical and mechanical characteristics of plastics are reduced - by 2-3% (in comparison with Table 18);

- increases the water absorption of plastic - by 1.5-2% (compared with table 16);

- the adhesive characteristics of the binder are reduced - by 20-40%;

- plastic shear strength decreases - by 10-15% and separation - by 20-40%;

- increases the viscosity of the binder - by 20-30%;

- the manufacturability of its processing into “prepregs” and further into structural products is deteriorating.

The effectiveness of the hybrid binder according to claim 8 of the claims, the method for its preparation

In the prepared hybrid binder according to claim 1, add flame retardant additives - 12-23 wt.h. trichloroethyl phosphate, 12-23 parts by weight hexachlorobenzene, 12-23 parts by weight carbon tetrachloride, 12-23 wt.h. antimony trioxide and 12-23 wt.h. freon (for one ton of the prepared hybrid binder according to claim 1, we introduce 40-50 kg of each of the components), heat the mixture to temperatures of 40-70 ° C and mix at these temperatures for 30-60 minutes, then cool the mixture evenly to temperatures of 20 ± 1 ° C.

The resulting hybrid binder must meet the following requirements:

a) appearance - a homogeneous solution from dark brown to black, not containing inclusions and insoluble particles;

b) mass fraction of non-volatile substances,% - 56-74;

c) the density of the hybrid binder at a temperature of 20 ± 1 ° C, g / cm ³ - 0.95-1.1;

g) indicator "gelatinization time" at a temperature of 180 ± 1 ° C, min - 3-6.

We impregnate the tissue filler with a hybrid binder according to claim 8 of the claims and check for compliance with the following requirements:

a) mass fraction of resin,% - 35-56;

c) mass fraction of soluble resin,% - 79-85.

According to the modes presented in table 14 or 15, we manufacture the product by winding or pressing from "prepreg" on the basis of a hybrid binder with flame retardant additives and fabric fillers by winding the "prepreg" filler onto the mandrel, curing it on the mandrel according to the mode of curing the binder, removal finished product and cutting samples from it with their subsequent testing. The obtained characteristics of plastics are similar to the characteristics of plastics, set forth in table 13, 16-18, with the exception of:

- increased fire resistance and reduced combustibility of plastic - by 25-40%;

- increases the heat resistance and thermal stability of plastic - by 20-25%;

- the drop in the characteristics of plastic during its aging is reduced by 7–13% (compared to Table 18);

- increases the wear resistance and corrosion resistance of plastics;

- the physical and mechanical characteristics of plastics are reduced - by 4-6% (in comparison with Table 18);

- increased water absorption of plastic - by 3-4% (in comparison with table 16);

- the adhesive characteristics of the binder are reduced - by 25-45%;

- plastic shear strength decreases - by 14-20% and separation - by 23-43%;

- increases the viscosity of the binder by 25-35%;

- the manufacturability of its processing into “prepregs” and further into structural products is deteriorating.

The effectiveness of the use of hybrid binders according to claims 9, 10 of the claims, methods for their preparation

In the hybrid binder of claim 9, copper phthalcyanines in an amount of 1-1.5 parts by weight are used as an additive.

In the hybrid binder according to claim 10 of the claims, chlorine-containing nickel compounds in an amount of 1-6 parts by weight are used as an additive.

Compounds of copper (Cu) can be introduced into the hybrid binder according to claim 9 in the form of several formations:

- in the form of copper oxide (CuO); it is the main copper oxide, representing red insoluble fine crystals, introduced into the hybrid binder as a pigment to give plastics red color, as well as giving them increased electrical conductivity, improving their antistatic, heat-shielding and other properties;

- in the form of copper oxide (Cu ₂ O); it is also the main copper oxide, which is a black finely dispersed crystals, insoluble in water. Copper oxide (Cu ₂ O) can be used to give plastics (in combination with carbon black and / or carbon-graphite mixtures and / or carbon filaments and / or powder fillers from metal oxides) electrically conductive, heating and antistatic properties. Hybrid binder based plastics according to claim 1 of the invention with additives of copper oxide can be used in large and low energy, when creating electrodes and other products used in atomic, electrical, automotive and aerospace engineering.

Copper oxide (Cu ₂ O) can be used:

- as a pigment for plastics, giving them a specific black color;

- as a filler for binders, acting in the form of conductive coatings used in homing, radar, etc .;

- in the form of some other copper compounds, for example, in the form of copper phthalcyanines (claim 9 of the claims), which simultaneously increase the heat resistance and thermal stability of plastics based on this hybrid binder. By introducing copper phthalcyanines (1-1.5 parts by weight) into the hybrid binder according to claim 9, many other properties of plastics based on it are improved: fire resistance, physical, thermophysical, electrostatic, heat-shielding, electromagnetic and other properties.

The most effective use of copper phthalcyanines in the form of carboxyphthalcyanines and / or aminophthalcyanines introduced into the hybrid binder according to claim 9 in the form of additives in the amount of 1-1.5 wt.h.

The technical result from the introduction of these additives into a hybrid binder according to claim 9 of the formula of the invention is a significant increase in the heat resistance and thermal stability of plastics based on it. In addition, the use of such a hybrid binder (with additives of copper phthalcyanines) allows one to obtain colored structural composites with enhanced technical and operational characteristics.

Tests for comparison were subjected to epoxy resin ED-20 (GOST 10587-84) of the structural formula:

Resin ED-20 at temperatures of 20 ± 1 ° C has a molecular weight of 340-430, an epoxy content of 20-22% and a dynamic viscosity of η _dyn = 16-22Pa · s

Resin ED-20 is a condensation product of diphenylolpropane with epichlohydrin in an alkaline medium. SF-340A phenol-formaldehyde resin, GOST 18694-80, was used as a hardener for ED-20 resin, copper carboxyphthalcyanines or aminophthalcyanines were used as additives.

Example 1. To obtain a hybrid binder was prepared acetone-alcohol-toluene mixture (1: 0.5: 0.1) of the following composition, in parts by weight:

Example 1a:

- epoxy resin ED-20 - 100;

- phenol-formaldehyde resin SF-340A (hardener) - 70;

- copper carboxyphthalcianine - 0.9.

Example 1b:

- epoxy resin ED-20 - 100;

- phenol-formaldehyde resin SF-340A (hardener) - 70;

- carboxyphthalcyanine copper - 1.0.

Example 1c:

- epoxy resin ED-20 - 100;

- phenol-formaldehyde resin SF-340A (hardener) - 70;

- carboxyphthalcyanine copper - 1.1.

Example 1g:

- epoxy resin ED-20 - 100;

- phenol-formaldehyde resin SF-340A (hardener) - 70;

- copper aminophthalcianine - 0.9.

Example 1d:

- epoxy resin ED-20 - 100;

- phenol-formaldehyde resin SF-340A (hardener) - 70;

- aminophthalcyanine copper - 1.0.

Example 1g:

- epoxy resin ED-20 - 100;

- phenol-formaldehyde resin SF-340A (hardener) - 70;

- aminophthalcyanine copper - 1.1.

The obtained solutions at the impregnation plant of the Central Plant Laboratory (CZL) of the Avangard FSUE were impregnated with CBM fiber and dried in air for 15-20 minutes. Then, the samples were cured in a taut state in a heating cabinet in the mode:

- at a temperature of 70 ° C - 30 min;

- at a temperature of 100 ° C - 60 minutes;

- at a temperature of 130 ° C - 60 minutes;

- at a temperature of 180 ° C - 120 minutes.

Then, the heat resistance of the samples was determined on a special device, the Paulik Erden system derivatograph (Hungary).

The heating rate of the samples in air was 5 ° C / min. Heat resistance was determined by the temperature at the onset of mass loss.

The thermal stability of the samples obtained according to the above technological regulations was determined as follows: first, the samples were kept in a heat chamber at a temperature of 200 ° C for 12 hours; then, the strength and elongation of the samples were measured by means of a dynamometer with a clamping length of the samples of 10 cm and a travel speed of 300 mm / sec.

Then, for comparison, similar tests were carried out on samples based on heat-resistant epoxy alkylresorcinol AREM-2-20, phenol-formaldehyde resin SF-340A and additives - copper or amino carboxyphthalcyanines.

Epoxy alkylresorcinol resin AREM-2-20 (TU 38-30955-78) is a condensation product of epichlorohydrin with a mixture of alkylresorcinol and flotation reagent T-65 of the structural formula:

Example 2. To obtain this hybrid binder was prepared a solution of acetone-alcohol-toluene mixture (1: 0.5: 0.1) of the following composition, in parts by weight:

Example 2a:

- epoxy alkylresorcinol resin AREM-2-20 - 100;

- phenol-formaldehyde resin SF-340A - 70;

- copper carboxyphthalcianine - 0.9.

Example 2b:

- epoxy alkylresorcinol resin AREM-2-20 - 100;

- phenol-formaldehyde resin SF-340A - 70;

- carboxyphthalcyanine copper - 1.0.

Example 2c:

- epoxy alkylresorcinol resin AREM-2-20 - 100;

- phenol-formaldehyde resin SF-340A - 70;

- carboxyphthalcyanine copper - 1.1.

Example 2g:

- epoxy alkylresorcinol resin AREM-2-20 - 100;

- phenol-formaldehyde resin SF-340A - 70;

- copper aminophthalcianine - 0.9.

Example 2d:

- epoxy alkylresorcinol resin AREM-2-20 - 100;

- phenol-formaldehyde resin SF-340A - 70;

- aminophthalcyanine copper - 1.0.

Example 2g:

- epoxy alkylresorcinol resin AREM-2-20 - 100;

- phenol-formaldehyde resin SF-340A - 70;

- aminophthalcyanine copper - 1.1.

Example 3. Further, for comparison, tests were similarly carried out on samples based on heat-resistant chloraliphatic resin brand "Oxilin 6", TU 6-02-1376-87, structural formula:

with the content of epoxy groups of 7-8%.

To obtain this binder, a solution of an acetone-alcohol-toluene mixture (1: 0.5: 0.1) of the following composition was prepared, in parts by weight:

Example 3a:

- chloraliphatic resin brand "Oxiline 6" - 97-103;

- phenol-formaldehyde resin SF-340A (hardener) - 40-70;

- solvent - 140-180;

Example 3b:

- chloraliphatic resin brand "Oxiline 6" - 97-103;

- phenol-formaldehyde resin SF-340A (hardener) - 40-70;

- solvent - 140-180;

- additive (copper carboxyphthalcianine) - 0.9-1.1.

Example 3c:

- chloraliphatic resin brand "Oxiline 6" - 97-103;

- phenol-formaldehyde resin SF-340A (hardener) - 40-70;

- solvent - 140-180;

- additive (aminophthalcyanine copper) - 0.9-1.1.

Further, the obtained solutions in examples 3a, 3b, and 3c in the CZL impregnation facility of FSUE Avangard PO were impregnated with CBM fiber and dried in air at temperatures of 20 ± 1 ° С for 15-20 minutes. Then, curing of the CBM fiber with the binder in tension was carried out in a heat chamber in the following mode:

- at a temperature of 70 ° C - 30 min;

- at a temperature of 100 ° C - 60 minutes;

- at a temperature of 130 ° C - 60 minutes;

- at a temperature of 180 ° C - 120 minutes.

Next, we tested the samples for thermal stability and thermal stability according to the previously described methods. The test results (examples 5A, 5B and 5C) in comparison with the prototype (example 4) are given in table.19.

As a prototype for comparison, we tested samples based on a binder - a prototype - according to the author. testimonial. SU No. 1036730A, cl. C 08 L 63/00, 32 V 17/04 and CBM fibers.

To obtain a hybrid binder, a solution of an acetone-alcohol-toluene mixture (1: 0.5: 0.1) of the following composition was prepared (example 4), in parts by weight:

- epoxytriphenol resin ETF - 100;

- phenolaniline formaldehyde resin FAF (hardener) - 40-70;

- acetone-alcohol-toluene solvent (1: 0.5: 0.1) - 140-180;

- additive - linear oligoester with terminal phenyl carbonate groups in an amount of 21-37% - 3.5-9.0.

The obtained solution of the prototype resin was impregnated with the CBM fiber at the TsZL impregnation facility of the Avangard Production Association Federal State Unitary Enterprise and dried in air for 15-20 minutes at temperatures of 20 ± 1 ° С. Then, the samples were cured in tension in a heat chamber according to the regime:

- at a temperature of 70 ° C - 30 min,

- at a temperature of 100 ° C - 60 minutes;

- at a temperature of 130 ° C - 60 minutes;

- at a temperature of 180 ° C - 120 minutes.

Then, the obtained samples were tested for heat resistance and thermal stability according to the previously described test modes. The test results of the obtained composition are shown in table.19.

Example 5. The inventive hybrid binder according to claim 9 was prepared as follows: epoxytriphenol ETF, epoxyaliphatic DEG-1 and phenol-formaldehyde SF- were added to an acetone-alcohol-toluene solution with an ingredient ratio of 1: 0.5: 0.1 340A resin in the following ratio, in parts by weight:

Example 5a:

- epoxytriphenol resin ETF - 97-103;

- epoxyaliphatic resin DEG-1 - 9-15;

- phenol-formaldehyde resin SF-340A (hardener) - 31-37;

- acetone - 87-93;

- ethyl alcohol - 43-49;

- toluene oil and / or coal - 7-13.

Example 5b:

- epoxytriphenol resin ETF - 97-103;

- epoxyaliphatic resin DEG-1 - 9-15;

- phenol-formaldehyde resin SF-340A (hardener) - 31-37;

- acetone - 87-93;

- ethyl alcohol - 43-49;

- toluene oil and / or coal - 7-13;

- copper carboxyphthalcianine - 0.9-1.1.

Example 5c:

- epoxytriphenol resin ETF - 97-103;

- epoxyaliphatic resin DEG-1 - 9-15;

- phenol-formaldehyde resin SF-340A (hardener) - 31-37;

- acetone - 87-93;

- ethyl alcohol - 43-49;

- toluene oil and / or coal - 7-13;

- copper aminophthalcianine - 0.9-1.1.

The obtained solutions of a hybrid binder (examples 5a, 5b, 5c) on an impregnation machine TsZL FSUE Avangard PO were impregnated with CBM fiber and dried in air at temperatures of 20 ± 1 ° C for 15-20 minutes. Then, the binder was cured together with the CBM fiber in its tensioned state in a heat chamber according to the regime

- at a temperature of 70 ° C - 30 min;

- at a temperature of 100 ° C - 60 minutes;

- at a temperature of 130 ° C - 60 minutes;

- at a temperature of 180 ° C - 60 minutes;

- at a temperature of 210 ° C - 120 minutes.

Then, the obtained samples of CBM fibers impregnated with the compositions presented in examples 5a, 5b, 5c were subjected to tests for heat resistance and thermal stability. The test results are also summarized in table 19.

Table 19
Thermal stability and thermal stability of compositions Example composition Heat resistance (temperature of the beginning of mass loss, 0.8%), ° С Thermal stability strength, kgf elongation,% strength retention 1a 260 5.80 0.92 95.3 1b 263 5.86 0.95 95.4 1c 265 6.90 0.96 95.6 1g 261 6.97 0.93 95.4 1d 264 6.80 0.94 95.6 1g 266 6.82 0.96 95.5 2a 263 6.00 0.92 95.0 2b 264 6.10 0.95 95.3 2c 265 6.30 0.96 96.0 2g 262 5.83 0.93 94.3 2d 264 6.10 0.94 95.5 2g 268 6.30 0.95 96.1 3a 255 5.70 0.93 95.2 3b 263 5.85 0.92 95.6 3c 265 6.20 0.91 96.2 4 (prototype) 253 5.65 0.92 91.0 5a 267 6.85 0.91 94.0 5 B 272 6.95 0.90 97.0 5c 275 7.00 0.89 95.0

Analysis of the test results of the samples showed that the developed hybrid binder according to claim 9 of the claims (examples: 5a - without additives, 5b - with copper carboxyphthalcyanine additives, 5c - with copper aminophthalcyanine additives) surpasses known analogues in thermal stability (examples 1-3) and the prototype (example 4) - by 5-9%, and by thermal stability - by 10-15%, which, in turn, allows to increase the operational characteristics of products made of composite fibrous materials or their weight perfection, and therefore reduce their market value ≈ by 15-20%.

In addition, the use of a hybrid binder according to claim 9 of the invention with additives of copper phthalcyanines makes it possible to obtain composites with increased atmospheric corrosion resistance, high antistatic properties (resistance to the removal of static electric charges), high electrical conductivity, and other enhanced technical and operational characteristics.

The industrial method of producing a hybrid binder according to claim 9

In the hybrid binder according to claim 1, 1-1.5 parts by weight are added. copper phthalcyanine (≈3.6-3.8 kg of copper phthalcyanine is introduced per tonne of the prepared hybrid binder according to claim 1), the resulting mixture is heated to temperatures of 40-70 ° C and mixed at these temperatures for 30-60 minutes , then the mixture is evenly cooled to a temperature of 20 ± 1 ° C.

In a hybrid binder for 97-103 parts by weight ETF epoxytriphenol resin, 9-15 parts by weight epoxyaliphatic resin DEG-1 and 31-37 parts by weight Resol phenol-formaldehyde resin SF-340A was introduced copper phthalcyanines in an amount of 1-1.5 wt.h. Two types of phthalcyanines were used as additives: copper tetra-4-aminophthalcianine and copper tetra-4-carboxyphthalcianine.

The industrial method of producing a hybrid binder according to claim 9 of the invention with additives of copper phthalcyanines: per tonne of the hybrid binder prepared according to claim 9 of the formula of the invention prepared in a mixing reactor: 365.5 kg of ETF epoxytriphenol resin, 43.8 kg of DEG-1 resin heated to temperatures of 180-200 ° C, as well as 305 kg of acetone, 170 kg of alcohol and 37 kg of toluene and all components are mixed at temperatures of 40-70 ° C for 3-6 hours, then 125 kg of finely dispersed or piece mass (with particle sizes up to 3 mm) phenolphor aldehyde resin SF-340A and mixed in a reactor-mixer with components previously introduced into it at temperatures of 40-70 ° C for 3-6 hours, then the resulting finished product is filtered off through a filter or special cloth "Excelsior", 3 is added to it, 6-3.8 kg of copper phthalcyanine (tetra-4-aminophthalcyanine or tetra-4-carboxyphthalcyanine) and its additional mixing with a hybrid binder is carried out at temperatures of 40-70 ° C for 30-60 minutes, followed by uniform cooling to 20 ± 1 ° C.

The hybrid binder according to claim 9 of the claims with copper phthalcyanines introduced into it must meet the following requirements:

a) appearance - a homogeneous solution from light brown to dark brown;

b) mass fraction of non-volatile substances,% - 50-64;

c) the density of the binder at a temperature of 20 ± 1 ° C, g / cm ³ - 0.95-1.1;

g) the indicator "gelatinization time" of the binder at a temperature of 180 ° C, min - 3-6.

The obtained solutions of the hybrid binder (examples 5a, 5b, 5c) on an impregnation machine TsZL FSUE Avangard PO were impregnated with CBM fiber and dried in air at a temperature of 20 ± 1 ° C for 15-20 minutes. Then, the hybrid binder was cured together with the CBM fiber in its tensioned state in a heat chamber according to the regime:

- at a temperature of 70 ° C - 30 min;

- at a temperature of 100 ° C - 60 minutes;

- at a temperature of 130 ° C - 60 minutes;

- at a temperature of 180 ° C - 60 minutes;

- at a temperature of 210 ° C - 120 min

and testing the samples obtained. The test results are shown in table.19.

The use in the proposed invention of modifiers - chlorine compounds of Nickel (NiL ₂ Cl ₂ ) - claim 10 of the claims, cobalt (CoL ₂ Cl ₂ ), copper (CuL ₂ Cl ₂ ) and iron (FeL ₂ Cl ₂ ), which have a set of valuable properties , allows you to conduct the curing process of a hybrid binder with uniform gas evolution with a minimum release of volatile substances at a sufficiently high technological curing rate. This allows one to obtain practically pore-free composites with the shortest possible heat-treatment cycle.

Studies were carried out on the effect of additives of complex compounds based on the ligand of 2-mercapto 5-trichloroacetylamino-1,2,3-thiadiazole and some transition metals - nickel (Ni), cobalt (Co), copper (Cu) and iron (Fe).

Note - Ligand is a mandatory component of complex compounds; in the structure of complexes it is directly related to the complexing agent, and when complexes are formed, it is a donor of electron pairs.

Studies of the effects of the above complex additives (table 20) were carried out in comparison with the hybrid binder according to claim 1 and the hybrid binder according to claim 9. In the hybrid binders according to claim 1, the following modified additives of complex chlorine-containing compounds were introduced in an amount of 1-6 parts by weight: nickel (NiL ₂ Cl ₂ ) - claim 10, and for comparison cobalt (CoL ₂ Cl ₂ ), copper (CuL ₂ Cl ₂ ) and iron (FeL ₂ Cl ₂ ), which were studied by gravimetric analysis in a thin layer of hybrid binders (claims 1, 9, 10 of the claims, etc.) in a heat chamber when the temperature rises at a rate of 2 ° C / min to a temperature of maximum cure of 200 ° C for 1 hour to a homogeneous mass. The analysis data are given in table.20.

Table 20
Thermal stability and thermal stability of the compositions of the hybrid binders according to claim 1, 9, 10 of the claims in comparison with the compositions of the hybrid binder according to claim 1 of the claims with additives: CoL ₂ Cl ₂ , CuL ₂ Cl ₂ , FeL ₂ Cl ₂ Example composition Heat resistance (temperature of the beginning of mass loss, 0.8%), ° С Thermal stability strength, kgf elongation,% strength retention 1. Hybrid binder according to claim 1 of the claims + CBM fiber 260 6.75 0.94 95.4 2. The hybrid binder according to claim 1 of the claims + NiL ₂ Cl ₂ (1-6 wt.h). + CBM fiber (hybrid binder according to claim 10) 280 6.85 0.96 98.0 3. The hybrid binder according to claim 1 of the claims + CoL ₂ Cl ₂ (1-6 wt.h). + CBM fiber (hybrid binder according to claim 10) 273 6.82 0.95 97.3 4. The hybrid binder according to claim 1 of the claims + FeL ₂ Cl ₂ (1-6 parts by weight) + CBM fiber (hybrid binder according to claim 10) 271 6.85 0.94 97.0 5. The hybrid binder according to claim 1, + CuL ₂ Cl ₂ (> 6 parts by weight) + CBM fiber (hybrid binder according to claim 10) 269 6.77 0.95 96.3 6. The hybrid binder according to claim 1 of the claims + copper phthalcyanines (1-1.5 parts by weight) + CBM fiber (hybrid binder according to claim 9) 278 6.82 0.95 98.5

Based on the data of Table 20, it can be concluded that in a thin layer of material when the hybrid binder is heated according to claim 1 (without additives) and with additives of various modifiers (claims 9, 10 of the claims, etc.) are practically non-porous are products with chlorine-containing nickel compounds (NiL ₂ Cl ₂ ) - claim 10, where L ₂ -2-mercapto 5-trichloroacetylamino-1,3,4 thiadisole.

Note - The temperature rise of the hybrid binders shown in Table 20 was carried out at a rate of 2 ° C / min (one of the most acceptable high heating rates during curing of composites based on hybrid binders prepared on acetone-alcohol-toluene solvents with an ingredient ratio of 1: 0.5: 0.1).

For the synthesis of the nickel-chlorine-nickel complex dichloro-bis-mercapto-5-trichloroacetylamino-1,3,4 thiadisole NiL ₂ Cl _{2, the} ratio of NiCl ₂ · 2H ₂ O to ligand was taken as 1: 2, i.e. 0.45 g of NiCl ₂ · 6H ₂ O and 1 g of ligand.

The ligand was dissolved in 2-3 ml of acetone, and NiCl ₂ · 2H ₂ O in 50 ml of discyclicated water, then the ligand dissolved in acetone was added in portions to the solution of nickel chloride NiCl ₂ · 6H ₂ O. The reaction product was filtered off as a yellowish powder from solution on a special filter (Schott filter), washed with distilled water, and then dried in a desiccator (a special vessel for slow drying and preservation of substances that easily absorb moisture from the air) under an extract at room temperature.

In the same way, modifiers based on CoL ₂ Cl ₂ , CuL ₂ Cl ₂ and FeL ₂ Cl _{2 were} obtained. Next, the limiting quantitative ratio of the above ingredients introduced into the hybrid binder according to claim 1 was determined.

To this end, 1-6 parts by weight were added to 25 ml of the hybrid binder with a concentration of 60-65%. the resulting complexes — chlorine-nickel (NiL ₂ Cl ₂ ), chlorocobalt (CoL ₂ Cl ₂ ), chlorinated (CuL ₂ Cl ₂ ) and chlorine-iron (FeL ₂ Cl ₂ ), the solutions were thoroughly mixed for 1-3 minutes until completely dissolved, then the solutions immersed in a glass electrolytic cell with a working electrode diameter of 1 cm and heated in a heat chamber at a speed of 2 ° C / min to a temperature of 200 ° C with exposure at this temperature to complete cure, characterized by the achievement of constant values of dielectric constant (G) and dielectric loss tangent (tg ) Is continuously measured during solidification on a special meter using parallel plate copper electrodes immersed in hybrid binder and missing to the vessel bottom ≈ 1.5 cm.

The amount of additives introduced into the formulations of hybrid binders was evaluated by the type of final products during curing according to the above regime. The experimental data are given in table 20.

As can be seen from the data of table 20 (examples 2-5), when introducing into the hybrid binder according to claim 1 the additives of complex modifiers NiL ₂ Cl ₂ , CoL ₂ Cl ₂ , CuL ₂ Cl ₂ and FeL ₂ Cl ₂ in the amount of 1 -6 parts by weight and conducting optimal modes of curing binders at a heating rate of 2 ° C / min to a temperature of 200 ° C with holding at this temperature until constant dielectric constant (G) and dielectric loss tangent (tan δ) are obtained, visually uniform, without air inclusions and pore materials.

The introduction of modifiers NiL ₂ Cl ₂ , CoL ₂ Cl ₂ , FeL ₂ Cl ₂ and CuL ₂ Cl ₂ in an amount of 1-6 wt.h. (examples 2-4 table 20) practically does not cause the formation of pores and air inclusions in plastic, and their increase in excess of 6 parts by weight (Example 5 of Table 20) causes the formation of a significant number of pores in the final curing product.

The hybrid binder according to claim 1 (without additives) when heated at a speed of 2 ° C / min to a temperature of 200 ° C also swells, that is, a low-quality curing product (highly porous) is obtained, therefore, taking into account the identified shortcomings, a new stepwise method has been developed for it curing according to the mode: first, the fibers (woven or unidirectional) after impregnation are dried in air in a taut state for 15-20 minutes, then the cured “dried” prepreg is cured in a stretched state in impregnation m Ashin in mode:

- at a temperature of 70 ° C - 30 min,

- at a temperature of 100 ° C - 60 minutes;

- at a temperature of 130 ° C - 60 minutes;

- at a temperature of 180 ° C - 120 minutes;

- at a temperature of 210 ° C - 120 minutes.

The hybrid binder according to claim 1 (without additives) when heated at a speed of 2 ° C / min to a temperature of 200 ° C is prone to swelling, and the composites obtained on its basis are of low quality, since many pores, microcracks, and delaminations form in them and other defects that reduce their quality and operational reliability.

Due to the introduction of an additive in the hybrid binder according to claim 10 of the claims, a chlorine-containing nickel compound (NiL ₂ Cl ₂ ), the mobility of molecules is almost halved in it, and therefore, its hot cure processes more uniformly without swelling at all structuring sites, which makes it possible to obtain composite materials based on this binder with improved thermophysical, electrostatic, heat-shielding and physico-mechanical characteristics, and structures based on these materials - with high quality tion and operational reliability.

The method of testing samples for thermal stability

Samples are kept in a heat chamber at a temperature of 200 ° C for 12 hours. Then their strength and elongation are measured on a dynamometer with a clamping length of 10 cm and a speed of 300 mm / min. The test results of the samples in comparison with samples based on a hybrid binder according to claim 1 of the claims are given in table 20.

An analysis of the data in Table 20 shows that the use of the proposed hybrid binder according to claim 10 with chlorine-containing nickel compounds has increased heat resistance (280 ° C) and increased thermal stability (maintaining the strength of the CBM-fiber composite binder at temperatures of 280 ° C - 98% ), which allows to increase the operational properties of products from composite fibrous materials based on a hybrid binder according to claim 10 of the claims and their operational reliability.

In addition, the use of the above hybrid binder options allows to obtain composite materials with improved characteristics - good electrical conductivity, as well as high antistatic properties and corrosion resistance.

To increase fire resistance, special chlorine-containing flame retardants: trichloroethyl phosphate, carbon tetrachloride, hexachlorobenzene and chlorine-containing freon, which slow down the burning of plastics due to endothermic effects, can be introduced into the hybrid binder according to claim 10 of the invention simultaneously with nickel-containing chlorine compounds. The gases released during this (ammonia, carbon dioxide, phosphoric and chlorine anhydrides, water vapor) also prevent combustion. The recommended amount of flame retardants additionally introduced into the hybrid binder according to claim 10 of the claims is 7-18 parts by weight. Allowed the introduction of the above flame retardants in a hybrid binder group, part of a group or one-component.

For plastics based on a hybrid binder according to claim 10 of the claims with chlorine-containing nickel compounds 1-6 parts by weight and flame retardants 7-18 wt.h. the combustion decay time after removal of the gas burner flame is not more than 3 s, and the oxygen index is 48-56%.

Such plastics have increased resistance to:

- corrosive gas environments;

- solutions of alkalis and basic salts;

- solutions of neutral and acid salts;

- solutions of sulfuric acid (H ₂ SO ₄ ) and with short-term exposure to solutions of 3% nitric (HNO ₃ ) and hydrochloric (HCl) acids.

Tests of the samples showed that the introduction of chlorine-containing compounds of Nickel in plastics over 6 wt.h. impractical, since the plastics become porous and have low separation and shear characteristics.

In addition, with increased amounts of chlorine-containing nickel compounds in plastics, many of their other properties deteriorate, in particular, their hygroscopicity, gas permeability, corrosion resistance, etc. decrease.

The hybrid binder according to claim 10 of the claims (or coatings based on it) can be most effectively used to obtain heat-protective coatings for rocket-space and aviation equipment, as well as plastic chimneys, gas exhaust trunks of blast furnaces, plastic elastic-flexible tape spirals ( UGLS) and other products from composite fibrous materials.

The effectiveness of the hybrid binder according to claim 11 of the claims, a method for its preparation

A method of obtaining a hybrid binder according to claim 11 of the claims is as follows: in the hybrid binder according to claim 1 of the claims located in the reactor-mixer, an additional amount of 0.001-0.003 wt.h. an antistatic additive in the form of an additive of the Sigbol type and is mixed with the components of the hybrid binder at temperatures of 40-70 ° C for 30-60 minutes per one ton of the product being prepared.

Sigbol additive is manufactured in accordance with TU 101741-78. It is introduced into the hybrid binder according to claim 11 of the claims to improve the electrostatic properties of plastics (their specific surface and bulk resistance) in order to give the plastics based on it improved antistatic properties.

Sigbol additive is a 32-40% solution of metal compounds of organic acids and polymer component in toluene (GOST 14710-78) or xylene (GOST 940-78).

In the hybrid binder according to claim 11, the invention proposes the use of only a solution of metal compounds of organic acids and a polymer component in toluene in an amount of 0.001-0.003 wt.h. The use of the hybrid binder according to claim 11 of the invention, a solution of these compounds in xylene is not recommended, since their introduction does not provide the required quality of the hybrid binder and plastics based on it: plastics are heterogeneous in composition, a large number of pores, microcracks, blisters and others are formed in them defects that reduce the quality of products made on the basis of this hybrid binder.

According to physico-chemical parameters, the antistatic additive "Sigbol" must meet the following requirements:

- Appearance - homogeneous dark mobile fluid;

- density at a temperature of 20 ± 1 ° C - not less than 0.9 g / cm ³ ;

- kinematic viscosity at a temperature of 80 ° C - not more than 30 cSt;

- the content of the active substance in the additive (a solution of metal compounds of organic acids and a polymer component in toluene) is 32-40%;

- content of solids - not more than 0.06%;

- water content - not more than 0.1%;

- ash content - 2.0-3.5%;

- specific electrical conductivity, pS / m:

at 0.003 parts by weight - not less than 2000,

at 0.002 parts by weight - not less than 1350,

at 0.001 parts by weight - not less than 1000,

at 0,0002 parts by weight - not less than 400.

The additive "Sigbol" in the form of additives is introduced into the hybrid binder according to claim 11 in the amount of 0.001-0.003 parts by weight; its smaller introduction does not provide the necessary effect to increase the electrostatic properties of plastics based on it, its larger introduction sharply reduces (up to 10-30%) the physicomechanical, thermophysical and physical characteristics of plastics, especially the heat-protective characteristics of plastics based on TEMS-k fabrics (p ) and a hybrid binder according to claim 11 of the claims with additives "Sigbol".

Note - Plastics based on a hybrid binder according to claim 11 of the claims and fabrics TEMS-k (p) (TU 6-06I82-85) belong to the class of antistatic materials; TEMS-k (p) fabrics are made from multicomponent complex electrically conductive threads (MKEN) - MKEN-k - nylon, MKEN-p - polyphene. These plastics belong to the class of heat-protective antistatic sublimation materials (TASM).

Recommended composition of the above TASM materials,% weight:

- fabrics TEMS-k (p) - 50-60,

- a hybrid binder according to claim 11 of the claims - 40-50.

Physical and thermophysical properties of TASM based on a hybrid binder according to claim 11 of the claims and TEMS-k (p) fabrics at temperatures of 20 ± 1 ° C:

- density, g / cm ³ - 1.21;

- water absorption within 24 hours,%, no more - 0.41;

- coefficient of thermal conductivity, W / m · K - 0.21-0.25;

- coefficient of thermal diffusivity, · 10 ⁶ , m ² / s - 0.15-0.21;

- specific heat, kJ / m · K - 0.92-1.42.

The purpose of using the hybrid binder according to claim 11 is to create plastics based on it that have high antistatic properties, heat resistance and thermal stability, as well as reduce explosion and fire safety, prepare a hybrid binder and process it into “prepregs” and further into structural products.

A method of obtaining a hybrid binder according to claim 11 of the claims is as follows:

For one ton of hybrid binder according to claim 1, which is in the reactor-mixer, an antistatic additive is added in an amount of 0.001-0.003 wt.h. in the form of additives "Sigbol" and mixed with a hybrid binder at temperatures of 40-70 ° C for 30-60 minutes, followed by uniform cooling to temperatures of 20 ± 1 ° C.

Then, the obtained composition of the hybrid binder according to claim 11 of the claims was used to impregnate tissue fillers (TEMS-k (p) and T-13 fiberglass) to obtain "prepregs" semi-finished products with the following properties:

- mass fraction of binder,% - 40-50;

- mass fraction of moisture and volatile substances,% - 3.5-5.0;

- warranty period of storage at a temperature of no more than 30 ° C, a day - 4.

Further, from the obtained "prepreg" fillers by winding or pressing methods according to the modes presented in tables 14 or 15, plastic products were made, and samples for testing were cut from them.

Introduced into the hybrid binder antistatic additive "Sigbol" (0.001-0.003 parts by weight) changes the characteristics of plastics based on it (in comparison with the characteristics of plastics based on a hybrid binder according to claim 1):

- improved electrostatic properties of plastics - by 20-30%;

- increase the heat resistance and thermal stability of plastics - by 5-10%;

- increased strength (table 13, 16-18):

tensile - by 1-2%,

for compression - by 2-5%,

on a bend - by 10%,

on interlayer separation and shift - by 15%.

The effectiveness of the hybrid binder according to item 12 of the claims, the method for its preparation

A method of obtaining a hybrid binder according to claim 12 of the claims is as follows.

In a hybrid binder according to claim 1, located in the reactor-mixer, an antistatic additive is additionally introduced in the form of ASP-1 additive in an amount of 0.001-0.005 wt.h. and mixed with it at temperatures of 40-70 ° C for 3-6 hours based on one ton of the finished product with subsequent uniform cooling to temperatures of 20 ± 1 ° C.

The purpose of the use of the ASP-1 additive is the creation of plastics on a hybrid binder according to claim 12, which have high antistatic properties, as well as high heat resistance and thermal stability. In addition, the antistatic additive ASP-1 is introduced into the hybrid binder according to claim 12 to increase its specific and volume conductivity and reduce static electrification during various technological operations of its processing.

The ASP-1 additive is a solution of chromium salts of synthetic fatty acids of the C ₁₇ -C ₂₀ fraction obtained by the double exchange reaction from synthetic fatty acids (GOST 2.3259-78) and chromium nitrate (GOST 4471-78) in BR-1 gasoline ( GOST 443-76) or any other hydrocarbon solvent with a concentration of 30 ± 5% by weight.

The quality of the additive must meet the following requirements:

- Appearance - homogeneous mobile fluid of dark green color;

- the content of the active substance in the additive,% wt., within - 30 ± 5;

- ash content,% wt., in the range of 2.0-3.5;

- content of mechanical impurities,% wt., not more than 0.2;

- the content of water-soluble acids and alkalis,% - 0.001;

- water content,% wt., not more than 0.1;

- specific volume electrical resistivity of BR-1 gasoline (GOST 443-76) with an additive content of 0.01% by weight, Ohm · m, not more than 2 · 10 ⁹ .

The hybrid binder according to claim 12 of the invention carried out the impregnation of tissue fillers (TEMS-k (p) and T-13 fiberglass) to obtain "prepregs" of semi-finished products with the following properties:

- mass fraction of hybrid binder,% - 40-50;

- mass fraction of moisture and volatile substances,% - 3.5-5.0;

warranty period of storage at a temperature of 30 ° C, a day - 4-5,

and of them, according to the processing regimes indicated in Table 14 or 15, plastic products were made by winding (Table 14) or pressing methods (Table 15), and samples for testing were cut from them.

The antistatic additive ASP-1 (0.001-0.005 parts by weight) introduced into the hybrid binder according to claim 12 claims changes the characteristics of plastics based on it (in comparison with the characteristics of plastics based on a hybrid binder according to claim 1, table 13 , 16-18):

- improves electrostatic properties of plastics - by 30-50%;

- increases the heat resistance and thermal stability of plastics - by 7-12%;

- increases strength:

tensile - by 2-3%,

for compression - by 5-6%,

on a bend - by 10-12%,

on interlayer separation and shift - by 12-20%.

The effectiveness of the hybrid binder according to item 13 of the claims, the method for its preparation

A method of obtaining a hybrid binder according to claim 13 of the claims consists in introducing an additive in an amount of 7-13 parts by weight of a hybrid binder according to claim 1, which is located in a rector-mixer, in the form of crystalline sodium aluminosilicate and its mixing with the components of the hybrid binder at temperatures of 40-70 ° C for 3-6 hours based on one ton of the finished product, followed by its filtration and cooling to temperatures of 20 ± 1 ° C.

This section discusses the effectiveness of the use of crystalline sodium aluminosilicate in a hybrid binder.

The purpose of the application is the creation of a hybrid binder and "prepregs" based on it, with high viability, as well as high physical, mechanical and thermal characteristics.

Then, with the obtained composition of the hybrid binder according to claim 13 of the claims, the tissue fillers (TEMS-k (p) and T-13 fiberglass) are impregnated to obtain “prepregs” - semi-finished products with the following properties:

- mass fraction of binder,% - 40-50;

- mass fraction of moisture and volatile substances,% - 3.5-5.0;

- warranty period of storage at a temperature of no more than 30 ° C, a day - 15-30.

Further, from the obtained “prepreg” filler by means of winding or pressing according to the modes given in Table 14 or 15, plastic products were made, and samples for testing were cut from them.

The additive in the form of crystalline sodium aluminosilicate (7-13 parts by weight) introduced into the hybrid binder according to claim 13 of the invention changes the characteristics of plastics based on it (in comparison with the characteristics of plastics based on a hybrid binder according to claim 1, table. 13, 16-18):

- improved electrostatic properties of plastics - by 10-15%;

- increase the heat resistance and thermal stability of plastics - by 5-10%;

- strengths increase:

tensile - by 1-2%,

for compression - by 2-5%,

bending - up to 10%,

on interlayer separation and shift - up to 15%;

- toughness increases - by 10-15%;

- the viability of the hybrid binder is increased by 2-3.5 times (in comparison with the hybrid binder according to claim 1).

The effectiveness of the use of a hybrid binder according to claim 14, a method for its preparation

The most effective plastics based on a hybrid binder according to claim 14 and TEMS-k (p) fabrics, having in their composition crystalline sodium aluminosilicates of 7-13 parts by weight and antimony trioxide 7-23 wt.h. Plastics of this type belong to the class of heat-shielding, antistatic and sublimating materials (TASM); in addition, these plastics have high antifriction, thermophysical, electrostatic and heat-shielding characteristics.

Table 21 below shows the heat-shielding properties of plastics based on a hybrid binder according to claim 14 and fabrics TEMS-k (p) in comparison with the prototype plastic based on a hybrid binder according to ed. testimonial. No. 1036730A and T-13 fiberglass.

Table 21
Thermal protective properties of plastics based on a hybrid binder according to claim 14 of the claims and TEMS-k fabrics (p) Name of material Density, g / cm ³ Thermal conductivity, W / m Heat capacity, kJ / kg Thermal diffusivity, m ² / s A plastic based on a hybrid binder according to claim 14 (40-50 parts by weight). and polyphene tissue TEMS-p (50-60 parts by weight) 1.78-1.9 0.282-0.285 1.16-1.19 1.3-1.41 A plastic based on a hybrid binder according to claim 14 (40-50 parts by weight). and caproamide tissue TEMS-k (50-60 parts by weight) 1.26-1.34 0.24-0.25 1.25-1.27 1.53-1.55 Hybrid Binder-Based Plastic by Auth. testimonial. 1036730A (30 parts by weight) and fiberglass T-13 (70 parts by weight) 1.48-1.6 0.26-0.28 1.2-1.4 1.3-1.5 Note - For a prototype hybrid binder according to claim 14, plastics based on a hybrid binder according to ed. testimonial. No. 1036730A according to class C 08 L 63/00, 32 V 17/04 and fiberglass T-13. The prototype binder contains 100 parts by weight. ETF resin, 40-70 parts by weight phenolaniline formaldehyde resin, 140-180 parts by weight solvent and additive - linear oligoester with terminal phenyl carbonate groups in an amount of 21-37%.

The plastic prototype is intended for the manufacture of fiberglass cylindrical shells with enhanced heat and flame retardant properties and improved electrical and electrostatic characteristics.

The introduction of oligoester in the composition of the hybrid binder of the prototype (ETF + FAF) dramatically reduces its fluidity when winding cylindrical shells with T-13 fiberglass impregnated with this binder, and, in addition, increases the life of the semi-finished product - "prepreg" (its viability) in the process storage for 30-50%.

The manufacturing technology of plastics based on fiberglass T-13 and a binder according to ed. testimonial. No. 1036730A and plastics based on TEMS-k (p) fabrics and a hybrid binder according to claim 14 are similar in technical execution, that is, the fabrics are impregnated with the aforementioned hybrid binders on a vertical impregnation machine at 90-110 ° C and a speed of 1-3 m / min (for TEMS-k tissues (p) the impregnation rate is 0.9-1.1 m / min); from an impregnated semifinished product on a horizontal winding machine, cylinders with a diameter of 50-100 mm and a thickness of 3-5 mm are wound onto a cylindrical mandrel at a winding speed of 2-4 m / min (for TEMS-k (p) fabrics, the winding speed is 1-2 m / min) , at a shaft temperature of 110-130 ° C and a pressure of the clamping shaft of 3-8 kgf / cm along the contact line of the clamping shaft and the wound product.

Modes of heat treatment of the wound cylinders on the prototype binder and on the hybrid binder according to claim 14 are close in cycles: first, the cylinders are heated in a heat chamber to temperatures of 130-140 ° C for 6 hours, then the cylinders are heated to temperatures of 180-200 ° C for 3 hours and holding at these temperatures for 18-24 hours, followed by uniform cooling of the cylinders with mandrels for 4-6 hours.

Significant technological differences in the manufacturing processes of the plastic prototype and plastics based on a hybrid binder according to claim 14:

- in the ratio of the mass fractions of hybrid binders in plastics: the mass fraction of the prototype binder is 25-40%, and the hybrid binder according to claim 14 is 40-50%;

- in different tension of the cloth fillers when they are impregnated: for fiberglass fillers impregnated with a hybrid binder according to ed. testimonial. No. 1036730A, the value of the nominal tension per 1 cm of the width of the web of material is 2-3 kgf, for fabrics TEMS-k (p) - 1-1.5 kgf.

Therefore, a hybrid binder according to ed. testimonial. No. 1036730A is used for the manufacture of structural power plastics of the SKN type (structural winding fiberglass), and the hybrid binder of claim 14 is most effective for producing TASM type heat-protective plastics with high electrostatic and heat-protective properties.

Below in table.22, 23 of this description are comparative indicators of these properties.

Table 22
The electrostatic properties of plastics based on a hybrid binder according to claim 14 of the claims and fabrics TEMS-k (p) in comparison with the prototype plastic based on a hybrid binder according to ed. testimonial. No. 1036730A and linen fiberglass T-13 Name of material σ _o ⁺ σ _about ^- σ _about τ ⁺ τ ^- τ ρ _v ρ _s K / m ² K / m ² K / m ² sec sec sec Ohm cm Ohm Plastics based on a hybrid binder according to claim 14 of the claims (40-50%) and polyphene tissue TEMS-p (50-60%) 0 about about 0 0 0 5,410 ⁴ 1.810 ⁵ Plastics based on a hybrid binder according to claim 14 (40-50%) and caproamide tissue TEMS-k (50-60%) about about 0 0 0 0 5.910 ⁴ 2.7 · 10 ⁵ Hybrid binder based plastics testimonial. No. 1036730A (25-40%) and fiberglass 0.3 · 10 ^-10 1,110 ^-10 0.7510 ^-10 eighteen 23 19.7 0.810 ¹³ 1.810 ¹³ T-13 (60-75%) - prototype Explanations:
σ _o - initial surface charge density;
σ _o ⁺ , σ _o ^- - respectively, the initial surface density of the positive and negative charges;
τ is the half-period of charge leakage (half-life of the charge);
τ ⁺ , τ ^- -, respectively, half-periods of leakage of positive and negative charges;
ρ _v is the volume resistivity;
ρ _s - surface resistivity

Table 23
Thermal protective properties of plastics based on a hybrid binder according to claim 14 of the claims and fabrics TEMS-k (p) in comparison with a prototype plastic based on a hybrid binder according to ed. testimonial. No. 1036730A and linen fiberglass T-13 Name of material Heat flow, W / m ² , at a gas flow rate of 500 m / s Average linear ablation by temperature sensor, mm / s The average speed of ablation by weight loss, mm / s Thermal resistance, sec / (kg / m ² ) ² Effective enthalpy, J / kg Sublimation temperature, ° С Plastics based on a hybrid binder according to claim 14 of the claims (40-50%) and polyphene tissue TEMS-p (50-60%) 3,510 ⁶ 0.79 0.74 2.2-2.4 2.6 · 10 ⁶ 650-700 Plastics based on a hybrid binder according to claim 14 (40-50%) and caproamide tissue TEMS-k (50-60%) 3,510 ⁶ 0.65-0.7 0.51-0.54 4.0-4.2 3.6 · 10 ⁶ 350-400 Hybrid binder based plastics testimonial. No. 1036730A (25-40%) and fiberglass T-13 (60-75%) - prototype 3,510 ⁶ 1.1-1.3 1.09-1.25 3,5-4,2 1.810 ⁶ 160-180

Thus, plastics based on a hybrid binder according to claim 14 and the TEMC-k (p) fabrics have, in comparison with the prototype:

- higher heat-shielding, electrostatic and sublimating characteristics;

- do not require special safety measures during processing and operation and provide a higher quality of the internal surfaces of structural products;

- provide a higher and longer anti-static effect.

As a result of the studies, it was found that TASM based on TEMS-p polyphene fabric and a hybrid binder according to claim 14 has a higher density and thermal conductivity than TASM based on TEMS-k caproamide tissue and a hybrid binder according to claim 14, but both types of heat-protective plastic work as sublimators and absorb a large amount of heat during decomposition, that is, they have high enthalpy (plastic based on TEMS-p fabric - 2.6 · 10 ⁶ J / kg, plastic based on TEMS-k fabric - 3.6 10 ⁶ J / kg).

Both plastics do not accumulate charges of static electricity on their surfaces and are practically related to electrically conductive materials. Both plastics are high-tech when processed into composites, shorten the manufacturing cycle of products and dramatically improve working conditions in their manufacture. They are more effective (1.5-2.5 times) in thermal, antistatic and antifriction properties than plastic prototype based on a hybrid binder according to the author. testimonial. No. 1036730A and fiberglass T-13 (GOST 19170-73). According to these indicators, they are more effective than plastics based on the heat-resistant binder grade EHD (TU 6-05-041-321-7) and fiberglass twill (TSU 8/3-VM-78), satin (T-10), linen (T- 13) and even cord (T-25VM) weaving of threads.

However, from the point of view of heat-shielding properties, composites based on TEMS-p polyphene fabric are more effective than composites based on TEMS-k caproamide fabric, since the thermal diffusivity of these composites is somewhat lower.

The nature of thermal deformations in both plastics is the same with increasing temperature, however, the thermal deformations of composites based on TEMS-k fabrics are higher than those of composites based on TEMS-k fabrics. The sublimation temperature of plastics based on TEMS-p fabrics (650-750 ° C) is about 2 times higher than that of plastics based on TEMS-k fabrics (350-400 ° C). Plastics based on TEMS-p fabrics are superior to plastics based on TEMS-k in average ablation rate: 0.74 versus 0.51.

Plastics based on TEMS-k (p) fabrics and a hybrid binder according to claim 14 are more effective than plastics based on a hybrid binder-prototype and according to antifriction properties, the coefficient of sliding friction of a pair: thermal protection coating from TAMS - antifriction coating 0,091-0,095, for plastic -prototype 2-3 times higher.

However, the physico-mechanical properties of plastics based on a hybrid binder according to claim 14 are significantly inferior to the prototype plastics based on a hybrid binder according to ed. testimonial. No. 1036730 A and T-13 fiberglass, since the breaking stress of these plastics when stretched in the direction of the base is only 125-130 MPa, the tensile modulus in the direction of the base is only 2.8-3 GPa, the breaking stress in bending is 89-90 MPa, breaking stress at crushing - 105-110 MPa, breaking stress at separation from SKN-24 fiberglass - 10.5-12 GPa, and from SKN-21 fiberglass - 6.5-10 GPa.

The above data show that plastics based on TEMS-k (p) fabrics and a hybrid binder according to claim 14 are more effective in comparison with the prototype plastic in terms of heat protection, antifriction, and antistatic properties, and less physically effective -mechanical properties, their direct purpose is to protect the internal surfaces of products: chimneys and starting pipes and other structures from the effects of heat fluxes and aggressive environments.

The method of producing a hybrid binder according to claim 14 consists of three key steps.

First, the hybrid binder according to claim 1 (the first step) is obtained by the known method described above (the first step), then it is saturated with sodium aluminosilicate vapors to obtain the hybrid binder according to claim 13 (the second step), and then this hybrid binder is introduced into the mixer reactor, add a flame-retardant additive to it - antimony trioxide in an amount of 7-23 wt.h. and mix it with the components of the hybrid binder according to item 13 of the claims at temperatures of 40-70 ° C for 3-6 hours based on one ton of the finished product, followed by uniform cooling to temperatures of 20 ± 1 ° C (third stage).

The effectiveness of the hybrid binder according to clause 15 of the claims, the method for its preparation

The hybrid binder of claim 15 has the following composition, in parts by weight:

- epoxytriphenol resin ETF - 97-103;

- epoxyaliphatic resin DEG-1 - 9-15;

- resol phenol-formaldehyde resin SF-340A - 31-37;

- acetone - 87-93;

- ethyl alcohol - 43-49;

- toluene oil and / or coal - 7-13;

- crystalline sodium aluminosilicate - 7-13;

- hexachlorobenzene - 7-23.

The most effective plastics based on a hybrid binder according to claim 15 of the claims and TEMS-k tissues (p). Plastics of this type also belong to the class of heat-protective antistatic sublimation (TASM) materials with high performance characteristics: fire-heat resistance, erosion resistance and wear resistance.

Crystalline sodium aluminosilicates included in the composition of the hybrid binder in an amount of 7-13 parts by weight increase the viability of the binder according to claim 15 in comparison with the hybrid binder according to claim 1 by a factor of 2-3.5, and the flame retardant addition of hexachlorobenzene in an amount of 7-23 parts by weight increases fire-erosion resistance, heat resistance and thermal stability of plastics based on it and TEMS-k fabrics (p).

Hexachlorobenzene (C ₆ Cl ₆ ) is a water-insoluble liquid, used in the hybrid binder according to claim 15 as an additional solvent and as a flame retardant that enhances the heat and flame retardant properties of plastics based on it.

Typically, fiberglass plastic on hybrid binders according to claim 1 (without additives) have insufficient fire resistance, for such plastics, their burning time after removal of the flame of a gas burner is 3-5 seconds, and their oxygen index is in the range 38-42%.

In foreign practice, bromine-containing resin compositions in the amount of 45-55 parts by weight are added to such binders to increase their fire resistance, in such hybrid binders the bromine content is 5-22%. However, fiberglass based on such a hybrid binder have low rates of heat resistance and thermal stability. A decrease in the bromine content in the hybrid binder leads to an increase in the thermal stability and heat resistance of fiberglass based on it, but at the same time its fire resistance decreases.

The use of rezol phenol-formaldehyde resin SF-340A allows to reduce the bromine content in plastics based on a hybrid binder according to claim 15 to 2-5% and only due to its application it is possible to increase the heat resistance and thermal stability of plastics by 10-15%.

The use in a hybrid binder according to claim 15 of the invention of rezol phenol-formaldehyde resin SF-340A as a hardener in an amount of 31-37 parts by weight allows you to increase the fire resistance of plastics based on it to a fairly high level (their oxygen index is in the range of ≈38-42%). To further increase its fire resistance, a flame retardant is introduced into it - hexachlorobenzene, which slows down the burning of plastics due to the endothermic effect during its thermal decomposition. Gases released during plastic burning (ammonia, carbon dioxide, phosphoric anhydride, water vapor, etc.) also prevent their burning.

One of the best flame retardants is boric acid H ₃ VO ₃ , the disadvantage of its introduction into a hybrid binder is that it precipitates when introduced into the resin, which complicates its processing into “prepregs” and further into structural products.

One of the best flame retardants is hexachlorobenzene, which does not give a precipitate when it is introduced into the hybrid binder according to claim 15.

Its recommended introduction is 7-23 parts by weight, its lesser introduction into a hybrid binder according to claim 15 does not give the desired effect on increasing the fire resistance of plastics, and more - it worsens the technological properties of processing a hybrid binder into "prepregs" and further into structural products winding methods.

In addition, due to the increased content of hexachlorobenzene (over 23 parts by weight), many physical and mechanical characteristics of plastics based on such hybrid binders are reduced - plastics after curing have micropores, air bubbles, microcracks and other defects that reduce their quality and operational reliability.

The most effective application of the hybrid binder according to claim 15 for the production of heat-protective plastics based on TEMS-k (p) fabrics formed from multicomponent electrically conductive caproamide or polyphene fibers assembled in a “core-shell” containing a tetrafluoroethylene copolymer with vinylidene fluoride, hexachlorobenzene, antimony trioxide and soot in the following ratios of components, in parts by weight

- a copolymer of tetrafluoroethylene with vinylidene fluoride - 50-55;

- hexachlorobenzene - 15-20;

- antimony trioxide - 10-15;

- soot - 15-20,

and in the "core" - a fiber made of polymers with a low coke number - polyphene or caproamide (kapron).

The presence of an electrically conductive filler (carbon black) in the composition of the copolymer coating of threads provides a specific surface resistance of not more than 1.0 ohms; the presence of filaments in the composition of the copolymer coating is flame retardants (hexachlorobenzene, antimony trioxide), and the formation of the filaments themselves from fibers with a low coke number (capron and polyphene) provides a high sublimation effect.

The presence of a flame retardant additive - hexachlorobenzene - in the composition of the hybrid binder according to claim 15 of the invention also increases the fire resistance of plastics based on it and TEMC-k fabrics (p). Obtained on the basis of these materials "prepregs" have the following technological characteristics, in parts by weight:

- mass fraction of the hybrid binder according to claim 15 of the claims is 40-50;

- mass fraction of tissues TEMS-k (p) - 50-60;

- mass fraction of moisture and volatile substances - 3.5-5;

- mass fraction of crystalline sodium aluminosilicates - 7-13;

- mass fraction of flame retardant - hexachlorobenzene - 7-23;

- the density of the solution of the hybrid binder according to clause 15 of the claims, g / cm ³ - 0.95-1.1.

The method and mode of manufacture of the "prepreg" TAM semi-finished product based on a hybrid binder according to claim 15 and TEMS-k fabrics (p):

- impregnation speed, m / min - 0.9-1.2;

- the temperature in the drying shafts of the impregnation machine, ° C - 130-200.

The method and processing regimes of the "prepreg" TAM semi-finished product based on a hybrid binder according to claim 15 and TEMS-k fabrics (p):

- the temperature of the heating shaft with short-term contact for no more than 3 minutes, ° C - 90-150;

- recommended rolling pressure, N / linear m - 10000-15000;

- heat treatment temperature, ° С - 120-200;

- recommended exposure time for products with wall thickness from 5 to 15 mm at heat treatment temperatures:

from 120 to 160 ° C, h - 13-20;

from 160 to 200 ° C, h - 3-8;

- the recommended rate of temperature change in the polymerization chamber during heating and cooling, ° C / h, not more than 30;

- the value of the nominal tension per 1 cm of the width of the material, kgf - 1-1.2 (for TECS-p fabrics), 1.2-1.5 (for TECS-k fabrics);

- overlap of fabrics when winding on a mandrel, mm - 10-30.

The test results of heat-protective plastics based on a hybrid binder according to claim 15 of the claims and TEMS-k (p) fabrics are presented below:

1) Physical and thermophysical properties:

- density, g / cm ³ - 1.2-1.4;

- water absorption within 24 hours,%, no more - 0.3-0.4;

- the sliding coefficient of friction of the pair: heat-resistant coating - anti-friction coating - 0,093-0,095;

- coefficient of thermal conductivity, W / m · K - 0.2-0.24;

- coefficient of thermal diffusivity, · 10 ⁶ , m ² / s - 0.14-0.18;

- specific heat, kJ / kg · K - 0.95-1.55.

2) Thermal protective and antistatic properties:

- effective enthalpy, · 10 ⁶ , J / kg - 3.25-4.1;

- the average linear ablation at a gas flow velocity of 500 m / s and a heat flux of 3.5 · 10 ⁶ W / m ² - 0.5-0.7;

- sublimation temperature, ° С - 350-750;

- thermal resistance, sec / (kg / m ² ) ² - 2.5-4.3;

3) Electrostatic characteristics:

- specific surface resistance, · 10 ⁵ , Ohm - 1.8-2.7;

- specific volume resistance, · 10 ⁴ , Ohm · cm - 5.2-6.0.

4) Physico-mechanical characteristics of plastics at temperatures of 20 ± 1 ° C:

- ultimate tensile stress in the direction of the base, MPa (kgf / mm ² ) - 130-145 (13-14.5);

- modulus of tensile elasticity in the direction of the base, GPa (kgf / mm ² ) - 2.87-3.0 (287-300);

- breaking stress in bending, MPa (kgf / mm ² ) - 920-950 (9.2-9.5);

- breaking stress during crushing, MPa (kgf / mm ² ) - 109-112 (10.9-11.2);

- breaking stress at separation, GPa (kgf / mm ² ):

from structural fiberglass SKN-21 - 7.0-10.2 (70-102);

from structural fiberglass SKN-24 - 10.8-15.0 (108-150);

- density, g / cm ³ - 1.25-1.32 (for TEMS-k fabrics), 1.79-1.81 (for TEMS-p fabrics).

5) Gas evolution products from plastics at operating temperatures:

at 20 ± 5 ° С - ethyl alcohol, acetone, toluene;

at 50 ± 5 ° С - ethyl alcohol, butyl alcohol, acetone, toluene, phenol, aniline, formaldehyde, epichlorohydrin.

The method for producing a hybrid binder according to claim 15 consists of three key steps.

First, the hybrid binder according to claim 1 (the first step) is obtained by the known method described above (the first step), then it is saturated with sodium aluminosilicate vapors to obtain the hybrid binder according to claim 13 (the second step), and then this hybrid binder is introduced into the mixer reactor, add to it a flame-retardant additive - hexachlorobenzene in an amount of 7-23 parts by weight and mix it with the components of the hybrid binder according to item 13 of the claims at temperatures of 40-70 ° C for 3-6 hours based on one ton of the finished product, followed by uniform cooling to temperatures of 20 ± 1 ° C (third stage).

The effectiveness of the hybrid binder according to clause 16 of the claims, the method for its preparation

Hybrid binder plastics according to claim 16 and TEMC-k (p) fabrics additionally contain crystalline sodium aluminosilicates of 7-13 parts by weight, as well as carbon tetrachloride and / or freon, 7-23 parts by weight.

Plastics of this type also belong to TASM, that is, heat-protective antistatic sublimation materials.

Crystalline sodium aluminosilicates are used in the hybrid binder according to claim 16 as adsorbents; they increase the viability of the hybrid binder by 2-3.5 times.

Carbon tetrachloride and / or chladone are included in this hybrid binder as flame retardants, slowing down the combustion of plastics due to endothermic effects during their thermal decomposition, as well as due to the release of ammonia, carbon dioxide, water vapor, chloride, fluoride and phosphoric anhydrides and other gas emissions.

Carbon tetrachloride (CCl ₄ ) - flame retardant, is introduced into the hybrid binder according to clause 16 of the claims to increase the fire resistance of plastics based on it. Its introduction into a hybrid binder in an amount of 7-23 parts by weight increases the oxygen index of plastics based on this binder up to 40-45%, thereby increasing their fire-resistance by 10-20% in comparison with plastics formed on the basis of a hybrid binder according to claim 1 and TEMS-k fabrics (p) .

Plastics on such a binder have low heat resistance and thermal stability. To increase these indicators, in addition to the carbon tetrachloride according to clause 16 of the claims, freon of the grades Ф114В _{1,2 is} introduced. Freons can be introduced into the hybrid binder according to claim 16 in a ratio of 1: 1 to 1: 0.1 and without carbon tetrachloride. Their joint introduction into a hybrid binder according to claim 16 of the claims increases the fire resistance of plastics based on it and TEMS-k (p) fabrics by 10-15%, and heat resistance and thermal stability by 5-10%.

The introduction into the hybrid binder according to claim 16 of the claims only freon grades F 114B _1.2 increases the fire resistance of plastics based on it by 15-20%, and the oxygen index of such plastics is in the range of 50-52%. The burning time of such plastics after the removal of the flame of a gas burner is no more than 3 seconds. It should be noted that in the hybrid binder according to claim 16, two types of fluorine-containing freons can be introduced: a Freon brand Ф114B ₁ , which contains bromine molecules, and then a bromine-containing Freon C ₂ Br ₂ F _{4 is formed} , and a Freon brand H114B ₂ , which contains chlorine molecules, and then a chlorine-containing freon C ₂ Cl ₂ F _{4 is formed} .

Both brands of chladones are introduced into the hybrid binder according to claim 16 with the aim of increasing the fire-erosion resistance of plastics to heat fluxes of 3.5 · 10 ⁶ W / m and flow rates of 500 m / s.

Both types of chladones can be introduced into the hybrid binder according to claim 16 together, in groups with a ratio of components from 1: 1 to 1: 0.1 or component-wise, that is, with the introduction of only Freon C ₂ Br ₂ F ₄ , or Freon C ₂ Cl ₂ F ₄ .

The introduction of bromine-containing freon in the amount of 7-23 wt.h. it allows significantly - up to 30% or more to increase the fire resistance of plastics of this type, and at the same time increase their heat resistance and thermal stability by 10-15%.

The introduction into the hybrid binder according to clause 16 of the claims of chlorine-containing freon can increase the heat resistance and thermal stability of plastics based on it by 30-50% and at the same time maintain their fire resistance at a sufficiently high level.

The oxygen index of plastics based on a hybrid binder according to clause 16 of the claims with additives C ₂ Br ₂ F ₄ - 52-54%, and with additives C ₂ Cl ₂ F ₄ - 51-53%. Combustion decay time for plastics based on a hybrid binder with C ₂ Br ₂ F ₄ additives — after removal of the gas burner flame from them, is within 1-2 seconds, and for plastics on a hybrid binder according to claim 16 with C ₂ Cl additives ₂ F ₄ - 2-3 sec.

At the same time, the thermophysical, electrostatic, sublimating and heat-shielding properties of plastics are kept at a high level; these properties are at the level of characteristics achieved in plastics formed on the basis of hybrid binders according to claims 13-15 of the claims and TEMS-k fabrics (p).

However, plastics of this composition have significant disadvantages:

- water absorption in such plastics within 24 hours - 0.2-0.6%;

- coefficient of friction-slip of a pair: heat-proof coating - anti-friction coating - 0,095-0,096;

- ultimate breaking stresses are reduced when separated from fiberglass type SKN-24 - by 10-15%, from fiberglass type SKN-21 - by 15-20%.

In addition, plastics of this composition are less reliable from the point of view of their long-term storage and operation, since they have higher hygroscopicity and gas permeability. The presence in the hybrid binder of claim 16 of aluminosilicates in excess of 23 parts by weight slows down the curing of plastics based on this binder and TEMC-k (p) fabrics, leads to an increase in the viscosity of the hybrid binder and the technological difficulties of its processing into “prepregs” and further into structural products.

The method for producing a hybrid binder according to claim 16 consists of three key steps.

First, the hybrid binder according to claim 1 (the first step) is obtained by the known method described above (the first step), then it is saturated with sodium aluminosilicate vapors to obtain the hybrid binder according to claim 13 (the second step), and then this hybrid binder is introduced into the mixer reactor, add to it a flame retardant additive - hexachlorobenzene and / or freon in an amount of 7-23 parts by weight and mix it with the components of the hybrid binder according to item 13 of the claims at temperatures of 40-70 ° C for 3-6 hours based on one ton of the finished product, followed by uniform cooling to temperatures of 20 ± 1 ° C (third stage).

The effectiveness of the hybrid binder according to claim 17, a method for its preparation

Crystalline sodium aluminosilicates 7-13 parts by weight and flame retardant additive 7-23 wt.h. - trichloroethyl phosphate - are introduced into the hybrid binder according to claim 17 with the aim of:

- increase the fire-erosion resistance of composites based on it;

- increase the corrosion resistance of plastics based on it;

- improving the thermophysical and heat-shielding properties of plastics based on it and TEMS-k fabrics (p);

- increase the viability of the hybrid binder and the manufacturability of its processing into "prepregs" and further into structural products.

In accordance with the goal, 7-13 parts by weight of the hybrid binder according to claim 17 are introduced. crystalline sodium aluminosilicate and 7-23 wt.h. trichloroethyl phosphate.

Trichloroethyl phosphate (TCEP) - С ₂ Cl ₃ Н ₄ PO ₄ - flame retardant additive, formed on the basis of salts of phosphoric acid; TCEP - an unsaturated chlorine-containing hydrocarbon, a water-insoluble liquid, is introduced into the composition of the hybrid binder according to claim 17 in the following ratio of components, in parts by weight:

- epoxytriphenol resin ETF - 97-103;

- epoxyaliphatic resin DEG-1 - 9-15;

- resol phenol-formaldehyde resin (hardener) SF-340A - 31-37;

- acetone - 87-93;

- ethyl alcohol - 43-49;

- toluene oil and / or coal - 7-13;

- crystalline sodium aluminosilicate - 7-13;

- trichloroethyl phosphate - 7-23.

Introduction to the hybrid binder according to claim 17 of the claims of the above components allows you to maximize the advantages of each of them and at the same time avoid their inherent disadvantages.

Of particular importance for the production of wound plastics is the ETF epoxytriphenol resin. Due to its low molecular weight (300-600), ETF resin is a viscous liquid at ordinary temperature, which is especially important in the technology of forming large-sized large-tonnage products from composite fiber materials manufactured by Avangard FSUE.

Having a high content of epoxy groups (13-27%), this resin is reactive and can be cured in the presence of an amine type hardener, for example, polyethylene polyamine - H ₂ N (CH ₂ CH ₂ NH) _n H, where n = 1,5, used for cold curing of epoxy resins with a minimum release of volatile products from them (up to 2.5%).

Lateral hydroxyl groups in the ETF resin molecule allow one to realize another mechanism of its curing, for example, when using rezol phenol-formaldehyde resin SF-340A as a hardener. Hot curing allows you to get a more durable and tough product.

Table 24 below shows the main characteristics of cold and hot cured ETF epoxy resin.

Table 24
The main characteristics of epoxytriphenol resin ETF cold and hot curing Indicator Name ETF Binder cold curing (hardener - polyethylene polyamine) hot curing (hardener - resin SF-340A) Density, g / cm ³ 1.1-1.23 1.2-1.27 Destructive stress, MPa:
- in tension
- during compression
- when bending
35-70
110-130
60-100
70-100
130-160
90-130 Elongation at break,% 3-6.5 1.2-4.0 Impact strength, kJ / m ² 2.9-10.8 3.9-24.5 Operating temperature for continuous operation, K 450 500 Heat resistance, K
- by WIKA
- according to Martens
660-695
383-450
770-850
390-550 The viability of the prepared binder less than a day up to 6 months Tensile modulus, GPa 1.5-1.9 1.9-4.9 Shear modulus, GPa 0.12-0.14 0.15-0.19 Poisson's ratio 0.13-0.14 0.14-0.27 Hardness, MPa - 2.45-196 Shrinkage during curing,% 2,5 0.5-3.6 Water absorption,% 1,5-5 0.03-0.5 Thermal diffusivity, m ² / g - (0.1-4) · 10 ³ Specific heat, kJ (kg · K) - 0.46-2.93 The coefficient of thermal conductivity, W / m · K - 0.17-0.92 The coefficient of thermal expansion · 10 ³ , K ^-1 - 3-12 Volume resistivity, Ohm · m - (5.5-6) · 10 ⁴ Surface resistivity, Ohm - 1.610 ¹³ Thermal resistance, sec / (kg / m ² ) ² - 2.5-4.5 Dielectric constant at 10 ⁶ Hz - 2.4-6.0 Dielectric loss tangent at 10 ⁶ Hz - 0.00015-0.05 Viscosity, Pa · s - 1-5

The disadvantages of ETF epoxytriphenol resin: the resin has high viscosity, insufficiently high heat resistance (180-200 ° C) and water resistance (0.4-0.5%), as well as low fire resistance (oxygen index 38-42%).

To reduce the viscosity of the ETF resin and improve its impregnation of tissue fillers, an ETF resin (97-103 parts by weight) is introduced into the ETF resin - epoxyaliphatic resin DEG-1 (9-15 parts by weight); this resin is a low viscosity liquid with a viscosity of 0.1-0.2 Pa · s; DEG-1 resin contains 19-29% of epoxy groups, has a molecular weight of 240-320, is very well compatible with ETF resin, hydrocarbon solvents (acetone, alcohol, toluene, etc.), fillers from metal oxides and nitrides, and carbon-graphite fillers.

Other advantages of the mixture of resins ETF + DEG-1:

- the mixture has high stability, practically does not change its properties even under conditions of long-term (up to 3 years) storage;

- the mixture is cured according to the "polymerization" scheme, in which no by-products are emitted;

- the mixture has an optimal viscosity (0.1-1 Pa · s), when controlling the viscosity with a B3-4 viscometer, this corresponds to 15-85 s.

A mixture of ETF + DEG-1 resins with such viscosity easily fills pores (cells) with a diameter of 5-6 microns. The viscosity of the resin mixture required during winding can be ensured by concomitant winding heating, the temperature of which for different resin compositions is 232-353 K, and can be maintained by the temperature control system of the impregnating bath with an accuracy of ± 5 K.

The viability of the ETF + DEG-1 resin mixture depends on the viscosity, which can change during the winding process due to the structuring process, and its initial value depends on the cooking time and storage conditions. These factors should be taken into account when working out the technological regulations for its processing into “prepregs”.

Especially strongly on the viability of the resin mixture has a temperature. For a mixture of resins ETF (103 parts by weight), DEG-1 (15 parts by weight) and SF-340A (37 parts by weight), this dependence is as follows:

Temperature, K 293 313 353 393 413 Temperature ° C twenty 40 80 120 140 Viability 6 days 3 days 120 min 15 minutes 8 min

Thus, careful control of the temperature of the hybrid binder is one of the ways to maintain its optimal viscosity and, consequently, the quality of the impregnation.

Heating the hybrid binder within its operating temperature (40-70 ° C) significantly improves the impregnation even with lower amounts of hybrid binder applied to the reinforcement, which allows some control of the volumetric content of the fibrous filler in the composition. As hardener of the mixture of ETF-DEG-1 resins in the hybrid binder according to claim 17, the rezol phenol-formaldehyde resin SF-340A was used, which is well compatible with ETF and DEG-1 resins with a minimum phenol and aniline content of up to 4% (Table 7) .

Under the conditions of FSUE PA Avangard, that is, under the conditions of industrial production of plastics, the optimum amount of hardener should be: up to 10% for cold cured resins, up to 40% for hot cured resins.

A more accurate amount of hardener - SF-340A resin (31-37 parts by weight) introduced into the mixture of ETF + DEG-1 resins was determined in the process of testing the manufacturing technology for specific products: chimneys and launch tubes, containers, tanks, elastic flexible tape spirals (UGLS) and others. It was assumed that an excess of SF-340A resin (more than 37 parts by weight) does not lead to faster or more complete curing of the resin mixture, but causes corrosion of metals, reduces the water resistance and heat resistance of the composites obtained on their basis. The lack of resin SF-340A (less than 31 parts by weight) slows down the curing process of the hybrid binder according to claim 17 or completely stops it. It is already impossible to introduce additionally or withdraw excess hardener, which is why the dosage accuracy of the introduced hardener - resin SF-340A should be high and be in the range of 31-37 parts by weight.

The efficiency of the curing process of the hybrid binder increases significantly when, along with the hardener (resin SF-340A), other chemically active substances are added - crystalline sodium aluminosilicates (7-13 parts by weight), which act as initiator and catalyst of the reaction and affect the speed and depth of the process curing.

The discussion given here about the accuracy of the dosage of the added additives is valid for almost all compositions of the hybrid binder according to claims 1-38 of the claims, and especially for compositions according to claims 13-18, 29-38 of the claims.

Crystalline aluminosilicates introduced into the hybrid binder according to claims 13-18 of the invention act as molecular sieves. Their introduction into the hybrid binder can be carried out both by direct mixing with the hardener resin SF-340A, and by pre-saturation of the ETF and DEG-1 resins with pairs of adsorbed hardener. Molecular sieves of the N-zeolite type (or sodium aluminosilicates) increase the viability of hybrid binders according to claims 13-18 and 29, 32, 35, where finely dispersed alumina powder (claim 32) or whiskers are used as molecular sieves crystals (p. 35 claims).

The hybrid binder according to claim 17 of the claims without a flame retardant additive - trichloroethyl phosphate, has low fire resistance, the oxygen index of such a binder is in the range of 45-50%, the addition of a flame retardant additive in the form of trichloroethyl phosphate in the amount of trichloroethyl phosphate in the hybrid binder according to claim 17 7-23 parts by weight increases the fire resistance of composites based on it by 10-20%, the oxygen index (CI) characterizing the fire resistance of materials is already in the range of 51-55%.

In addition, the introduction of trichloroethyl phosphate in the hybrid binder according to claim 17 reduces its viscosity, i.e., a hybrid binder with a flame retardant additive (trichlorethyl phosphate) becomes a low viscosity binder with a viscosity of up to 0.1-1 Pa · s, which contributes (in addition to the viability of the hybrid binder) to increase the manufacturability and economy of production, the curing process of such a hybrid binder can occur according to the "polymerization" scheme, in which no by-products are emitted. In addition, the "polymerization" of the hybrid binder according to claim 17 with trichloroethyl phosphate additives can take place at sufficiently low pressures (0.1-0.5 MPa) and in plastic materials based on the hybrid binder according to claim 17 and during "polymerization" of tissue fillers, pores, cracks and other defects that reduce their strength do not appear in plastics.

The main method of curing the hybrid binder according to claim 17 is a thermochemical. Thermochemical curing of plastics is usually carried out by convectively heating them in furnaces, most often in electric, autoclaves, by contact heating in molds heated by heating elements - thermoelectric heaters, as well as gaseous and / or liquid heat carriers.

The intensification of the thermochemical curing method, for example, the evacuation of a cured product, allows to improve not only the properties of the material obtained (increase the strength by 10-15%, reduce the dispersion of strength values by 40-50%, reduce the porosity by 2 times), but also the technological characteristics of the process: reduce the curing temperature by 30-50 ° C and reduce the duration of the curing process by 0.5-1 hours. More actively, the processes of thermochemical curing of hybrid binders according to claims 13-38 of the claims can be intensified under the influence of a magnetic field with a strength of 120-1100 E.

The most effective is the use of a hybrid binder according to claim 17 for obtaining heat-protective plastics based on TEMC-k fabrics (p). This hybrid binder contains (unlike the hybrid binder according to claim 1) crystalline sodium aluminosilicates (7-13 parts by weight) and trichloroethyl phosphate (7-23 parts by weight).

Sodium aluminosilicates are used in this composition of the hybrid binder to increase its viability (in comparison with the composition according to claim 1) by about 2-3.5 times, and trichloroethyl phosphate - to increase the fire resistance of plastics based on the hybrid binder according to claim 17 and fabrics TEMS-k (p), as well as improving their heat resistance, thermal stability and processability of processing.

Trichloroethyl phosphate is a flame retardant, a fluid with a viscosity of 0.1-1 Pa · s, a drug that protects plastics based on a hybrid binder according to claim 17 from self-ignition and self-combustion. The most effective is the use of trichloroethyl phosphate and sodium aluminosilicates as part of a hybrid binder according to claim 17 for the preparation of plastics based on it and TEMC-k fabrics (p).

These fabrics, consisting of nylon and polyphene filaments, are coated with a copolymer of tetrafluoroethylene with vinylidene fluoride (40-55 parts by weight)., Containing in its composition: hexachlorobenzene (15-20 parts by weight), antimony trioxide (15-20 parts by weight) .) and soot (15-20 parts by weight).

Impregnated with the heat-resistant hybrid binder according to claim 17 of the claims (with trichloroethyl phosphate and aluminosilicates of the composition Al ₂ O ₃ + SiO ₃ in ratios from 1: 1 to 1: 0.1), these fabrics form heat-protective plastics with high sublimation during processing (effective enthalpy - (3.5-4.5) · 10 ⁶ J / kg, electrostatic (specific surface resistance (2.5-3.6) · 10 ⁵ Ohm, specific volume resistance (5.6-6.2) · 10 ⁴ Ohm · cm) and heat-refractory (oxygen index 55-60%) properties.

These materials absorb a large amount of heat during decomposition and, in addition, effectively protect products made from composite fibrous materials from the appearance and accumulation of static electricity charges on their surfaces that occurs during their operation.

Plastics based on a hybrid binder according to claim 17 of the claims and TEMC-k (p) tissues have the following properties:

- they are technological in the manufacture, molding of coating materials is carried out by winding methods of manufacturing technology of power shells of products (table 14) or by pressing methods (table 15);

- they guarantee stable geometric dimensions of the products (with an accuracy of ± 0.1-0.25 mm), since their dimensions are provided only by the number of layers and the geometry of the technological equipment;

- they have a long-term antistatic effect (up to 25 years) at operating temperatures of ± 50 ° C and relative humidity up to 98%;

- they retain an antistatic effect under various operating conditions;

- they are resistant to ultraviolet, ultrasonic, electromagnetic, radiation and microwave radiation;

- they are resistant to water, various aggressive environments (acids, alkalis, sea water, etc.), various hydrocarbon solvents, oils, lubricants, oil products, as well as DDD (degassing, deactivating and disinfecting) and explosives (fire).

The presence of trichlorethylphosphate, hexachlorobenzene, antimony trioxide, as well as polyphene and / or kapron fibers with a low coke number and carbon black in the composites based on the hybrid binder according to claim 17 and the TECS-k (p) fabrics provides materials with a high sublimating effect.

The sublimation temperature for plastics based on TEMS-k fabrics and a hybrid binder according to claim 17 is 650-800 ° C, and for plastics based on TEMS-k fabrics and a hybrid binder according to claim 17 is 350-450 ° C .

In addition, such plastics have high physical, thermophysical, electrostatic and heat-shielding properties (Tables 25, 26), and during operation have insignificant gas emissions: at 20 ± 5 ° C - ethyl alcohol, acetone; at 50 ± 5 ° С - ethyl alcohol, butyl alcohol, acetone, formaldehyde, phenol, epichlorohydrin, aniline.

Table 25
Physical and thermophysical properties of plastics based on a hybrid binder according to claim 17 of the claims and TEMS-k (p) fabrics at temperatures of 20 ± 1 ° С Name of characteristic Characteristic Value Hybrid binder based plastics according to claim 17 of the claims (40-50 parts by weight) and TEMS-p polyphene fabric (50-60 parts by weight) Plastics based on a hybrid binder according to claim 17 of the claims (40-50 parts by weight) and caproamide tissue TEMS-k (50-60 parts by weight) Density, g / cm ³ 1.7-1.82 1.27-1.31 Water absorption within 24 hours,%, no more 0.3 0.4 Pair sliding friction coefficient: heat-proof coating - anti-friction coating 0,092 0,094 The coefficient of thermal conductivity, W / m · K 0.19-0.23 0.18-0.19 The coefficient of thermal diffusivity, · 10 ⁶ , m ² / s 0.12-0.13 0.13-0.17 Specific heat, kJ / kg · K 0.91-1.36 0.89-0.9

Table 26
Thermal protective and antistatic properties of plastics based on a hybrid binder according to claim 17 of the claims and TEMS-k fabrics (p) Name of characteristic Characteristic Values Hybrid binder based plastics according to claim 17 of the claims (40-50 parts by weight) and TEMS-p polyphene fabric (50-60 parts by weight) Plastics based on a hybrid binder according to claim 17 of the claims (40-50 parts by weight) and caproamide tissue TEMS-k (50-60 parts by weight) Effective enthalpy, · 10 ⁶ , J / kg 2.5-2.8 3,5-4,2 The average linear ablation at a gas flow velocity of 500 m / s and a heat flux of 3.5 · 10 ⁶ W / m ² , mm / s 0.6 0.5 Sublimation temperature, ° С 700-800 350-450 Thermal resistance, sec / (kg / m ² ) ² 2.3-2.7 4.1-4.3 Surface resistivity, · 10 ⁵ , Ohm 1.7-1.9 2.6-2.8 The specific volume resistance, · 10 ⁴ , Ohm · cm 5.3-5.4 5.8-6.1

Conclusions and recommendations

The materials based on the hybrid binder according to claim 17 and the TEMC-k (p) fabrics can be attributed to:

- to the class of heat-protective antistatic sublimation materials (TASM), since they absorb a large amount of heat during decomposition and do not accumulate on their surfaces during the operation of charges of static electricity;

- more technological in processing into composites by winding methods;

- more effective in heat-shielding and antistatic properties than a plastic prototype based on a hybrid binder according to ed. testimonial. No. 1036730A and fiberglass T-13;

- on the surfaces of both plastics based on TEMS-k (p) fabrics and a hybrid binder according to claim 17, no charges of static electricity accumulate - the electric charge disappears from the surfaces of these plastics before it can be determined, that is, these plastics can be attributed to the class of antistatic polymers;

- both materials are biocomponent composites, they are biostable, resistant to almost all radiation (except for radiation and microwave radiation);

- both materials have high corrosion and wear resistance, and are resistant to the effects of DDD, OV, sea water, acids, alkalis, almost all hydrocarbon solvents, as well as oils, lubricants, antistatic additives such as ASP-1 and Sigbol and other aggressive wednesday

However, both materials have low physical and mechanical characteristics:

- ultimate tensile stress in the direction of the base, MPa (kgf / mm ² ) - 130-160 (13-16);

- modulus of tensile elasticity in the direction of the base, GPa (kgf / mm ² ) - 3.0-3.2 (300-320);

- destructive stress during bending, MPa (kgf / mm ² ) - 100-120 (10-12);

- destructive stress during crushing, MPa (kgf / mm ² ) - 110-130 (11-13);

- breaking stress at separation, GPa (kgf / mm ² ):

from structural fiberglass SKN-21 - 10-15 (100-150),

from structural fiberglass SKN-24 - 15-20 (150-200);

- the temperature of the onset of intense distraction, ° C - 300-800;

- temperature of long-term operation, ° C - 250-350.

The plastics based on the hybrid binder according to claim 17 and the TEMS-k (p) fabrics practically do not reduce their physical, mechanical and thermophysical characteristics for 10 years (when stored in a heated room) and for 3 years (under unheated premises). A decrease in the heat-shielding properties of plastics during long-term storage was noted by 10-15%, electrical and electrostatic properties by 15-20%, and interlayer shear and tear strengths by 10-20% and 25-30%, respectively.

The warranty period of operation of such plastics at temperatures ± 50 ° С and relative humidity up to 98% is 20 years. Plastics of this type are recommended by the applicant - FSUE PO Avangard as heat-protective wear-corrosion-resistant materials for protecting the internal or external surfaces of glass-carbon-boron-organoplastics from high-temperature gas-dynamic heating, the accumulation of static electricity and exposure to aggressive environments.

The method for producing a hybrid binder according to claim 17 consists of three key steps.

First, the hybrid binder according to claim 1 (the first step) is obtained by the known method described above (the first step), then it is saturated with sodium aluminosilicate vapors to obtain the hybrid binder according to claim 13 (the second step), and then this hybrid binder is introduced into the mixer reactor, add to it a flame retardant additive - trichloroethyl phosphate in the amount of 7-23 parts by weight and mix it with the components of the hybrid binder according to item 13 of the claims at temperatures of 40-70 ° C for 3-6 hours based on one ton of the finished product, followed by uniform cooling to temperatures of 20 ± 1 ° C (third stage).

The effectiveness of the hybrid binder according to claim 18, a method for its preparation

The hybrid binder according to claim 18 differs from the main hybrid binder according to claim 1 by the added additives: crystalline sodium aluminosilicate - 7-13 parts by weight (introduced into the hybrid binder to increase its viability) and a whole group of flame retardants consisting of hexachlorobenzene (2-13 parts by weight), trichloroethyl phosphate (2-13 parts by weight), carbon tetrachloride (2-13 parts by weight) antimony trioxide (2-13 parts by weight) and freon (2-13 parts by weight).

The most effective use of the hybrid binder according to claim 18 for the production of TEMS-k (p) heat-protective antistatic sublimation materials (TASM) based on it and fabrics, since they are in their composition (in a coating copolymer of tetrafluoroethylene with vinyl fluoride (50-55 wt. .h.) of polyphene and kapron filaments) contains an additional group of flame retardants consisting of hexachlorobenzene (15-20 parts by weight), antimony trioxide (10-15 parts by weight) and soot (15-20 parts by weight). Polyphene and kapron fibers form the "core" of polymer filaments with a low coke number.

The presence of an electrically conductive filler - soot in the composition of composites based on a hybrid binder according to claim 18 and TEMS-k (p) fabrics provides plastics with high electrostatic characteristics (specific surface resistance - 1.9-3.5 · 10 ⁵ Ohms and high specific volume resistance - 6-6.5 · 10 ⁴ Ohm · cm).

The presence of flame retardants in the composites: hexachlorobenzene, trichloroethyl phosphate, carbon tetrachloride, antimony trioxide, chladone and fibers with a low coke number - from capron and polyphene - provides plastics with a high sublimation effect (effective enthalpy for plastics based on a hybrid binder according to claim 18 and TEMS-p fabrics - 3.5 · 10 ⁶ J / kg, sublimation temperature - 750-800 ° С; effective enthalpy for plastics based on a hybrid binder according to claim 18 and TEMS-k fabrics - 4.5 · 10 ⁶ J / kg, temperature su limatsii - 350-450 ° C).

The above composites also have high fire resistance: the oxygen index for plastics based on TEMS-p fabrics and a hybrid binder according to claim 18 is 57-59%, for plastics based on TEMS-k fabrics and a hybrid binder according to claim 18 55-57%.

In addition, the introduction of hexachlorobenzene, trichloroethyl phosphate, carbon tetrachloride and chladone in 2-13 wt.h. each type of flame retardant reduces the viscosity of the hybrid binder to 0.1-0.5 Pa · s and improves its technological properties: adhesion to the fibers, their good wettability, and also increases shear (by 20-30%) and tear-off (by 30-40 %) characteristics of plastics based on TEMC-k (p) fabrics and a hybrid binder according to claim 18.

The double addition of antimony trioxide (2-13 parts by weight in a hybrid binder according to claim 18 and 10-15 parts by weight as a part of the coating of polyphene or kapron fabrics TEMS-k (p) - allows to increase the wear and corrosion resistance plastics based on a hybrid binder according to claim 18, as well as to improve their antifriction properties (pair sliding friction coefficient: thermal protection coating based on TEMS-k fabrics (p) - antifriction coating - 0.089-0.96).

Plastics of this composition have high physical, thermophysical, heat-shielding, sublimating and antistatic properties, which are at the level of plastic indicators based on the hybrid binder according to claim 17 (Tables 25, 26).

The method for producing the hybrid binder of claim 18 consists of three key steps.

First, the hybrid binder according to claim 1 (the first step) is obtained by the known method described above (the first step), then it is saturated with sodium aluminosilicate vapors to obtain the hybrid binder according to claim 13 (the second step), and then this hybrid binder is introduced into the mixer reactor, add flame retardants to it: 2-13 parts by weight trichloroethyl phosphate, 2-13 parts by weight hexachlorobenzene, 2-13 parts by weight carbon tetrachloride, 2-13 parts by weight antimony trioxide, 2-13 parts by weight hladon and mix them with the components of the hybrid binder according to item 13 of the claims at temperatures of 40-70 ° C for 3-6 hours per one ton of the finished product, followed by uniform cooling to 20 ± 1 ° C (third stage).

The effectiveness of the hybrid binder according to claim 19, a method for its preparation

In the hybrid binder according to claim 19 for the modification of the properties of plastics based on it, an antistatic additive is used - carbon black and / or carbon-graphite mixtures with a ratio of carbon to graphite ingredients from 1: 1 to 1: 0.1 in the amount of 7-18 wt.h .

Soot and carbon-graphite mixtures are carbon compounds, over 85% of all known chemical compounds contain carbon, and organic chemistry is essentially carbon chemistry.

Soot is carbon black, a black particulate material resulting from the combustion and / or thermal decomposition of hydrocarbons. Consists of spherical particles up to 300 microns in size.

Carbon (C) is a chemical element, the main crystalline modifications of carbon are diamond and graphite. Under normal conditions, carbon is chemically inert, at high temperatures it combines with many elements, carbon is a strong oxidizing agent.

A significant amount of carbon is a part of natural resources - coal, natural gases - methane, butane, acetylene, etc., oil, alcohol, acetone, toluene, etc.

Carbon has the unique ability to form a huge number of compounds, which can consist practically of an inorganic number of carbon atoms.

The main carbon-containing minerals are carbonates. Carbon has a number of valuable properties, which include:

- heat resistance;

- high melting and boiling points;

- good heat and electrical conductivity;

- chemical inertness.

The main raw materials for the industrial production of carbon are petroleum coke, lamp and gas soot, etc.

By treating these materials with binders (resins), various types of carbon are obtained, which are then purified and converted into graphite under the influence of a temperature of ≈2700 ° С. Table 27 summarizes the main physicomechanical, electrostatic, and electrical properties of carbon and graphite.

Table 27
The main physicomechanical, electrostatic and electrical properties of carbon and graphite The name of indicators Carbon Graphite Structure heterogeneous ordered Density, g / cm ³ 1.3-1.8 1.5-2.0 Scleroscope hardness 70-90 (for carbon from coke) 24-45 (for graphite electrical) Melting point, ° С > 3600 > 3600 The modulus of elasticity, kgf / mm ² 300-660 470-980 Electrical conductivity at 20 ° С, cal (cm · sec · deg) 0.1 0.38 The specific volume resistance, · 10 ⁶ , Ohm · cm 5080 700

There are several modifications of graphite, of which the most common:

- natural graphite, mineral - the most common and stable hexagonal polymorphic carbon modification in the earth’s crust, produced in powder form, the structure is layered, it is dark gray to black crystals of different dispersion with a hardness of 1-2 MPa, density up to 2.2 g / cm ³ . Natural graphite contains various impurities and is characterized by insufficient density, and therefore its introduction into a hybrid binder according to claim 19 of the claims (in order to increase the heat resistance of plastics based on it) is not effective enough;

- technical graphite is a polycrystalline refractory material obtained by mixing a filler - calcined petroleum coke and a binder - coal tar pitch. Such a mixture is molded and fired in an inert medium, and to accelerate the growth of crystals, the material is heated to temperatures of 1900-3100 ° C. The introduction of such mixtures into hybrid binders according to claim 19 in order to increase their heat resistance is highly effective, but very expensive;

- dry colloidal graphite preparations, which are highly dispersed powders of thermographite or natural graphite (TU 113-08048-63-90). Such dry colloidal graphite preparations can be used:

- as components for the preparation of graphite mixtures and technological lubricants;

- as an additive to obtain chemically resistant and anti-corrosion plastic coatings;

- as an additive - a plasticizer;

- as a filler in the production of antifriction plastics from composite fibrous materials;

- as a component of binders (resins) for the impregnation of glass and rubberized fabrics;

- as a component of binders used to protect the surfaces of products from highly enthalpy gas flows;

- as a component of binders used to protect products from composite materials from the occurrence and accumulation of static electricity on their surfaces, which occurs during their operation.

Note - The phenomenon of formation of charges of static electricity on the surfaces of composite materials is undesirable, and in many cases, for example, in aerospace and aviation technology, and unacceptable, since their presence can lead to disruption of the processes of operation of products, and sometimes to their exit out of service.

In technology, materials that prevent the occurrence and accumulation of static electricity are commonly called antistatic agents. Antistatic should have the following properties:

- long-term antistatic action of up to 50 years or more - for coating parts and assemblies of exhaust pipes from composite fiber materials of chimneys, and up to 20 years - for parts and assemblies of aerospace engineering;

- maintain an antistatic effect under various operating conditions;

- be resistant to ultraviolet radiation, friction, moisture, various aggressive environments and solvents.

The purpose of introducing into the hybrid binder according to claim 19 the carbon-containing components was the development on the basis of this binder and TEMS-k (p) fabrics of antistatic plastics of the sublimation type that satisfy the above requirements.

To obtain a hybrid binder according to claim 19, 50% solutions of the hybrid binder according to claim 1 in solvent mixtures (acetone-alcohol-toluene in a ratio of 1: (0.5-0.6) :( 0.1- 0.2) of the following compositions, in parts by weight:

- epoxytriphenol resin ETF - 97-103;

- epoxyaliphatic resin DEG-1 - 9-15;

- resol phenol-formaldehyde resin SF-340A (hardener) - 31-37;

- acetone - 87-93;

- ethyl alcohol - 43-49;

- toluene oil and / or coal - 7-13;

- carbon black in the form of spherical particles with a size of 1-100 microns - 7-18.

The resulting solutions were impregnated with CBM fiber and dried in air for 15-20 minutes. Then spent the curing of the binder on the fiber, which is in a tense state in the heat chamber, in the mode:

- at a temperature of 70 ° C - 30 min;

- at a temperature of 100 ° C - 60 minutes;

- at a temperature of 130 ° C - 60 minutes;

- at a temperature of 180 ° C - 60 minutes;

- at a temperature of 210 ° C - 120 minutes.

The heat resistance of the samples was determined on a derivatograph of the Paulik system (Hungary). Heat resistance was determined by the temperature at the onset of mass loss (0.8%).

The thermal stability of the samples was determined as follows: the samples were kept in a heat chamber at a temperature of 200 ° C for 12 hours. Then, their strength and elongation were determined on a dynamometer with a clamping length of 10 cm and a displacement speed of 300 mm / min.

The test results of the obtained plastics based on the hybrid binder according to claim 19 of the claims with the addition of soot (7-18 parts by weight) and CBM fibers in comparison with plastics based on the hybrid binder according to claim 1 and the CBM fibers are presented in table 28.

Table 28
Heat resistance and thermal stability of plastics based on a hybrid binder according to claim 19 with soot additives (7-18 parts by weight) and CBM fibers in comparison with plastics based on a hybrid binder according to claim 1 and CBM fibers

Name of plastics Heat resistance (temperature at the beginning of mass loss 0.8%), ° С Thermal stability strength, kgf elongation,% strength retention,% Plastic based on CBM fiber and hybrid binder according to claim 1 260 6.79 0.99 95.5 Plastic based on CBM fiber and hybrid binder according to claim 19 of the claims with soot additives of the PN-100 brand (7 wt.h.) 275 7.15 0.98 95.6 Plastic based on CBM fiber and hybrid binder according to claim 19 of the claims with soot additives of the PN-100 brand (10 parts by weight) 279 7.18 0.97 95.7 Plastic based on CBM fiber and a hybrid binder according to claim 19 of the claims with soot additives of the PN-100 brand (18 parts by weight) 285 7.23 0.96 96.1 Notes
1 Introduction to the hybrid binder according to claim 19, soot additives of the PN-100 brand are less than 7 parts by weight does not give a noticeable increase in heat resistance and thermal stability to plastics formed from CBM fibers and a hybrid binder according to claim 19.
2 Introduction to the hybrid binder according to claim 19 of the claims of the soot additives of the PN-100 brand more than 18 parts by weight sharply worsens the technological characteristics of this binder by increasing its viscosity (the conditions for its processing into “prepregs” and further into structural products are sharply worsened).
At the same time, dry carbon-graphite mixtures were introduced into the hybrid binder according to claim 19 to study its properties in terms of heat resistance and thermal stability, which are highly dispersed carbonographite powders of four types of dispersion: 0.9-10 μm, 10-60 μm, 60-120 μm and 120-300 microns, TU 113-08-48-63-90.

The main physicochemical parameters of the carbon-graphite mixtures introduced into the hybrid binder according to claim 19 are given in Table 29.

Table 29
The main physico-chemical characteristics of carbonographic mixtures introduced into the hybrid binder according to claim 19 Name of indicator Particle sizes of carbon-graphite mixtures, microns 0.9-10 10-60 60-120 120-300 Mass fraction of ash,%, no more 1 1 1,5 2 Mass fraction of soluble substances insoluble in hydrochloric acid in terms of carbon graphite mixtures,%, not more than 0.2 0.4 0.6 1,0 Balance on the filter or mesh No. 0063,%, no more 0.1 0.3 0.4 0.5 Mass fraction of moisture,%, no more 0.5 0.5 0.5 0.3 Decrease in the mass fraction of carbon-graphite mixtures in an aqueous suspension after settling,%, no more: within 1 hour
- within 25 minutes 10
not normal. 40
not normal. not normal.
40 not normal.
45 Note: Before introducing into the hybrid binder according to claim 19, carbon-graphite mixtures were placed in a muffle furnace cold or heated to a temperature of no higher than 300 ° C, then the temperature in the muffle furnace was raised to 850 ± 20 ° C and calcined at this temperature for at least 3 hours, and then carbon-graphite mixtures heat-treated in this way were cooled to temperatures of 20 ± 1 ° С, introduced into the hybrid binder according to claim 19, located in the reactor-mixer, and uniformly mixed with it at temperatures of 40-70 ° С during 30-60 minutes

To obtain a hybrid binder according to claim 19 of the claims with additives of carbon-graphite mixtures, a 50% solution of the hybrid binder according to claim 1 in a solvent (acetone-alcohol-toluene with a ratio of 1: (0.5-0.6) :( 0 , 1-0.2) of the following composition, in parts by weight:

- epoxytriphenol resin ETF - 97-103;

- epoxyaliphatic resin DEG-1 - 9-15;

- resol phenol-formaldehyde resin SF-340A (hardener) - 31-37;

- acetone - 87-93;

- ethyl alcohol - 43-49;

- toluene oil and / or coal - 7-13;

- carbon-graphite mixtures with the properties listed in table 29, - 7-18.

The obtained solutions were impregnated with CBM fiber at the TsZL impregnation facility of the Federal State Unitary Enterprise PO Avangard and dried in air for 15-20 minutes.

Then, the hybrid binder according to claim 19 was cured on a CBM fiber in tension in a heat chamber in the mode:

- at a temperature of 70 ° C - 30 min;

- at a temperature of 100 ° C - 60 minutes;

- at a temperature of 130 ° C - 60 minutes;

- at a temperature of 180 ° C - 60 minutes;

- at a temperature of 210 ° C - 120 minutes.

Then, the thermal stability of the samples was determined on a Paulik system derivatograph. The heating rate of the samples in air was 5 ° C / min. Heat resistance was determined by the temperature at the onset of mass loss (0.8%).

The thermal stability of the samples was determined according to the method described above: cured samples were kept in a heat chamber at a temperature of 200 ° C for 12 hours, then the strength and elongation of the samples were measured on a dynamometer with a clamp length of 10 cm and a travel speed of 300 mm / min.

The test results of the properties of the obtained composites, in comparison with the properties of composites based on a hybrid binder according to claim 1, are presented in table 30.

Table 30
Heat resistance and thermal stability of plastics based on a hybrid binder according to claim 19 of the claims with additives of carbon-graphite mixture (7-18 parts by weight) and CBM fibers in comparison with plastics based on a hybrid binder according to claim 1 and CBM fibers Name of plastics Heat resistance (temperature at the beginning of mass loss 0.8%), ° С Thermal stability strength, kgf elongation,% strength retention,% Plastic based on CBM fiber and hybrid binder according to claim 1 260 6.79 0.99 95.5 Plastic based on CBM fiber and a hybrid binder according to claim 19 with additives of carbon-graphite mixture (7 parts by weight) 280 7.2 0.97 96.1 Plastic based on CBM fiber and hybrid binder according to claim 19 with additives of carbon-graphite mixture (10 parts by weight) 285 7.3 0.96 96.5 Plastic based on CBM fiber and a hybrid binder according to claim 19 with additives of carbon-graphite mixture (18 parts by weight) 300 7.6 0.95 97.0 Note - Preliminary studies have shown that the amount of carbon-graphite mixture introduced into the hybrid binder according to claim 19 is up to 7 parts by weight does not significantly affect the heat resistance and thermal stability of plastics based on it

The heat resistance and thermal stability of the hybrid binder according to claim 19 of the claims increases with an increase in the mass of the carbon-graphite mixture to 18 parts by weight, an increase in the carbon-graphite mixture in the hybrid binder exceeds 18 parts by weight. sharply reduces the physicomechanical characteristics of plastics based on it, and also increases its viscosity, which sharply worsens the manufacturability of its processing into "prepregs" and further into structural products based on it.

In addition, the introduction of a hybrid binder according to claim 19 of the claims of an increased amount of carbon-graphite mixture in excess of 18 parts by weight sharply reduces its adhesive strength (by about 30-40%), which, in turn, reduces the operational reliability of structures made of composite fibrous materials based on such a binder.

The data in Table 31 below shows the effect of the dispersion of soot particles and / or carbon-graphite mixtures introduced into the hybrid binder according to claim 19 on the tensile strength of the compositions (σ _rast ), average linear ablation of the material (V _y ) from the influence of the heat flux 3.5 · 10 ⁶ W / m ² and speeds of 500 m / s, the average rate of ablation by weight loss (m _y ) (for plastics based on a hybrid binder with additives of carbon-graphite mixtures and heat-protective fabrics TEMS-k (p).

Table 31
The properties of plastics based on a hybrid binder according to claim 19 of the claims containing in its composition a finely divided filler - carbon black and / or carbon-graphite mixtures (7-18 parts by weight), depending on its dispersion Name of additives Dispersion, microns Tensile strength, σ _rast , kgf / cm ² Oxygen Index, CI,% Average linear ablation by temperature sensor V _y , mm / s The average speed of ablation by weight loss, m _y , mm / s Soot and / or carbon-graphite mixtures (7-18 parts by weight) 0.9-10 180 49.4 0.65 0.64 10-60 130 52 0.75 0.73 60-120 95 53 1,0 0.95 120-300 <40 49 1,2 1,1

The analysis of table 31 shows that the introduction into the hybrid binder of carbon-graphite mixtures in excess of 18 wt.h. it does not give a technical effect, since the strength of the cured binder decreases sharply (σ _growth <40 kgf / cm ² ), the average linear weight loss (V _y ) and the average weight loss loss rate (m _y ) increase significantly.

The sizes of the soot particles and / or carbon-graphite mixture introduced into the hybrid binder according to claim 19 on the strength and ablation of the binder also have a significant effect (Table 31), and the introduction of particles with sizes greater than 300 μm into the hybrid binder is generally impractical, since they deteriorate sharply physical and mechanical properties of plastic in strength, mainly tear-off, shear and bending.

In addition, the introduction of an excessive amount of soot or carbon-graphite mixtures into a hybrid binder in excess of 18 parts by weight worsens many other characteristics of plastics based on it, for example, adhesive strength.

An excessive amount of soot and / or carbon-graphite mixtures in a hybrid binder according to claim 19 (over 18 parts by weight) leads to a deterioration in a number of special properties of plastics: fire resistance, fire resistance, radiation and aging, hygroscopicity, gas permeability, viscosity and etc.

However, despite the above disadvantages, the introduction of finely dispersed carbon-containing fillers (carbon black and carbon-graphite mixtures) in the compositions of plastics up to 18 wt.h. (especially for carbon plastics), it allows to reduce the exothermic effect during curing, reduce shrinkage, as well as improve their physical, thermophysical, electrostatic, heat-protective, electrical, electromagnetic and other properties.

It is very effective to use a hybrid binder according to claim 19 to obtain carbon plastics produced by winding or pressing from carbon fabrics, for example, fabrics of the type UT-900-2.5.

The physical and mechanical characteristics of carbon plastics based on carbon fabric UT-900-2.5 and the hybrid binder according to claim 19 of the claims formed by winding methods (Table 32) and pressing (Table 33) are given in Tables 32, 33 below.

Table 32
Physico-mechanical characteristics of winding carbon fiber based on carbon fabric UT-900-2.5 (50-60%) and hybrid binder according to claim 19 of the claims (40-50%) Name of characteristics Test direction Test temperature, ° С The percentage of performance at 200 ° C (operating temperature) 80 160 320 1 Tensile strength of carbon fiber, kgf / mm ² based
by duck 55-60
53-54 51-52
50.1-51 49-50
47-48 93
94 2 The tensile strength of carbon fiber under compression, kgf / mm ² based
by duck 50-51
49-49.5 48-49
47-48 45-47
43-46 95.5
94 3 Tensile strength of carbon fiber in bending, kgf / mm ² based
by duck 45-50
43-45 42-43
41-42 40-40.1
39-39.5 92
91 4 The tensile strength of carbon fiber during crushing, kgf / mm ² based
by duck 53-54.1
51-52 51.1-52.3
50.09-51.2 49.2-49.8
48.1-49.8 93
94 5 The tensile strength of carbon fiber with a chip, kgf / mm ² based
by duck 3.4-3.5
4.1-6.5 3.2-3.45
3.92-5.91 3.1-3.2
3.7-3.81 94
95 6 The tensile strength of carbon fiber during shear, kgf / mm ² based
by duck 14.1-15.3
13.8-14.09 13.9-14
13.1-13.32 12.8-13.35
11.9-12.3 96
94 7 The tensile strength of carbon fiber shear, kgf / mm ² based
by duck 4.6-5.1
3.9-4.3 4.3-4.41
3.81-3.85 4.1-4.23
3.75-3.79 95
93 8 Density, g / cm ³ 1.45 - - - Notes: 1 Carbon fiber is made by winding according to the modes specified in table.14.
2 Additives were introduced into the hybrid binder according to claim 19: soot of PN-100 grade with a fineness of 100 microns, carbon technical element grade A144E, TU 14-106-357-90 and pencil powder graphite, GOST 4404-78 with a fineness of 10 microns taken with a ratio of ingredients of 1: 1: 1. Table 33
Physico-mechanical characteristics of pressed carbon fiber based on carbon fabric UT-900-2.5 (50-60%) and a hybrid binder according to claim 19 of the claims (40-50%) Name of characteristics Test direction Test temperature, ° С The percentage of performance at 200 ° C (operating temperature) 1 Tensile strength of carbon fiber, kgf / mm ² based
by duck 56-61
54-55 52-53
51-52 45-51
48-49 94
95 2 The tensile strength of carbon fiber under compression, kgf / mm ² based
by duck 51-52
49-50 49-50
48-49 46-48
44-47 96.5
95 3 Tensile strength of carbon fiber in bending, kgf / mm ² based
by duck 46-51
44-46 43-44
42-43 41-41.9
40-40.5 93
92 4 The tensile strength of carbon fiber during crushing, kgf / mm ² based
by duck 54-55
52-53 52.1-53.3
50.3-52.2 49.9-50.2
49.1-50.1 94
95 5 The tensile strength of carbon fiber with a chip, kgf / mm ² based
by duck 4-4.5
5-7 3,5-4
4.7-4.9 3.4-3.3
4.6-4.8 95
96 6 The tensile strength of carbon fiber during shear, kgf / mm ² based
by duck 15,1-16
14-14.2 14-14.5
13.8-14 13-13.25
12-12.1 97
95 7 The tensile strength of carbon fiber shear, kgf / mm ² based
by duck 4.9-5.2
4-4.5 4.8-5.1
3.9-4.1 4-4,2
3.6-3.7 96
94 8 Density, g / cm ³ 1,5 - - - Notes: 1 Carbon fiber is made by winding according to the modes specified in table 15. 2 Additives were introduced into the hybrid binder according to claim 19: soot of PN-100 grade with a fineness of 100 microns, carbon technical element grade A144E, TU 14-106-357-90 and pencil powder graphite, GOST 4404-78 with a fineness of 10 microns taken with a ratio of ingredients of 1: 1: 1.

Heat-shielding properties of plastics formed by winding methods based on a hybrid binder according to claim 19 (40-50%) and TEMS-k (p) and UT-900-2.5 (50-60%) fabrics in comparison with heat-shielding properties plastics formed on the basis of a hybrid binder (prototype) according to ed. testimonial. No. 1036730A (70%) and fiberglass T-13 (30%) are presented in table 34.

Table 34
Thermal protective properties of plastics Plastic material Heat flux, · 10 ⁶ , W / m ² Heat flow rate, m / s Average linear ablation by temperature sensor, mm / s The average speed of ablation by weight loss, mm / s Thermal resistance, sec / (kg / m ² ) ² Effective enthalpy, · 10 ⁶ , J / kg Sublimation temperature, ° С The plastic based on the hybrid binder according to claim 19 of the claims and polyphene tissue 3.6 500 0.8 0.75 2,3 2,5 600-700 The plastic based on the hybrid binder according to claim 19 and the caproamide fabric TEMS-k 3.6 500 0.7 0.55 4.1 3,5 300-400 Carbon fiber based on a hybrid binder according to claim 19 and carbon fabric UT-900-2.5 3.6 500 0.5 0.5 3.2 4.2 > 700 Hybrid Binder-Based Plastic by Auth. testimonial. No. 1036730A and fiberglass T-13 (prototype) 3.6 500 0.9-1.1 09-1,1 2.1 <2.4 <200

The electrostatic properties of plastics based on a hybrid binder according to claim 19 of the claims (40-50%) and fabrics TEMS-k (p), UT-900-2.5 (50-60%) in comparison with the prototype are given in table.35 .

Table 35
Electrostatic properties of plastics Name of characteristic A plastic based on a hybrid binder according to claim 19 and TEMS-p fabric The plastic based on the hybrid binder according to claim 19 and the TEMS-k fabric CFRP based on a hybrid binder according to claim 19 and fabric UT-900-2.5 Fiberglass - a prototype based on a hybrid binder according to ed. testimonial. No. 1036730A (30%) and fiberglass T-13 (70%) Volume resistivity, Ohm · cm (4.6-6.4) · 10 ⁴ (4.9-6.3) · 10 ⁴ (4.7-6.5) 10 ⁴ (0.75-0.85) 10 ¹³ Surface resistivity, Ohm (0.9-2.7) · 10 ⁵ (1.8-3.2) · 10 ⁵ (4.0-6.3) · 10 ⁵ (1.5-2.5) 10 ¹³ The average indicator of specific volume resistance, Ohm · cm 5.310 ⁴ 5.8610 ⁴ 5.210 ⁴ 0.810 ¹³ The average specific surface resistance, Ohm 1.7 · 10 ⁵ 2.6210 ⁵ 1.54 · 10 ⁵ 2 · 10 ¹³

The hybrid binder of claim 19 may be cured by various methods. It can be cured by the usual thermochemical method, for example, by convectively heating it (and plastics based on it) in thermal furnaces, most often in electric furnaces, autoclaves, when convectively heating in molds heated by thermoelectric heaters (TENs), as well as gaseous or liquid coolants.

The thermochemical curing of the hybrid binder according to claim 19 using a special hardener - resol phenol-formaldehyde resin SF-340A is the main way to change the properties and structure of the binder.

However, both induction (high-frequency) and radiation heating can be applied to it. The hybrid binder according to claim 19 has high electrical conductivity, and therefore, when it is cured, heating can be applied by passing an electric current through it.

This hybrid binder can also be used in solving many new technical problems, for example, in carrying out the reaction of curing it at sub-zero temperatures, in water, in space, etc.

In this regard, it is of certain interest for its radiation curing, since it is possible at low temperatures and does not require heating. The radiation curing process of the hybrid binder according to claim 19 of the claims is characterized by low energy consumption.

More uniformly in time and in the volume of the polymer, the formation of initiating curing centers occurs, and not associated with the presence of specially introduced hardeners. The initiation of a chemical reaction of curing from the outside makes it possible to accurately meter the input energy, including repeated energy, and expands the temperature region of a stable (without danger of thermal explosion) reaction, with a much higher speed.

The level of energy required for radiation curing a hybrid binder is 3-4 times lower than for thermochemical. In particular, in the radiation curing of a hybrid binder according to claim 19, the energy costs are 21.5-26.5 kJ / mol.

The high-intensity action during curing makes it possible to more fully and at a new qualitative level (densely crosslinked, the formation of chemical and other adhesive bonds of the hybrid binder with other components) to structure the polymer and improve its properties. In addition, it is possible to carry out processes such as solid state polymerization, and as a result, high purity material can be obtained.

Fundamentally, the processes of radiation polymerization of a hybrid binder according to claim 19 of the claims can be carried out under the influence of radiation of various types with adjustable intensity and dose. In this case, the pressure required for the implementation of the curing process can be significantly lower. Processing time can also be significantly reduced due to the higher than during thermochemical curing, the rate of formation of active polymerization centers.

The relatively low cost of radiation energy determines the economic efficiency and feasibility of such a curing method.

The initial stage of irradiation, causing the structuring of the polymer up to the achievement of the limit values of the properties, is replaced by the stage at which destruction occurs, which is characterized by a catastrophic decrease in the radiation resistance of the material with continued irradiation. The doses corresponding to the first stage for the hybrid binder according to claim 19 are in the range of 0.05-1.4 mGy; doses of 1.5-8 mGy, improving some properties of plastics based on this binder, worsen a number of other indicators.

For the curing of the hybrid binder according to claim 19, doses of 0.6-1.8 mGy are needed, but even with these doses, the curing process does not fully take place. The radiation polymerization process is affected by: DEG-1 plasticizer resin, soot and carbon-graphite mixtures in a hybrid binder, SF-340A resin hardener, etc.

The behavior of a hybrid binder during radiation curing is strongly influenced by the presence of a fiberglass filler. Contained in fiberglass (Table 3), as well as in lubricants and sizing (Table 2), some compounds (for example, boron oxide В ₂ О ₃ ) are capable of absorbing large doses of radiation energy (about 1.5-3 mGy), as a result of which the radiation doses necessary for curing the hybrid binder according to claim 19 with such fillers sharply (3-4 times) increase in comparison with the radiation doses for curing the hybrid binder without fillers. This complicates the curing process.

In addition, under conditions of more intense irradiation, destruction begins, as a result of which the properties of the resulting material deteriorate. The use of stabilizing additives (carbon black, carbon-graphite mixtures, etc.) reduces the radiation dose level required for curing, but at the same time worsens a number of physicomechanical properties of the cured polymer, for example, its bending, tearing, and shear strengths.

The introduction of radiation curing technology for the hybrid binder according to claim 19 and other hybrid binders based on it (according to claims 20-24 of the claims) is limited by a number of factors. In particular, not all polymer compositions can be cured by radiation. Hybrid binders based on epoxy and phenol-formaldehyde resins are easiest to radiation cure, but satisfactory modes of their radiation treatment have not yet been found.

For radiation curing, γ- and β-radiation with an energy of 1.6-8 meV are most often used. Moreover, for a number of properties, fiberglass based on these binders, cured by the radiation method, significantly surpass fiberglass cured by the thermochemical method (Table 36).

Table 36
Fiberglass properties depending on curing methods Name of indicator Curing methods Thermochemical combined (thermochemical curing with the simultaneous action of a magnetic field with a strength of 120-1100 Oe) heat curing by passing electric current through a hybrid binder radiation Destructive stress in compression, MPa 165-285 200-300 230-310 260-380 Hardness, MPa 90-140 110-160 140-175 170-180 Heat resistance according to Vika, K 410-460 430-490 450-510 470-560 The temperature of destruction, K 590-630 610-650 630-675 600-700

In some cases, infrared and microwave radiation can be used for radiation curing the hybrid binder of claim 19. They are inferior in effectiveness to penetrating γ- and β-radiation, but have a number of advantages compared to conventional thermochemical curing. First of all, they are more productive and efficient.

Microwave heating makes it possible to cure the hybrid binder according to claim 19 uniformly over the entire thickness of the product, which is especially important when curing thick-walled structures.

During normal heating, curing starts from the surface of the product. The resulting polymerized crust of the outer layer prevents heat transfer to the inner uncured layers of the material. When the thermal conditions of curing of the inner layers reach their optimum, the outer layer of the hybrid binder is often overheated and degradation processes begin in it.

The microwave curing of the hybrid binder according to claim 19 is carried out in alternating electric current (frequency 15-17 MHz) for 10-60 s. This method is expensive because it requires the use of special equipment and protective devices.

Good results can be obtained by combining the method of thermochemical curing of a hybrid binder in furnaces followed by radiation depolymerization.

However, the main method of curing the hybrid binder according to claim 19 of the claims (and all hybrid binders based on it according to claims 20-24 of the claims) currently remains thermochemical. Its intensification (for example, the evacuation of a cured product) can improve not only the properties of the material obtained (10-12% increase strength, 40-45% reduce the variation in strength values, 2-3 times reduce porosity), but also the technological characteristics of the process: reduce the curing temperature of the hybrid binder and reduce the duration of the curing process by 0.5-3 hours.

More actively, the process of thermochemical curing of a hybrid binder according to claim 19 of the claims (and all hybrid binders based on it according to claims 20-24 of the claims) can be intensified under the simultaneous action of a magnetic field with a strength of 120-1100 Oe (Table 36).

The hybrid binder according to claim 19 has insufficient fire resistance, in addition, the processes of its processing into "prepregs" and further into structural products do not meet the requirements for explosion and fire safety.

Fire resistance (resistance to fire) of the above compositions can be increased by introducing flame retardants into these compositions, for example, introducing hexachlorobenzene and / or antimony trioxide into them - 7-18 parts by weight (Claim 20), trichloroethyl phosphate — 7-18 parts by weight (Claim 21), carbon tetrachloride and / or freon - 7-18 wt.h. (Clause 22 of the claims), as well as flame retardant groups consisting of three flame retardants: trichlorethyl phosphate - 2-13 parts by weight, carbon tetrachloride - 2-13 parts by weight and freon - 2-13 parts by weight (Claim 23) and five flame retardants: hexachlorobenzene - 2-13 parts by weight, antimony trioxide - 2-13 parts by weight, trichloroethyl phosphate - 2-13 parts by weight, carbon tetrachloride - 2-13 parts by weight. hours and freon - 2-13 parts by weight (p. 24 claims).

Note - To increase the fire resistance of compositions based on hybrid binders according to items 22-24 of the claims, it is most effective to introduce carbon tetrachloride CCl ₄ into them; carbon tetrachloride is a chlorine derivative of methane, the final product of methane methane is chlorine, a water-insoluble non-combustible liquid, readily soluble in hybrid binders according to claims 22-24. Carbon tetrachloride can be used as an additional solvent to lower the viscosity of hybrid binders according to claims 22-24 and as a flame retardant.

To increase the strength of plastics based on hybrid binders according to items 20-24 of the claims and TEMS-k (p) fabrics, all flame retardants are most effectively used in the form of microcapsules formed from a copolymer based on resorcinol-formaldehyde-urea resins modified with polyvinyl alcohol .

The effectiveness of the hybrid binder according to claim 20, a method for its preparation

The hybrid binder according to claim 20 of the claims contains in its composition a flame retardant additive - 7-18 parts by weight hexachlorobenzene and / or antimony trioxide.

Based on this hybrid binder and TEMS-k (p) fabrics, it is possible to obtain anti-friction structural plastics and articles made of them that have a low coefficient of friction, high wear resistance in surface-active liquid media at high temperatures and high thermal fire resistance.

The hybrid binder compositions of claim 20 as an antistatic additive contain carbon black and / or carbon-graphite mixtures with a carbon to graphite ratio of 1: 1 to 1: 0.1 in an amount of 7-18 parts by weight, and as flame retardants (7-18 parts by weight) - hexachlorobenzene and / or antimony trioxide (SbO ₃ with a ratio of components from 1: 1 to 1: 0.1). The antistatic additives introduced into the hybrid binder according to claim 20 are powdery spherical particles of soot and / or carbon-graphite mixture with a size of 0.9-300 microns.

To study the properties of the hybrid binders according to claim 20 of the claims, the above additives were added to them, forming the following compositions, in parts by weight:

Composition 1

- epoxytriphenol resin ETF - 97-103;

- epoxyaliphatic resin DEG-1 - 9-15;

- resol phenol-formaldehyde resin SF-340A (hardener) - 31-37;

- acetone - 87-93;

- ethyl alcohol - 43-49;

- toluene oil and / or coal - 7-13;

- carbon black and / or carbon-graphite mixtures - 7-18;

- hexachlorobenzene - 7-18.

Composition 2

- epoxytriphenol resin ETF - 97-103;

- epoxyaliphatic resin DEG-1 - 9-15;

- resol phenol-formaldehyde resin SF-340A (hardener) - 31-37;

- acetone - 87-93;

- ethyl alcohol - 43-49;

- toluene oil and / or coal - 7-13;

- carbon black and / or carbon-graphite mixtures - 7-18;

- antimony trioxide - 7-18.

Composition 3

- epoxytriphenol resin ETF - 97-103;

- epoxyaliphatic resin DEG - 1-9-15;

- resol phenol-formaldehyde resin SF-340A (hardener) - 31-37;

- acetone - 87-93;

- ethyl alcohol - 43-49;

- toluene oil and / or coal - 7-13;

- carbon black and / or carbon-graphite mixtures - 7-18;

- hexachlorobenzene and antimony trioxide - 7-18.

As the base binder for the above compositions 1-3, ETF epoxy resin was used, which has high physicomechanical and heat-shielding properties and thermo-fire resistance, as well as good adhesion to almost all composite materials.

In order to reduce the initial viscosity of the binder, increase the heat and chemical resistance, improve the physicomechanical properties and reduce the cost, epoxyaliphatic resin DEG-1 (9-15 parts by weight) was introduced into the ETF epoxytriphenol resin (97-103 parts by weight).

The optimal percentage of hybrid binder according to claim 20 of the claims is determined experimentally based on the physicomechanical properties, heat and chemical resistance, and the processability of preparing composite materials based on it.

The percentage of hardener - resol phenol-formaldehyde resin SF-340A (31-37 parts by weight) for these hybrid binder compositions is determined by the degree of curing of the material by extraction (leaching), that is, the extraction of the alkaline components of the organic solvent from the binder under the influence of temperatures.

Soot and / or carbon-graphite mixtures in an amount of 7-18 parts by weight introduced into the composition of this binder to improve the antistatic, thermophysical and electrostatic properties of plastics based on it, as well as to stabilize their friction coefficients in violation of the boundary friction regime and stabilize the friction coefficient at elevated temperatures.

In order to increase the fire resistance of a plastic based on a hybrid binder according to claim 20 and TEMS-k fabrics (p), a flame retardant - hexachlorobenzene - 7-18 parts by weight was added to it. (composition 1). Some characteristics of a plastic based on a hybrid binder according to claim 20 of the claims of composition 1 and TEMS-k (p) fabrics are presented in Table 37.

Table 37
Characteristics of a plastic based on a hybrid binder according to claim 20 of the claims of composition 1 and TEMS-k fabrics (p) The total amount of carbon-graphite mixture introduced into the hybrid binder The dispersion of the carbon-graphite mixture, microns The dispersion of hexachlorobenzene, microns The tensile strength of a plastic based on a hybrid binder according to claim 20 Oxygen Index,% Average linear ablation by temperature sensor, mm / s The average speed of ablation of weight by weight loss, mm / sec according to claim 20 composition 1, parts by weight composition 1 (40-50%) and tissue TEMS-k (p) (50-60%), kgf / cm ² 7 0.9-10 0.9-10 210 49.5 0.75 0.7 14 10-60 10-60 185 50,2 0.9 0.8 eighteen 60-120 60-120 147 52,4 1,1 0.9 21 120-300 120-300 90 53.0 1.3 1,1 25 300-350 300-350 <40 51.3 1.7 1.3

In order to prevent the composites and counterbodies from setting up during the formation of counterbody films on the friction contact, a flame retardant additive, antimony trioxide (SbO ₃ ), 7-18 wt. (composition 2). Some characteristics of a plastic based on a hybrid binder according to claim 20 of the claims of composition 2 and TECS-k tissues (p) are presented in Table 38.

Table 38
Characteristics of a plastic based on a hybrid binder according to claim 20 of the claims of composition 2 and TEMS-k fabrics (p) The total amount of carbon-graphite mixture introduced into the hybrid binder according to claim 20 composition 1, parts by weight The dispersion of the carbon-graphite mixture, microns The dispersion of antimony trioxide, microns The tensile strength of a plastic based on a hybrid binder according to claim 20 composition 2 (40-50%) and TEMS-k tissues (p) (50-60%), kgf / cm ² Oxygen Index,% Average linear ablation by temperature sensor, mm / s The average speed of ablation of weight by weight loss, mm / sec 7 0.9-10 0.9-10 215 48.5 0.73 0.69 14 10-60 10-60 190 49.2 0.88 0.79 eighteen 60-120 60-120 150 51,4 1,0 0.89 21 120-300 120-300 95 52.0 1,1 1,0 25 300-350 300-350 <50 50.3 1,6 1,2

In order to increase the fire and wear resistance of the plastic based on the hybrid binder according to claim 20 and the TEMS-k (p) fabrics, fire-retardant additives - hexachlorobenzene and antimony trioxide - 7-18 wt.h. (composition 3). Some characteristics of a plastic based on a hybrid binder according to claim 20 of the claims of composition 3 and TECS-k fabrics (p) are given in Table 39.

Table 39
Characteristics of a plastic based on a hybrid binder according to claim 20 of the claims of composition 3 and TEMS-k fabrics (p) The total amount of carbon-graphite mixture introduced into the hybrid binder according to claim 20 composition 1, parts by weight The dispersion of the carbon-graphite mixture, microns The dispersion of hexachlorobenzene and antimony trioxide, microns The tensile strength of a plastic based on a hybrid binder according to claim 20 composition 3 (40-50%) and tissue TEMS-k (p) (50-60%), kgf / cm ² Oxygen Index,% Average linear ablation by temperature sensor, mm / s The average speed of ablation of weight by weight loss, mm / sec 7 0.9-10 0.9-10 215 49.2 0.74 0.69 14 10-60 10-60 190 50,0 0.89 0.78 eighteen 60-120 60-120 149 52.1 1,0 0.88 21 120-300 120-300 92 52.9 1,2 1,0 25 300-350 300-350 <42 51.1 1,6 1,2

The plastics based on the hybrid binder according to claim 20 of the claims have the following physical, thermophysical, heat-shielding and antistatic properties:

- water absorption within 24 hours,%, not more than 0.4;

- the sliding coefficient of friction of the pair: thermal insulation coating - antifriction coating: for composition 1 - 0.094, for composition 2 - 0.09, for composition 3 - 0.092;

- coefficient of thermal conductivity, W / m · K - 0.2-0.25;

- coefficient of thermal diffusivity, · 10 ⁶ , m ² / s - 0.15-0.2;

- specific heat, kJ / kg · K - 0.95-1.4;

- effective enthalpy, · 10 ⁶ , J / kg - 3.25-3.85;

- sublimation temperature, ° C: - for plastic based on TEMS-k fabrics (p) and a hybrid binder according to claim 20: composition 1 - 350-400, composition 2 - 300-350, composition 3 - 400-450;

- specific surface resistance, · 10 ⁵ , Ohm - 1.5-2.5;

- specific volume resistance, 10 ⁴ , Ohm · cm - 5.1-5.3.

The method of obtaining a hybrid binder according to claim 20 of the claims is carried out in the following order.

ETF epoxytriphenol resin - 97-103 parts by weight mixes in the reactor-mixer with resins DEG-1 - 9-15 wt.h. and SF-340A - 31-37 parts by weight in an acetone-alcohol-toluene solvent with a ratio of ingredients 1: (0.5-0.6) :( 0.1-0.2) at temperatures of 180-200 ° C, then the resulting mixture of resins is cooled to temperatures of 40-70 ° C and they are mixed at these temperatures for 3-6 hours per ton of the product being prepared, followed by filtration and cooling to 20 ± 1 ° C, and then they are introduced into the newly formed hybrid antistatic binder - 7-18 wt.h. (carbon black and / or carbon-graphite mixtures) and flame retardant - 7-18 wt.h. (hexachlorobenzene and antimony trioxide) additives, heat the resulting semi-finished hybrid binder to temperatures of 40-70 ° C and mix it with newly added additives for 3-6 hours per ton of the product being prepared.

In this method, soot with particle sizes of 0.9-300 microns and / or dry carbon-graphite mixtures (TU 113-08-48-63-90), which underwent preliminary heat treatment in a muffle furnace at temperatures of 300-500 ° C, were used as antistatic additives for 3-6 hours, followed by uniform cooling to normal temperature. As flame retardants, hexachlorobenzene in liquid and / or microencapsulated form and / or antimony trioxide in powder form with particle sizes of 0.9-300 microns were used. The shells for hexachlorobenzene microcapsules were made from a copolymer based on resorcinol-urea resins modified with polyvinyl alcohol.

The effectiveness of the use of hybrid binders according to claims 21-24 of the claims, methods for their preparation

Below in the text of the description, tables 40-43 show the effectiveness of introducing into the hybrid binders according to items 21-24 of the claims of carbon-containing flame retardants trichloroethyl phosphate - 7-18 parts by weight (Claim 21), carbon tetrachloride and / or freon - 7-18 wt.h. (Claim 22 of the claims), as well as their groups formed from three flame retardants - trichloroethyl phosphate - 2-13 parts by weight, carbon tetrachloride - 2-13 parts by weight and freon - 2-13 parts by weight (Claim 23) and of the five flame retardants - hexachlorobenzene - 2-13 parts by weight, antimony trioxide - 2-13 parts by weight, trichloroethyl phosphate - 2-13 parts by weight, carbon tetrachloride - 2-13 parts by weight .h. and freon - 2-13 parts by weight (paragraph 24 of the claims), introduced together with soot and / or carbon-graphite mixtures with a ratio of ingredients from 1: 1 to 1: 0.1, or from 1: 1: 1 to 1: 0.1: 0.1, or from 1: 1: 1: 1: 1 to 1: 0.1: 0.1: 0.1: 0.1.

As carbon-graphite mixtures, finely dispersed carbon-graphite mixtures (TU 113-08-48-63-90) with particle sizes of 0.9-300 μm were introduced into hybrid binders according to claims 21-24, with hexachlorobenzene as flame retardants antimony trioxide, trichloroethyl phosphate, carbon tetrachloride and two types of freon: Freon brand Ф114В ₁ containing chlorine (Cl ₂ ), chemical formula C ₂ (Cl ₂ F ₂ ) ₄ , structural formula:

and Freon brand F114B ₂ containing bromine (Br ₂ ), chemical formula C ₂ (Br ₂ F ₂ ) ₄ , structural formula:

Hexachlorobenzene, and / or antimony trioxide, and / or carbon tetrachloride, and / or trichloroethyl phosphate, and / or freon in hybrid binders according to claims 21-24 were introduced simultaneously with carbon-graphite mixtures in the form of liquids or microcapsules (microencapsules), formed on the basis of resorcinol-formaldehyde urea resins modified with polyvinyl alcohol.

All carbon-containing flame retardants were introduced into hybrid binders according to items 21-24 of the claims located in the mixer reactor, heated up at temperatures of 40-70 ° C, one-component (item 21 of the claims), two-component with a ratio of ingredients 1: 1 (paragraph 22 of the claims), three-component with a ratio of ingredients 1: 1: 1 (paragraph 23 of the claims) and five-component with a ratio of ingredients 1: 1: 1: 1: 1 (paragraph 24 of the claims) and mixed with them at these temperatures for 3-6 hours per ton of the prepared composition and followed by their uniform cooling to temperatures of 20 ± 1 ° C.

Further, the obtained compositions were impregnated with TEMS-k (p) fabrics with the formation of them "prepregs" semi-finished products with the properties:

- mass fractions of hybrid binders,% - 40-50;

- mass fraction of moisture or volatile substances,% - 3.5-5;

- warranty periods of storage at a temperature of no more than 30 ° C, a day - 4-5.

The manufacturing modes of "prepregs" of semi-finished products TASM formed on the basis of hybrid binders according to claims 21-24 of the claims and fabrics TECS-k (p), the following:

- density, g / cm ³ - 0.95-1.1;

- impregnation speed, m / min - 0.85-1.1;

- temperatures in drying heat chambers of the impregnating machine, ° С - 130-200.

Further, from the obtained "prepregs" of semi-finished products by the methods of winding or pressing according to the modes presented in Table 14 or 15, structural products were made from which the test specimens were cut.

The test results are presented below in table 40-43.

Table 40
Characteristics of a plastic based on a hybrid binder according to claim 21 of the claims and TEMS-k fabrics (p) The total amount of the carbon-graphite mixture introduced into the hybrid binder according to item 21 f.i., parts by weight The dispersion of the carbon-graphite mixture, microns The dispersion of trichloroethyl phosphate, microns The tensile strength of a plastic based on a hybrid binder according to claim 21 (40-50%) and TEMS-k tissues (p) (50-60%), kgf / cm ² Oxygen Index,% Average linear ablation by temperature sensor, mm / s The average speed of ablation of weight by weight loss, mm / sec 7 0.9-10 0.9-10 212 49.7 0.73 0.6 14 10-60 10-60 187 50,4 0.7 0.7 eighteen 60-120 60-120 149 52.6 0.9 0.8 21 120-300 120-300 92 52,2 1,1 1,0 25 300-350 300-350 <42 51.5 1,5 1,2 Table 41
Characteristics of a plastic based on a hybrid binder according to claim 22 of the claims and TEMS-k fabrics (p) The total amount of carbon-graphite mixture introduced into the hybrid binder according to claim 22 f.i., parts by weight The dispersion of the carbon-graphite mixture, microns Dispersion of carbon tetrachloride and / or freon, microns The tensile strength of a plastic based on a hybrid binder according to claim 22 (40-50%) and TEMS-k tissues (p) (50-60%), kgf / cm ² Oxygen Index,% Average linear ablation by temperature sensor, mm / s The average speed of ablation of weight by weight loss, mm / sec 7 0.9-10 0.9-10 213 49.8 0.72 0.59 14 10-60 10-60 188 50,5 0.69 0.69 eighteen 60-120 60-120 150 52.7 0.89 0.78 21 120-300 120-300 93 52.3 1.09 0.08 25 300-350 300-350 <40 51.6 - - Table 42
Characteristics of a plastic based on a hybrid binder according to claim 23 of the claims and TEMS-k fabrics (p) The total amount of carbon-graphite mixture introduced into the hybrid binder The dispersion of the carbon-graphite mixture, microns The dispersion of trichloroethyl phosphate, carbon tetrachloride and chladone, The tensile strength of a plastic based on a hybrid binder according to item 23 Oxygen Index,% Average linear ablation by temperature sensor, mm / s The average speed of ablation of weight by weight loss, mm / sec according to item 23 F.I., wt.h. μm (40-50%) and TEMS-k tissues (p) (50-60%), kgf / cm ² 7 0.9-10 0.9-10 214 49.9 0.71 0.59 14 10-60 10-60 189 50,5 0.68 0.69 eighteen 60-120 60-120 151 52.8 0.88 0.7 21 120-300 120-300 94 52,4 1,02 0.92 25 300-350 300-350 <40 51.6 - - Table 43
Characteristics of a plastic based on a hybrid binder according to paragraph 24 of the claims and tissue TEMS-k (p) The total amount of carbon-graphite mixture introduced into the hybrid binder according to paragraph 24 F.I., parts by weight The dispersion of the carbon-graphite mixture, microns The dispersion of hexachlorobenzene, antimony trioxide, trichloroethyl phosphate, carbon tetrachloride and freon, microns The tensile strength of a plastic based on a hybrid binder according to claim 24 (40-50%) and TEMS-k tissues (p) (50-60%), kgf / cm ² Oxygen Index,% Average linear ablation by temperature sensor, mm / s The average speed of ablation of weight by weight loss, mm / sec 7 0.9-10 0.9-10 216 50.1 0.7 0.58 14 10-60 10-60 190 50.7 0.67 0.67 eighteen 60-120 60-120 152 > 52.9 0.86 0.5 21 120-300 120-300 93 52,5 1,0 0.9 25 300-350 300-350 <40 51.7 - -

Plastics based on hybrid binders according to items 21-24 of the claims have the following physical, thermophysical, electrostatic and heat-shielding properties:

- water absorption within 24 hours,%, no more - 0.35;

- the sliding coefficient of friction of the pair: thermal protection coating - antifriction coating - 0.094 (plastic based on a hybrid binder according to item 21 of the name and fabric TEMS-k (p), - 0.093 (plastic based on a hybrid binder according to item 22 of the item. I. and fabrics TEMS-k (p), - 0,092 (plastic based on a hybrid binder according to item 23 f. and fabrics TEMS-k (p), - 0,085 (plastic based on a hybrid binder according to item 24 f. and. and tissues TEMS-k (p);

- coefficient of thermal conductivity, W / m · K - 0.23-0.27;

- coefficient of thermal diffusivity, · 10 ⁶ , m ² / s - 0.17-0.23;

- specific heat, kJ / kg · K - 0.96-1.5;

- effective enthalpy, · 10 ⁶ , J / kg - 3.3-3.9;

- sublimation temperature, ° C - for plastic based on a hybrid binder according to claim 21 of the claims and TEMS-k fabrics (p) - 370-650, for plastic based on hybrid binder according to claim 22 and the tissues of TEMS-k ( p) - 400-690, for plastic based on a hybrid binder according to claim 23 of the claims and TEMS-k fabrics (p) - 450-730, for plastic based on hybrid binder according to claim 24 and the tissues of TEMS-k ( n) - 750;

- specific surface resistance, · 10 ⁵ , Ohm - 1.4-2.7;

- specific volume resistance, 10 ⁴ , Ohm · cm - 5.0-5.4.

An analysis of Table 40-43 shows that the fire resistance of composites based on hybrid binders according to claims 21-24 and the added flame retardant and antistatic additives increases by 5-20%.

Moreover, composites with bromine-containing chladone have the highest fire resistance (KI> 52.9, Table 43). This binder belongs to the class of hybrid phenol-formaldehyde bromine-containing binders. The simultaneous presence in the hybrid binder of claim 24 of the chlorine-containing and bromine-containing ingredients of freon leads to a significant increase in the thermal stability, heat resistance and fire resistance of plastics based on it and TEMS-k fabrics (p).

The use of phenol-formaldehyde resin SF-340A allowed to reduce the bromine content in hybrid binders according to items 21-24 of the claims to minimum values and increase the fire resistance of plastics based on them by 2-5% (KI> 52.9, Table 43).

Apparently, this is due to the influence of phenol-formaldehyde resin SF-340A, which enhances the extinguishing characteristics of bromine during combustion due to the release of coal. The burning attenuation time of the cured hybrid binders of the above compositions after removal of the gas burner flame is not more than 1-3 seconds, that is, hybrid binders according to items 21-24 are self-extinguishing.

In addition, such hybrid binders make it possible to obtain plastics based on them with very high antistatic characteristics.

An advantage of plastics formed on hybrid binders of the above compositions is their high resistance to aggressive environments, including acidic at elevated temperatures.

However, the options for hybrid binders according to claims 21-24 of the claims (with carbon-containing antistatic and flame retardant additives) have significant disadvantages:

- low adhesive strength, low strength at interlayer shear and separation;

- high viscosity (more than 1 MPa · s) with a total amount of additives added to the hybrid binders over 18 parts by weight, which makes it difficult to impregnate tissue structures with cells less than 10 microns;

- plastics based on these hybrid binder options have low hygroscopicity and gas permeability, which, ultimately, reduces the quality and operational reliability of plastics based on them.

The above data show that hybrid binders with the above additives allow to obtain plastics and structural products based on them with a wide range of improved properties: physicomechanical, thermophysical, physicochemical, electrical, and special, such as fire resistance , aging, radiation, resistance to various atmospheric influences, action of various acid and alkaline environments, etc.

The combination of ETF epoxytriphenol resin with SF-340A phenol-formaldehyde resin and the introduction of hybrid carbon black binders, carbon-graphite mixtures into the compositions made it possible to obtain plastics based on them with high heat resistance and thermal stability.

The introduction of flame retardants into hybrid binders has significantly improved the fire resistance of plastics based on them, their self-extinguishing during combustion.

The developed hybrid binders according to claims 21-24 with the above additives allow to obtain products from composite fibrous materials based on them with high sublimation effect, high heat-shielding properties, as well as with high antistatic and electromagnetic properties, as well as with high impact viscosity (for GRP - 20-690 kJ / m ^2, for CFRP - 26-85 kJ / m ^2, for boroplastikov - 45-100 kJ / m ^2, for organic plastics - 157-195 kJ / m ²⁾ and with other operational properties: corrosion resistant capacity, radio transparency, wear resistance, resistance to aging, etc.

The advantages of hybrid binders according to items 21-24 of the claims should also include their high technological properties: relatively low viscosity, low shrinkage during curing, very good adhesion to almost all materials, high viability, high stability of properties even under prolonged conditions storage and operation.

These hybrid binders also have drawbacks: they are toxic, expensive (especially due to the introduction of carbon-graphite mixtures, graphite and other additives into their compositions), they require the use of special expensive equipment for processing, and have non-optimal viscosity (from the point of view of impregnating fillers).

However, the required viscosity for these hybrid binders is achieved by:

- the introduction of solvents, including flame retardants;

- heating, that is, it allows you to conduct technological processes of their processing at elevated temperatures, at which their viscosity decreases to the required values (from 0.1 to 1 Pa · s).

Hybrid solvent solvents according to claims 21-24 can be: acetone, alcohol, toluene and acetone-alcohol-toluene mixtures (acetone-alcohol-toluene solvent with an ingredient ratio of 1: (0.5-0.6) is recommended : (0.1-0.2). Solvents of epoxytriphenolformaldehyde binders ETF + DEG-1 + SF-340A can be aromatic hydrocarbons (benzene, xylene, etc.), as well as chlorinated hydrocarbons (dichloroethane, monochlorobenzene, etc.), active diluents based on phenyl glycidic and furfuryl glycidic ethers, as well as cyclohexane, dioxane, fu furol, methyl ethyl ketone, ethyl acetate, butyl acetate, and others.

Research work on the use of the above solvents in the creation of hybrid epoxytriphenolformaldehyde binders is underway, including at the Avangard Federal State Unitary Enterprise. However, an analysis of their effectiveness is not given in this description, since its implementation is beyond the scope of the claims presented in this description.

The amount of any solvents introduced into hybrid binders according to claims 21-24 of the claims (except flame retardants) is determined only by technological requirements and in any case should be minimal.

This circumstance is due to the fact that the volatile fractions of the solvent, released from the plastic during its molding and curing, form pores, delaminations, microcracks, significant internal stresses, which reduces the plastic bending strength (1.5-2 times) and, to a lesser extent degrees, tensile and shear strength (by 20-50%).

To eliminate, or at least to reduce these defects when creating hybrid binders, complex additives were tested: nickel chlorine-nickel Ni ₂ Cl ₂ - 1-6 parts by weight (claim 10 of the claims), chlorobalt CoL ₂ Cl ₂ , chlorinated CuL ₂ Cl ₂ and other complex metal chloride compounds.

To increase thermal stability, thermal stability and fire resistance, copper phthalcyanines (claims 9 and 1) and flame retardants (claims 2 to 8, 14–18, 20–24 of the claims) were introduced into hybrid binders, and powder mixtures were added to increase dynamic strength metal oxides and nitrides (pp. 26-33 of the claims), to increase transverse strength and stiffness, shear and tearing of plastics - whiskers (pp. 34-38 of the claims), to increase the viability of hybrid binders - aluminosilicates, Na zeolites (pp 13-18 forms Proceedings of the invention) and other molecular sieves.

And all of the above components introduced into the hybrid binders according to items 21-24 of the claims are well compatible with them, since the compositions of these binders have good adhesion to almost all of the above materials.

It should be borne in mind that in the materials of the description and the claims only certain possible preferred options for their implementation are presented, and other options (or combinations of options) can be used in relation to the compositions of the binders, methods for their preparation and processing, and including parts:

- methods for preparing hybrid binders and their individual components;

- methods for their processing (in terms of impregnation, preparation of "prepregs", winding and curing modes of specific structural plastic products).

The proposed hybrid binders according to claims 21-24 are highly versatile. They can be highly efficiently used to impregnate any filamentary fillers, including woven and unidirectional ones, with any structure and density of weaving of threads in woven fillers, and also with any known fibrous fillers: glass, polycaproamide, polyphene, organic, carbon boric and basaltic.

The hybrid binder variants presented in the description according to claims 21-24 can also be used to impregnate threads or fabrics lined with special surface coatings - lubricants, finishes and / or copolymers with certain additives.

The proposed hybrid binders in combination with other fillers can be used in the manufacture of plastic products by any means of winding and / or pressing.

In particular, the proposed hybrid binder options can be used in the manufacture of plastic products using wet and dry winding methods, using any combination of windings: direct fabric winding (PTN), longitudinally-transverse winding (PPN), spiral filament winding (SNN) et al. (Table 44).

Table 44
The influence of the winding scheme on the properties of fiberglass based on hybrid binders according to items 21-24 of the claims and fiberglass fillers: unidirectional and manufactured by the methods of PTN, PPN, SNN Name of indicator Unidirectional material Material from pipes made by various methods PTN PPN SNN Density, g / cm ³ 1.8-2.2 1.65-1.9 1.8-2.1 1.9-2.2 Tensile stress, MPa 690-2075

Tensile modulus, GPa

Specific Strength, km 60-100 25-38 37-60 30-60 Parameter (σ _p / E) · 10 ^-4 250-350 145-180 170-230 170-220 Elongation at break,% 0.7-2.5 0.5-2.2 0.5-2.5 1-2,5 Poisson's ratio

Water absorption,% 0.03-0.3 0.04-0.4 0.025-0.3 0.02-0.25 Elongation at break,% 1.5-2.8 1.55-2.9 1.4-2.5 1.45-2.55

Note - The numerator shows the material properties in the circumferential (ring) direction, in the denominator - in the axial direction

The compositions of the above hybrid binders according to items 21-24 of the claims, as well as methods for their preparation, as well as methods for producing unidirectional or woven “prepregs” based on them, and methods for producing plastic structural products from them can differ significantly from each other parts:

- temperature-speed winding modes;

- tensions and contact pressures used during winding;

- impregnation and drying of "prepregs" (for the "dry" method of manufacturing products from composite fibrous materials);

- modes of curing the binder (temperature and time);

- modes of preparation of individual components - additives introduced into hybrid binders;

- the sequence of their introduction into hybrid binders at various stages of their processing.

The effectiveness of the use of a hybrid binder according to claim 25, a method for its preparation

The hybrid binder of claim 25 of the claims contains a hybrid binder of claim 1 with flame retardants - 12-23 parts by weight: antimony trioxide and hexachlorobenzene.

This hybrid binder was created to produce fillers based on it from polyphene (TEMS-p) and caproamide (TEMS-k) fabrics (TU 6-I82-85), formed from multicomponent complex electrically conductive threads (MKEN), TU 6-06- 31-121-76, heat-protective plastics and / or plastic coatings based on them.

The multicomponent complex electrically conductive threads of these fabrics consist of a “core” formed of polymer fibers with a low coke number — polyphene or caproamide (capron).

The presence of an electrically conductive filler in the polymer coating of the “core” of soot PN-100 in an amount of 15-20% of the weight provides a specific resistance of plastic not more than 1 Ohm. The presence in the coating composition of the “core” also of antimony trioxide flame retardants - 10-15% and hexachlorobenzene - 15-20%, and in the composition of the “core” fibers - 40-50% with a low coke number of capron and polyphene provides a high sublimation material the effect. The coating of the “nuclei” of the fabric fibers is formed from a copolymer of tetrafluoroethylene with vinylidene fluoride - 50-55%.

Even with such ratios of ingredients in fillers of plastics based on them and known heat-resistant epoxy binders, for example, EHD or EHD-U - 40-50%, TU 6-06-1725-75, the rest of the TEMS-k fabric (p) - 50- 60% have very high physical, electrostatic and heat-shielding characteristics. The hybrid binder used in accordance with claim 25 of the claims used instead of a binder ECD or ECD-U gives an even greater technical effect.

Table 45 below shows the characteristics of plastics formed on the basis of a hybrid binder according to claim 25 of the claims and TEMS-k (p) fabrics in comparison with plastics based on epoxy binders ECD or EHD-U, taken as a prototype, and the same fabrics TEMS-k (p).

Table 45
Physical, thermophysical, electrostatic and heat-shielding properties of plastics based on a hybrid binder according to claim 25 of the invention and TEMS-k (p) fabrics in comparison with plastics based on epoxy binders ECD or EHD-U and the same TEMS-k fabrics (p) Name of characteristic Material Plastic - a prototype based on a binder EHD-U and TEMS-p fabrics Plastic - a prototype based on a binder ECD and TEMS-k tissues Plastic based on a hybrid binder according to claim 25 and tissues TEMS-p Plastic based on a hybrid binder according to claim 25 and tissues TEMS-k Density, g / cm ³ 1.77-1.8 1.27-1.28 1.77-1.8 1.27-1.3 Thermal conductivity, W / m 0.28-0.29 0.14-0.25 0.3-0.31 0.26-0.27 Heat capacity, kJ / kg 1.14-1.16 1.23-1.24 1.17-1.18 1.24-1.26 Thermal diffusivity, m ² / s 1.36-1.37 1.52-1.53 1.37-1.39 1.53-1.55 Surface resistivity, · 10 ⁴ , Ohm · cm 5.2-5.3 5.3-5.4 5.4-5.6 6.1-6.2 The specific volume resistance, · 10 ⁵ Ohms 1.7-1.8 2.6-2.7 1.9-2.0 2.7-2.8 Effective enthalpy, · 10 ⁶ , J / kg 2,5 3,5 2.6-2.7 3,5-3,9 The average linear ablation by a temperature sensor, mm / s, with a heat flux of 3.5 · 10 ⁶ , W / m ² , and a flow velocity of 500 m / s 0.8 0.75 0.7 0.65 The average linear ablation for weight loss, mm / s, with a heat flux of 3.5 · 10 ⁶ , W / m ² , and a flow velocity of 500 m / s 0.75 0.55 0.7 0.5 Sublimation temperature, ° С 600 300 650 350 Oxygen Index,% 55 53 56 54 Water absorption within 24 hours,%, no more 0.4 0.35 0.3 0.35 Coefficient of sliding friction of the plastic material over the anti-friction coating 0.094 0,095 0,093 0,092 The coefficient of thermal conductivity, W / m · K 0.17-0.18 0.13-0.15 0.19-0.21 0.16-0.17 Specific heat, kJ / kg · K 1.34-1.36 0.9-1.3 1.36-1.37 0.91-1.35 Destructive stress of plastic in the direction of the base, MPa 125-126 127-130 126-129 128-131 The tensile modulus in the direction of the base, GPa 2.7-2.8 2.75-2.85 2.8-2.9 2.85-2.95 Breaking stress, MPa 89-90 89.5-95 90-91 91-92 Breaking stress during crushing, MPa 100-105 105-110 101-106 106-115 Destructive stress at separation from structural plastic SKN-21, GPa 7.8 7.8 8-9 9-10 Breaking stress at separation from structural plastic SKN-24, GPa 10-11 eleven 10.5-11.5 11-12 Interlayer shear strength, MPa 6-8 8-9 10-11 12-15

The data in Table 45 show that the plastics of the binder according to claim 25 of the claims and fabrics based on hybrid TEMS-k (p) have very high heat-shielding, antifriction, and antistatic characteristics, all heat-shielding plastics have a long-term antistatic effect and retain an antistatic effect under various conditions operation; plastics are resistant to light, friction, the action of water, various solvents, solutions of acids and alkalis, DDD agents, etc.

Plastics based on a hybrid binder according to claim 25 and TEMS-k (p) fabrics have high fire resistance (oxygen index 54-56), and the hybrid binders themselves, when processed into "prepregs", have high fire and explosion safety.

However, these plastics have a number of significant drawbacks. They have very low physical and mechanical characteristics, especially interlayer ones for separation, shear and bending. Plastics have a low impact strength ≈25.5-85 kJ / m ² , and a large water absorption of 0.3-0.35%.

A method of obtaining a hybrid binder according to claim 25 of the claims is as follows.

In the hybrid binder according to claim 1, the claims are introduced in an amount of 12-23 parts by weight. antimony trioxide and hexachlorobenzene and mix them in a mixing reactor together with the components of the hybrid binder at temperatures of 40-70 ° C for 3-6 hours per ton of the product being prepared, followed by its uniform cooling to temperatures of 20 ± 1 ° C.

Methods for producing "prepregs" based on a hybrid binder according to claim 25 of the claims and TEMS-k (p) tissues are carried out in several stages.

At the first stage, polyphene and caproamide fabrics are impregnated with a binder in the following ratios: a copolymer of tetrafluoroethylene with vinylidene fluoride - 50-55%, hexachlorobenzene - 15-20%, antimony trioxide - 10-15%, soot PN-100 - 15-20%.

The impregnation of the threads is carried out according to the documentation at the closed-type horizontal impregnation machine operating at the FSUE PO Avangard enterprise, by pulling them through the impregnation bath with horizontally arranged pressure rollers in accordance with the following mode:

- contact pressure of the rollers, atm - 1;

- temperature in the impregnating bath, ° C - 60-80;

- impregnation speed, m / min - 0.8-1.1;

- the specific gravity of the binder in the bath, g / cm ³ - 0.85-0.97;

- the amount of tension - is optionally selected with non-sagging tissue.

The specified mode provides a preliminary "prepreg" with the following characteristics:

- binder content,% - 24-32;

- volatile content,% - 2.5-4.5.

Next, the preliminary "prepreg" is impregnated with a hybrid binder according to claim 25 in the following mode:

- the density of the hybrid binder, g / cm ³ - 0.95-1.1;

- impregnation speed, m / min - 0.85-1.1;

- the temperature in the drying heat chambers of the impregnation machine, ° C - 130-200.

As a result of secondary impregnation, a “prepreg” semi-finished product is formed with the following properties:

- mass fraction of binder,% - 40-50;

- mass fraction of moisture and volatile substances,% - 3.5-5.5;

- warranty period of storage at temperatures no more than 30 ° C, day - no more than 4-5.

Further, on the basis of the obtained "prepreg" semi-finished product according to the processing modes presented in Tables 14 or 15, structural products are made by the methods of "dry" tissue winding or pressing, followed by cutting out of them samples and carrying out their tests according to standard methods. The test results are given in table 45.

The effectiveness of the use of a hybrid binder according to claims 26-27 of the claims, a method for its preparation

This hybrid binder is dependent on the main hybrid binder according to claim 25.

The hybrid binder according to claims 26-27 of the claims contains 12-23 parts by weight flame retardant - antimony trioxide and hexachlorobenzene and 12-23 wt.h. powder additives in the form of monolithic, hollow, scaly and fibrous particles of metal oxides and / or nitrides and silicon oxides.

This hybrid binder, as well as the main one according to claim 25 of the claims, is most effective for impregnating heat-protective fabrics of the type TEMS-k (p) used to produce heat-protective plastics and / or plastic coatings to protect structural products from composite fibrous materials from exposure high-temperature gas flows (for gas flow rates - 500 m / s and heat flows - 3.5 · 10 ⁶ W / m ² ).

To increase the heat resistance and thermal stability of plastics based on a hybrid binder according to claim 26 and fabrics of the type TEMS-k (p), magnesium oxides (MgO) are used - burnt magnesia, which are introduced into this binder in an amount of 12-23 wt.h. as an additive.

Magnesium oxide (MgO) - the main oxide, a refractory fine powder, is used in the manufacture of heat-protective or refractory plastics, as well as as a vulcanizing agent in the production of viscoelastic polymer composites.

Magnesium oxide is a colorless crystalline substance with a melting point of 2800 ° C. Get magnesium oxide by burning minerals - magnesite and dolomite; is introduced into the hybrid binder according to claim 26 in the form of a powder filler mainly to modify the physical and thermophysical properties of plastics based on this binder and heat-protective fabrics TEMS-k (p).

Properties of magnesium oxide:

- molecular weight - 40.32;

- density, g / cm ³ - 3.38;

- melting point, K - 3073 (2800 ° С);

- boiling point, K - 3098 (2825 ° С);

- specific heat, kJ / (kg · K) - 209;

- coefficient of thermal conductivity, W / (m · K) - 34.2.

The hybrid binder according to paragraph 26 of the claims with additives of magnesium oxides has the following composition, in parts by weight:

- epoxytriphenol resin ETF - 97-103;

- epoxytriphenol resin DEG-1 - 9-15;

- resol phenol-formaldehyde resin SF-340A - 31-37;

- acetone - 87-93;

- ethyl alcohol - 43-49;

- toluene oil and / or coal - 7-13;

- flame retardants (hexachlorobenzene and antimony trioxide) - 12-23;

- magnesium oxide (MgO) - burnt magnesia - 12-23.

Fire-retardant additives - hexachlorobenzene and antimony trioxide (12-23 parts by weight) are introduced into the hybrid binder according to claim 26 to increase the heat-resistance of plastics based on this binder and TECS-k fabrics (p), as well as to improve their antifriction and antistatic properties.

Magnesium oxide is also introduced into the hybrid binder according to claim 26 to improve the above plastics and, in addition, to increase the toughness and vibration resistance.

Table 46 below summarizes the main thermophysical, heat-shielding, electrostatic, and physicomechanical properties of plastics based on a hybrid binder according to claim 26 with additions of magnesium oxide and TEMC-k fabrics (p).

Table 46
Properties of plastics based on a hybrid binder according to claim 26 with additives of magnesium oxide and tissues TEMC-k (p) Name of indicator Hybrid Binder Plastic according to Claim 26 with additives from magnesium oxide and tissues TEMS-p Hybrid Binder Plastic according to Claim 26 with additives from magnesium oxide and tissue TEMC-k Thermophysical properties of plastics Density, g / cm ³ 1.8-2.1 1.3-1.41 Thermal conductivity, W / (m · deg) 0.29-0.3 0.24-0.25 Heat capacity, kJ / kg 1.16-1.19 1.25-1.29 Thermal diffusivity, m ² / s 1.38-1.41 1.53-1.55 Thermal protective properties of plastics Heat flux, · 10 ⁶ , W / m ² 3,5 3,5 Heat flow rate, m / s 500 500 Average linear ablation by temperature sensor, mm / s 0.79-0.8 0.69-0.7 The average speed of ablation by weight loss, mm / s 0.71-0.73 0.51-0.53 Thermal resistance, sec / (kg / m ² ) ² 2.1-2.4 3.9-4.2 Effective enthalpy, · 10 ⁶ , J / kg 2.4-2.6 3.3-3.6 Oxygen Index,% 54-55 52-53 Sublimation temperature, ° С 610-630 320-350 Electrostatic properties of plastics Surface resistivity, · 10 ⁵ , Ohm 1.6-1.9 2.5-2.7 The specific volume resistance, · 10 ⁴ , Ohm · cm 5.1-5.4 5,6-5,9 Physico-mechanical properties of plastics Tensile stress in the direction of the base, MPa 126-128 128-130 Breaking stress at bending, MPa, not less 90-95 100-110 Breaking stress during crushing, MPa, not less 105-110 115-120 The tensile modulus in the direction of the base, GPa 2.8-2.9 3.0-3.1 Destructive stress at separation from fiberglass SKN-21, MPa 11-15 13-17 Destructive stress at separation from fiberglass SKN-24, MPa 9-10 11-13 Shear breaking stress, MPa 20-30 30-50 Dynamic viscosity, kJ / m ² 45-85 50-90 Specific Strength, km 20-40 25-45 Specific Stiffness, km 3500-4000 3600-4200

The method of preparation of a hybrid binder according to p. 26 claims with the addition of magnesium oxide is carried out in the following order of technological operations.

At the first stage, the hybrid binder according to claim 1 is introduced into the mixer reactor and heated to a temperature of 40-70 ° C.

At the second stage, flame retardants — hexachlorobenzene and antimony trioxide (12-23 parts by weight) with a ratio of components from 1: 1 to 1: 0.1 are loaded into the hybrid binder according to claim 1, and mixed with a hybrid binder at temperatures 40 -70 ° C for 3-6 hours based on one ton of the prepared semi-finished product.

In the third stage, 12-23 parts by weight are added to the semi-finished product. magnesium oxide and all components are mixed again at temperatures of 40-70 ° C for 3-6 hours per ton of the product being prepared.

At the fourth stage, an alcohol-acetone mixture with a component ratio of 1: 2 is introduced into the hybrid binder-semi-finished product and the prepared product is brought (by introducing this mixture) to a density of 0.95-1.1 g / cm ³ , followed by cooling to a temperature of 20 ± 1 ° C.

Further, from the obtained hybrid binder according to claim 26 with the addition of magnesium oxide and tissues, TEMC-k (p) is made by impregnation methods "prepregs" in the following modes:

- the density of the hybrid binder according to p. 26 in the bath of the impregnation machine, g / cm ³ - 0.95-1.1;

- impregnation speed, m / min - 0.85-1.1;

- the tension of the fabric webs TEMS-k (p) is optionally selected to ensure non-sagging fabrics when impregnated;

- the temperature in the drying heat chambers of the impregnation machine, ° C - 130-200.

The properties of the obtained TASM "prepreg" as a result of the impregnation operation are as follows:

- mass fraction of hybrid binder according to p. 26,% - 40-50;

- mass fraction of moisture and volatile substances,% - 3.5-5.5;

- the warranty period of storage of the "prepreg" at temperatures of 25 ± 5 ° C, at least 6 days.

Then, on a winding machine, winding or pressing methods according to the modes presented in Table 14 or 15 make plastics (or cylindrical tubular samples) and test them according to standard test methods developed at the Avangard FSUE enterprise. The test results are presented in table 46.

The resulting plastics have high sublimation (effective enthalpy - 2.4-3.6 J / kg), electrostatic (specific surface resistance - (1.6-2.7) · 10 ⁵ Ohm, specific volume resistance - (5.1- 5.9) · 10 ⁴ Ohm · cm) properties. In addition, the obtained plastics have increased corrosion resistance, water resistance, vibration resistance, resistance to aggressive environments, including DDD and OV environments, as well as to all carbon-hydrogen solvents.

The hybrid binder according to paragraph 26 of the claims with additives of magnesium oxide has significant drawbacks - the technological operations of its preparation and processing are explosive and fire hazard, therefore, when preparing and processing it, all necessary safety requirements must be observed.

The speed of obtaining from it and the TEMC-k (p) “prepreg” tissues should not be more than 1.1 m / min, all operations for preparing a hybrid binder should be carried out in the strict sequence of introducing components into it with the mixer turned off and the mixer reactor grounding.

As additional technological tools to ensure explosion and fire safety, the preparation of a hybrid binder according to paragraph 26 of the claims with additives from magnesium oxide, the following is recommended:

- the introduction of a hybrid binder antistatic additives such as "Sigbol" or ASP-1;

- introduction into the hybrid binder of chalk (up to 10 parts by weight), calcium sulfate (up to 20 parts by weight), ammonium (up to 5-7 parts by weight), diammonium phosphate and other ammonium-containing compounds, as well as compositions from aluminosilicates, consisting of oxides SiO ₄ and AlO ₄ , in the cavities of which the above components can be located.

In addition, to reduce the explosion and fire hazard of technological operations for the preparation of a hybrid binder according to claim 26 with magnesium oxide additives, it is recommended to moisten resin granules SF-340A and aluminosilicates from oxides SiO ₄ and AlO ₄ with water (up to 25%) and / or saturate them with the above components.

From the point of view of ensuring the viability of the hybrid binder according to claim 26, the most effective additives from SiO ₄ and AlO ₄ are the so-called zeolites (aluminosilicates). In zeolites, the crystalline structure is formed by tetrahedral fragments of SiO ₄ and AlO ₄ , united by common vertices into a three-dimensional framework pierced by cavities of channels. In the latter there are water molecules and cations of metals, ammonium and ammonium-containing compounds. They are able to selectively select and reabsorb various substances, as well as exchange cations.

Zeolites (SiO ₄ and AlO ₄ ) are found in nature (they are mainly low-temperature hydrothermal minerals by origin); and get them artificially.

In the hybrid binder of claim 26, the zeolites act as adsorbents, ion exchangers, molecular sieves. Their introduction into the hybrid binder according to paragraph 26 of the claims can be carried out both by direct mixing with the hardener - resin granules SF-340A, and by pre-saturation with pairs of adsorbed hardener.

Molecular sieves such as Na zeolite (and / or sodium aluminosilicate) increase the viability of the hybrid binder according to claim 26 by a factor of 2-2.5. At the same time, the aluminosilicates introduced into the hybrid binder according to claim 26 increase some physical and mechanical characteristics of plastics, for example, plastics based on the hybrid binder according to claim 26 with aluminosilicates and TECS-k fabrics (p). Such plastics, in comparison with plastics based on a hybrid binder according to claim 25, have higher shear - 15-20 MPa and transverse (tear-off) - 60-90 MPa characteristics.

In a hybrid binder according to paragraphs 26-27 of the claims, in order to modify mainly the physical properties of the composites based on it, other finely dispersed additives can be introduced:

- aluminum oxide (Al ₂ About ₃ ) - alumina;

- titanium oxide (TiO ₂ ) - rutile;

- silicon oxide (SiO ₂ ) - silica (aerosil);

- boron nitrides: graphitized boron nitride (BN), borazon and borazole (B ₃ N ₃ H ₆ ).

Each of the above ingredients can be introduced into a hybrid binder according to items 26-27 of the claims, componentwise or in groups, with a total amount of 12-23 parts by weight.

Aerosil (SiO ₂ ) is a highly dispersed amorphous silicon dioxide, can be used in a hybrid binder according to claim 27 as a filler, a carrier in the manufacture of catalysts (together with SiO ₄ ), and also as a thickener for a hybrid binder. Aerosil is introduced into the hybrid binder mainly to give it thixotropic properties.

Before introduction into the hybrid binder, Aerosil must be dried at temperatures of 115 ± 5 ° С; It is recommended that heat treatment of Aerosil at temperatures of 400-500 ° C for 4-5 hours, followed by cooling to temperatures of 20 ± 1 ° C.

When working with aerosil, it is possible to release glass dust into the air of the working area. Dust causes respiratory disease (silicosis) and irritates the skin. The maximum permissible concentration of aerosil dust is 1 mg / m ³ .

The recommended amount of introduced aerosil is 5-7% per 100% hybrid binder according to claim 27. The main properties of aerosil are given in table 10.

Alumina (Al ₂ O ₃ ) is an amphoteric oxide, a refractory and fine powder with the properties shown in table 10; exists in the form of several modifications, it is used in a hybrid binder according to claim 26 to increase the refractoriness of plastics based on it and TEMS-k (p) fabrics, as well as as an adsorbent, catalyst, etc.

The hybrid binder according to items 26-27 of the claims with additives of SiO ₂ and Al ₂ O ₃ has a high viability of up to 6 months at a temperature of 298 K (without resin SF-340A).

Plastics based on this binder have the following properties:

- heat resistance according to VIKA, K - 770-820;

- temperature of the beginning of intensive destruction, ° С - 300;

- operating temperature for continuous operation, ° С - 180-250;

- destructive stress, MPa:

tensile - 23-90;

under compression - 70-200;

when bending - 80-89;

- elongation at break,% - 0.4-3;

- modulus of tensile elasticity, GPa - 2.5-7.

Thermal protective characteristics of a plastic based on a hybrid binder according to items 26-27 of the claims with additions of SiO ₂ and Al ₂ O ₃ (12-23 parts by weight) and TEMC-k fabrics (p) are presented in Table 47.

Table 47
Thermal protective characteristics of plastic Name of indicator Hybrid Binder Plastic according to Claim 26 with additives of SiO ₂ and Al ₂ O ₃ and TEMS-p fabrics Hybrid Binder Plastic according to Claim 26 with additives of SiO ₂ and Al ₂ O ₃ and TECS-k fabrics Heat flux, · 10 ⁶ , W / m ² 3,5 3,5 Gas flow rate, m / s 500 500 Average linear ablation by temperature sensor, mm / s 0.75 0.65 The average speed of ablation by weight loss, mm / s 0.7 0.5 Thermal resistance, sec / (kg / m ² ) ² 2,5 4.2 Effective enthalpy, · 10 ⁶ , J / kg 2.6-2.7 3.6-4 Sublimation temperature, ° С 650-700 350-400 Oxygen Index,% 56 55

The effectiveness of introducing into a hybrid binder according to claim 26 the finely divided titanium oxide (TiO ₂ ) - rutile.

Rutile is a mineral powder with a fineness of up to 300 microns with a crystalline tetragonal form (the most stable modification of rutile). The hardness of rutile is 6.5-7.5, the density is 4.2-4.4 g / cm ³ , the remaining properties of rutile are presented in table 10.

Varieties of rutile:

- nigrin, which contains up to 11-12% Fe ₂ O ₃ ;

- rutile leucoxene - cryptocrystalline products of titanium minerals;

- hairy - hairy inclusions of rutile in crystal, magmatic, metaphorical, hydrothermal in origin, extracted from titanium placers.

All types of rutile as a filler are used to increase the thermal strength and thermal stability of plastics based on a hybrid binder according to claim 26 and TEMS-k fabrics (p), as well as giving them high corrosion resistance.

Plastics based on this hybrid binder with rutile additives (12-23 parts by weight) are recommended for use in rocket science, mechanical engineering, architecture, large and small energy, etc.

The heat-shielding properties of plastics based on a hybrid binder according to claim 26 with the addition of rutile and TEMC-k (p) fabrics are presented in Table 48.

Table 48
Thermal protective properties of plastics Name of indicator Hybrid binder based plastics according to claim 26 with additives of rutile and tissues TEMS-p Hybrid binder based plastics according to claim 26 with additives of rutile and tissues TEMS-k Average linear ablation by temperature sensor, mm / s 0.8 0.7 The average speed of ablation by weight loss, mm / s 0.75 0.55 Thermal resistance, sec / (kg / m ² ) ² 2.6 4.3 Effective enthalpy, · 10 ⁶ , J / kg 2.6-2.9 3.6-4.2 Sublimation temperature, ° С 600-700 300-400 Oxygen Index,% 55 54 Surface resistivity, · 10 ⁵ , Ohm 1.8-1.9 2.7-2.8 The specific volume resistance, · 10 ⁴ , Ohm · cm 5.2-5.3 5.7-5.9 Heat flow, · 10, W / m ² 3,5 3,5 Gas flow rate, m / s 500 500

Plastics based on a hybrid binder according to claim 26 with rutile additives and TECS-k (p) fabrics have enhanced thermal and erosion and corrosion resistance. In addition, these plastics have a long-term antistatic effect and retain an antistatic effect under various operating conditions; plastics are resistant to light, aggressive environments, various solvents, as well as DDD and SIO.

Plastics based on a hybrid binder according to claim 26 with rutile additives and TECS-k (p) fabrics also have high thermophysical and physico-mechanical properties, which are presented below in Table 49.

Table 49
Properties of plastics based on a hybrid binder according to claim 26 with additives of rutile and tissues TEMS-k (p) Name of indicator Hybrid binder based plastics according to claim 26 with additives of rutile and tissues TEMS-p Hybrid binder based plastics according to claim 26 with additives of rutile and tissues TEMS-k Thermophysical properties of plastics Density, g / cm ³ 1.78-1.9 1.27-1.4 Thermal conductivity, W / m 0.27-0.29 0.22-0.24 Heat capacity, kJ / kg 1.1-1.15 1.23-1.25 Thermal diffusivity, m ² / s 1.3-1.33 1.5-1.53 Physico-mechanical properties of plastics Tensile stress in the direction of the base, MPa 125-130 126-135 The modulus of elasticity in the direction of the base, GPa 2.8-3 2.9-3.2 Breaking stress, MPa 90-100 95-110 Breaking stress during crushing, MPa 110-120 115-125 Density, g / cm ³ 1.78-1.9 1.27-1.4 Destructive separation stresses, MPa 65-70 70-90 Destructive shear stress, MPa 15-20 25-30

Plastics based on a hybrid binder according to claim 26 with rutile additives and TEMS-k (p) fabrics have the following advantages compared to plastics of this type with other additives:

- do not corrode from the action of aggressive environments;

- do not lose physical, mechanical and thermophysical properties during 20 years of operation;

- have a slight loss of heat-shielding properties during 20 years of operation - 5-10%;

- have a slight loss of electrical properties during 20 years of operation - 7-15%;

- have a slight loss of electrostatic properties during 20 years of operation - 10-20%;

- loss of destructive separation stresses during 10 years of operation is 10-20%;

- the loss of destructive shear stresses during 10 years of operation is 5-15%.

Hybrid binder based plastics according to claim 26 with rutile additives and TECS-k (p) fabrics:

- to the effect of a 3% solution of hydrochloric acid in sea water;

- to the effects of almost all hydrocarbon solvents;

- to radiation exposure (γ-irradiation with a dose of 0.1 Mrad), and also have high wear resistance (friction coefficient - 0.093-0.095) and water resistance (0.1-3%).

The method of producing a hybrid binder according to claim 26 with rutile additives is carried out in the following sequence.

12-23 parts by weight of the hybrid binder according to claim 1 of the claims located in the mixer reactor are introduced. hexachlorobenzene and antimony trioxide and mixed with each other and the hybrid binder according to claim 1 at temperatures of 40-70 ° C for 3-6 hours per ton of the product being prepared, then rutile is introduced into the product thus prepared in an amount of 12-23 wt.h . and mixed with the previously introduced components there at temperatures of 40-70 ° C for 3-6 hours, followed by cooling to temperatures of 20 ± 1 ° C.

NOTE In the same way, all compositions of hybrid binders according to claim 26 are made.

The efficiency of introducing into the hybrid binder according to claim 26 the additives of boron nitrides introduced into the hybrid binder in an amount of 12-23 parts by weight in the form of finely divided graphite boron nitride (BN), borazon and boiling borazole (B ₃ N ₃ H ₆ ).

Graphite boron nitride (BN) is a colorless crystalline fine (up to 300 microns) powder with increased hardness. Due to the impurities of the carbon in its composition, it may have a grayish-black color. The density of boron nitride is 2.3 g / cm ³ , the melting point is 3023 K (2750 ° C). The remaining characteristics of graphite boron nitride are given in table 10. Boron nitride is chemically neutral at ordinary temperatures.

In a hybrid binder according to claim 26, boron nitride is introduced to obtain plastics based on it and TEMS-k (p) fabrics with increased hardness, as well as for boronation of these plastics, that is, their surface saturation with boron nitride to increase their hardness and / or only their surface hardening.

Borazon is one of the modifications of boron nitride. In nature, borazon does not occur. In terms of density (3.5 g / cm ³ ) and hardness, borazon is not inferior to diamond, one of the polymorphic crystalline modifications of carbon. Borazon has a high refractive index of 2.417, is a good semiconductor, withstands temperatures up to 200 ° C. Borazon is obtained by pressing under a pressure of 6000 MPa at temperatures of 1350 ± 5 ° C from ordinary graphite boron nitride (BN). In a hybrid binder according to claim 26, borazon is introduced to increase the abrasive properties of plastics based on it.

Borazole (B ₃ N ₃ H ₆ ) is an inorganic cyclic compound, low-boiling (at temperatures of 250 ± 5 ° C) liquid, is used as an additive in a hybrid binder according to paragraph 26 of the claims to obtain on its basis and TEMS-k fabrics ( o) heat-resistant plastics and plastic coatings based on them. The viscosity of borazole is 5-7 Pa · s, that is, it is a low viscosity fluid.

The hybrid binder according to claim 26 with additives of boron nitride and / or borazon is obtained in the following process sequence:

- at the first stage, the hybrid binder according to claim 1 is poured into the reactor-mixer and heated to a temperature of 40-70 ° C;

- at the second stage, hexachlorobenzene and antimony trioxide (12-23 parts by weight) with a ratio of components from 1: 1 to 1: 0.1 are introduced into the preheated hybrid binder according to claim 1 of the invention and mixed with a hybrid binder at temperatures 40 -70 ° C for 3-6 hours based on one ton of the prepared semi-finished hybrid binder;

- at the third stage, a powdered mass of boron nitride (12-23 parts by weight) or borazon (12-23 parts by weight) or a mixture thereof (12-23 parts by weight) with a ratio of components from 1: 1 to 1: 0.1 and again all the introduced components are mixed with the semi-finished hybrid binder by means of a mixer at temperatures of 40-70 ° C for 3-6 hours based on one ton of the prepared product;

- at the fourth stage, an alcohol-acetone mixture with a component ratio of 1: 2 is additionally poured into this product and the density of the prepared product is adjusted to 0.95-1.1 g / cm ³ by mixing the introduced alcohol-acetone mixture with the product at temperatures of 40-70 ° C for 3-6 hours based on one ton of the finished product with its subsequent cooling to temperatures of 20 ± 1 ° C.

The hybrid binder according to claim 26 with borazole additives is prepared in the following somewhat altered (compared with the introduction of boron nitride and / or borazone) sequence of operations:

- at the first stage, the hybrid binder according to claim 1 is poured into the reactor-mixer, then borazole is poured into it in an amount of 12-23 wt.h. and mix both liquid composition at temperatures of 40-70 ° C for 30-60 minutes based on one ton of the prepared product;

- at the second stage, hexachlorobenzene with the addition of antimony trioxide (12-23 parts by weight) is added to the product thus prepared and mixed again with the product at temperatures of 40-70 ° C for 30-60 minutes;

- at the third stage, an alcohol-acetone mixture with a component ratio of 1: 2 is introduced into this product and again all the components introduced into the reactor-mixer are mixed at temperatures of 40-70 ° C for 3-6 hours based on one ton of prepared product with bringing its density due to the introduced alcohol-acetone mixture to 0.95-1.1 g / cm ³ , followed by cooling to a temperature of 20 ± 1 ° C.

Further, on the basis of the prepared hybrid binders according to claim 26 with additives of boron nitride, and / or borazon, and / or borazole and TEMC-k (p) fabrics, “prepregs” are made according to the following modes:

- the density of the hybrid binder, g / cm ³ - 0.95-1.1;

- impregnation rate, m / min - 0.85-1.1 (for a hybrid binder according to claim 26 with additives of boron or borazon nitride) and 1.0-1.3 (for a hybrid binder according to claim 26 with borazole additives);

- the temperature in the drying heat chambers of the impregnation machine is 130-200 ° C, with the following properties:

- mass fraction of the hybrid binder according to p. 26 claims - 40-50%;

- mass fraction of moisture and volatile substances - 3.5-5%;

- the warranty period of storage of the "prepreg" at temperatures of 25 ± 5 ° C - not more than 6 days.

Further, from the obtained “prepregs” by winding or pressing methods according to the modes given in Table 14 or 15 of this description, plastic samples and / or plastic cylindrical products are obtained and tested according to the testing methods operating at the FSUE “Avangard” enterprise with obtaining characteristics, presented in tables 50-52.

Table 50
Physical, thermophysical, heat-shielding, electrostatic and physico-mechanical properties of plastics based on a hybrid binder according to claim 26 with the addition of boron nitride, borazon and borazole Indicator Name Hybrid based plastic. communication according to item 26 with additives of boron nitride and fabric TEMS-p Hybrid based plastic. communication according to item 26 with additives of boron nitride and fabric TEMS-k Hybrid based plastic. communication according to item 26 with the addition of borazon and tissue TEMS-p Hybrid based plastic. communication according to item 26 with the addition of borazon and tissue TEMS-k Hybrid based plastic. communication according to item 26 with borazole and TEMS-p tissue additives Hybrid based plastic. communication according to item 26 with borazole and TEMS-k tissue additives Physical and thermophysical properties of plastics Water absorption,% 0.4 0.38 0.36 0.35 0.32 0.3 The sliding coefficient of friction of a pair is plastic based on gibr. communication according to item 26 and anti-friction coating based on TEMS-k fabric (p) 0,096 0,095 0,097 0,096 0.09 0,085 The coefficient of thermal conductivity, W / m · K 0.23-0.24 0.24-0.25 0.22-0.23 0.25-0.26 0.23-0.24 0.26-0.27 The coefficient of thermal diffusivity, · 10 ⁶ , m ² / s 0.13-0.14 0.14-0.18 0.13-0.17 0.21-0.22 0.24-0.25 0.18-0.19 Specific heat, kJ / kg · K 0.91-0.92 0.92-1.36 0.91-1.35 0.93-1.4 0.93-1.38 0.92-1.36 Thermal protective properties of plastics Heat flux, · 10 ⁶ , W / m ² 3,5 3,5 3,5 3,5 3,5 3,5 Heat flow rate, m / s 500 500 500 500 500 500 Average linear ablation by temperature sensor, mm / s 0.7 0.65 0.63 0.6 0.55 0.5 The average speed of ablation by weight loss, mm / s 0.65 0.61 0.6 0.55 0.53 0.51 Effective enthalpy, · 10 ⁶ , J / kg 2,5 3.6 2.6 3,7 2.9 3.95 Oxygen Index,% 56 55 58 57 60 58 Sublimation temperature, ° С 450 370 550 450 850 470 Electrostatic properties of plastics The specific volume resistance, · 10 ⁴ Ohms 1.8-1.9 1.9-2.1 2-2,1 2.2-2.3 2.3-2.4 2.4-2.6 Surface resistivity, · 10 ⁵ , Ohm · cm 5.1-5.3 5.3-5.4 5.35-5.45 5.4-5.5 5.5-5.6 5,6-5,7 Physico-mechanical properties of plastics Tensile stress tensile along the base, MPa 150-155 160-170 175-185 185-190 195-200 205-210 Breaking stress, MPa 100-130 130-150 135-160 160-170 200-210 215-220 Breaking stress during crushing, MPa 110-120 120-125 125-130 135-140 145-150 155-170 Breaking tensile stress, MPa 60-70 70-75 75-80 82-85 90-95 97-100 Destructive shear stress, MPa 20-25 27-31 35-42 45-51 52-55 61-65

The data given in Table 50 show that all plastics based on the hybrid binder according to claim 26 with additives of boron nitride, borazon and borazole (12-23 parts by weight) have increased (compared to plastics previously given in this section) ) physical, thermophysical, heat-shielding, electrostatic and physico-mechanical characteristics. In addition, these plastics have enhanced anti-corrosion and anti-static characteristics.

All plastics based on the hybrid binder according to claim 26 with additives of boron nitride, borazon and borazole more effectively (in comparison with plastics previously given in this section) protect the inner surfaces of glass-carbon-boron-organoplastics from high-temperature heating and accumulation of static electricity.

All these plastics retain their properties over a long period of use (10 years). However, these hybrid binders and plastics based on them have significant disadvantages:

- they do not have radiation resistance even with γ-radiation of 0.1 Mrad;

- the hybrid binder according to claim 26 with additives of boron nitride, borazon and borazole cannot be subjected to radiation curing, since plastics during radiation curing sharply reduce their operational properties (in comparison with other curing methods);

- the following plastics impregnated with the hybrid binder according to claim 26 with additives of boron nitride, borazon and borazole cannot be cured by the radiation method: boroplastics, as well as fiberglass with a high content of boron oxide (Table 3);

- plastics based on this binder emit a significant amount of volatile substances:

- at 20 ± 5 ° C - ethyl alcohol, acetone, toluene,

- at 50 ± 5 ° C - ethyl alcohol, butyl alcohol, acetone, toluene, phenol, aniline, formaldehydes, epichlorohydrin.

In addition, such plastics are poorly processed with a cutting tool equipped with conventional VK hard alloys.

Despite the above disadvantages, these plastics are highly effective and can be used in many industries to protect the internal or external surfaces of products made of composite materials from aggressive environments and high-enthalpy high-speed flows.

The effectiveness of the hybrid binder according to p. 28 claims, a method for its preparation

The hybrid binder according to claim 28 in its composition contains the following components, in parts by weight:

- epoxytriphenol resin ETF - 97-103;

- epoxyaliphatic resin DEG-1 - 9-15;

- resol phenol-formaldehyde resin SF-340F - 31-37;

- acetone - 87-93;

- ethyl alcohol - 43-49;

- toluene oil or coal - 7-13;

- flame retardants - hexachlorobenzene and / or antimony trioxide - 12-23;

- discrete fillers in the form of whiskers (NK) - 2-13: from aluminum oxide (Al ₂ O ₃ ), and / or carbon silicon (SiC), and / or chromium oxides (CrO and / or Cr ₂ O), and / or iron oxides (FeO and / or Fe ₂ O ₃ and / or Fe ₃ O ₄ ).

Fire retardants - hexachlorobenzene and / or antimony trioxide - are introduced into the hybrid binder according to claim 28 to increase the fire resistance and fire safety of plastics based on this binder and fabric fillers, as well as to reduce the levels of explosion and fire hazard of its preparation and processing, as well as to increase heat resistance and improving the antifriction and antistatic properties of plastics based on it and, for example, heat-protective fabrics such as TEMS-k (p).

The whiskers are introduced into the hybrid binder according to claim 28 in order to increase the strength of plastics, mainly with interlayer separation, shear and bending. The amount of each component introduced from whiskers should be no more than 2-10%, which is 2-13 wt.h.

The whiskers can be introduced into the hybrid binder according to claim 28 of the claims, component by component - 2-13 parts by weight and / or group - 2-13 wt.h. two to three components in a group with a ratio of ingredients from 1: 1 to 1: 0.1 (for a group of two components) and from 1: 1: 1 to 1: 0.1: 0.1 (for a group of three components )

The properties of the crystals introduced into the hybrid binder according to claim 28 of the claims are presented in Table 11.

Alumina whiskers are introduced into the hybrid binder according to claim 28 in an amount of 2-13 parts by weight.

Al ₂ O ₃ (alumina) - amphoteric oxide, refractory filament crystals; are introduced into the hybrid binder according to claim 28 in the form of several crystalline modifications (corundum, emery crystals, synthetic corundum crystals, etc.) to increase the strength of plastics based on this binder and various types of fillers, as well as to increase their fire resistance, heat resistance, and thermostability. At the same time, the introduced alumina strand crystals can play the role of adsorbents, catalysts, and other functions.

Aluminum oxides - colorless water-insoluble crystals, the melting temperature of whiskers is 2040 ° C; receive aluminum oxides from bauxite, nepheline and kaolin. Aluminum oxides are good catalysts and adsorbents.

The whiskers can be introduced into the hybrid binder in the form of corundum - aluminum oxide with impurities of chromium, titanium, iron and other elements. The hardness of corundum is 9, the density is 4 g / cm ³ , the origin of corundum is metosomatic, metomorphic material, accumulates in placers of the earth's crust; very good abrasive material, can be introduced into the hybrid binder in the form of emery crystals - a mixture of corundum (Al ₂ O ₃ ) - 60-70% with magnetite, hypatite and spinel.

Synthetic corundum crystals with Cr ³⁺ and Fe ³⁺ additives are manufactured on an industrial scale to produce plastics used, for example, in quantum electronics and the watch industry.

Alumina even in small doses (2-5 parts by weight) play the role of catalytically active structure-forming agents in the hybrid binder according to claim 28, regulate the size and number of formed elements of the supramolecular structure of the binder, and thereby improve the physicomechanical characteristics of the composites, mainly their shear, tear-off and bending.

Whiskers of aluminum oxides in an amount of more than 13 parts by weight can cause unwanted effects in plastics, such as a change in the hygroscopicity and gas permeability of reinforced plastics, as well as a significant slowdown in curing the hybrid binder according to claim 28.

In addition, the introduction of whiskers from aluminum oxides in amounts of more than 13 parts by weight leads to a thickening of the hybrid binder, increases its viscosity, which complicates its processing into "prepregs" and further into structural products from composite fibrous materials.

It is not possible to show the effectiveness of introducing into the hybrid binder according to claim 28 the claims of all whiskers of aluminum oxides on the properties of plastics within the framework of this description. Therefore, below will be considered the effectiveness of introducing into a hybrid binder according to claim 28 of the claims only whiskers of aluminum oxides in the form of corundums with the following properties:

- dispersion of nanocrystals, microns - up to 300;

- density NK, g / cm ³ - 3.95-4.1;

- hardness NK - 9;

- the melting temperature of the NC, K - 2313 (2040 ° C);

- NC breaking stress under tension, GPa - 21-275;

- modulus of elasticity NK, GPa - 415-510.

Introduction to the hybrid binder according to claim 28 of the claims of whiskers with the above properties improves the following properties of plastics based on this binder and TEMS-k (p) fabrics (plastics of this type are taken for consideration and comparison because the rationality of use is most effectively reflected in them NC from aluminum oxides):

- improves the viability of the hybrid binder and "prepregs" based on it in 2-2.5 times;

- the warranty period for storing “prepregs” on the basis of this binder and TEMS-k (p) fabrics is increased from 15 (when 2-3 parts by weight of aluminum oxides are introduced into them) to 30 (when 10-13 parts by weight of them are introduced .aluminium oxides) days;

- the toughness of these plastics increases to 25-85 kJ / m ² (instead of 20-75 kJ / m ² - for these plastics without additives of aluminum oxides);

- increases the vibration-shock-vandal resistance of plastics by 10-30%.

In addition, the strength and stiffness of these plastics significantly increases:

- tensile strength in the direction of the base - 140-150 MPa (instead of 125-130 MPa - for these plastics without additives of aluminum oxides);

- bending strength - 100-125 MPa (instead of 85-90 MPa - for these plastics without additives of aluminum oxides);

- crushing strength - 110-130 MPa (instead of 100-105 MPa - for these plastics without additives of aluminum oxides);

- tensile strength from fiberglass SKN-21 - 20-30 GPa - (instead of 7-10 GPa - for these plastics without additives of aluminum oxides);

- peel strength from fiberglass SKN-24 - 25-40 GPa - (instead of 9-15 GPa - for these plastics without additives of aluminum oxides);

- shear strength - 15-25 GPa (instead of 9-10 GPa - for these plastics without additives of aluminum oxides);

- tensile modulus of elasticity in the direction of the base - 3.0-3.2 GPa (instead of 2.8 GPa - for these plastics without additives of aluminum oxides).

In addition, from the introduction of NC from aluminum oxides into a hybrid binder according to claim 28, many physical, thermophysical, electrostatic, and heat-shielding properties of plastics based on this binder and TEMC-k fabrics (p) are also improved (Table 51).

Table 51
Physical, thermophysical, electrostatic and heat-shielding properties of plastics based on a hybrid binder according to claim 28 with the addition of nanocrystals from aluminum oxides and fabrics TEMS-k (p) Name of indicator Plastic material Flexible based on plastic. communication according to item 28 without additives NC aluminum oxides and fabric TEMS-p Flexible based on plastic. communication according to item 28 without additives NK of aluminum oxides and fabric TEMS-k Flexible based on plastic. communication according to item 28 with additives NK from aluminum oxides and fabric TEMS-p Flexible based on plastic. communication according to item 28 with additives NK from aluminum oxides and fabric TEMS-k Physical and thermophysical properties of plastics Density, g / cm ³ 1.78 1.4 1.85-1.9 1.45-1.5 Water absorption within 24 hours,%, no more 0.4 0.37 0.35 0.3 Pair sliding friction coefficient: heat-proof coating - anti-friction coating 0,093 0,094 0,097 0,099 Thermal conductivity, W / m 0.285 0.239 0.295 0.245 Heat capacity, kJ / kg 1.16 1.25 1.27-1.3 1.28-1.35 Thermal diffusivity, m ² / s 1.38 1,53 1.54-1.55 1.4-1.5 Electrostatic properties of plastics The specific volume resistance, · 10, Ohm · cm 5,4 5.9 5.4-5.5 6.0-6.2 Surface resistivity, · 10 ⁵ , Ohm 1.8 2.7 1.85-1.95 2.8-3.0 Thermal protective properties of plastics Heat flow, · 10 ⁵ , W / m ² 3,5 3,5 3,5 3,5 Heat flow rate, m / s 500 500 500 500 Average linear ablation by temperature sensor, mm / s 0.8 0.75 0.75-0.76 0.73-0.74 Thermal resistance, sec / (kg / m ² ) ² 2.29 4.09 2.3-2.35 4.1-4.2 Effective enthalpy, · 10 ⁶ , J / kg 2.6 3.6 2.65-2.75 3.65-3.8 Sublimation temperature, ° С 600 300 650-670 340-360 Oxygen Index,% 54 53 55-56 54-55

The effectiveness of introducing into a hybrid binder according to claim 28 claims of carbon silicon (SiC) whiskers.

Whiskers of carbon silicon are introduced into the hybrid binder according to claim 28 in an amount of 2-13 parts by weight. together with flame retardants - hexachlorobenzene and / or antimony trioxide in the amount of 12-23 wt.h. to increase mainly physical, thermophysical, electrostatic, heat-shielding and strength characteristics of plastics based on this binder and TEMS-k fabrics (p).

The main properties of nanocrystals made of carbon silicon:

- density, g / cm ³ - 3.16-3.2;

- hardness - 8-9;

- ultimate tensile stress, GPa - 10.97-20.58;

- modulus of elasticity, GPa - 480.2-483.1;

- dispersion, microns - up to 300.

Fire retardants - hexachlorobenzene and / or antimony trioxide in an amount of 12-23 wt.h. - are introduced into the hybrid binder according to claim 28 of the claims mainly to increase the fire resistance and fire safety of plastics based on it, as well as to ensure the explosion safety of technological operations for the preparation and processing of the hybrid binder according to claim 28 of this composition.

The whiskers of carbon silicon have a dark gray metallic luster, the melting point is 2963 K (2690 ° C), they are resistant to aggressive environments, hydrocarbon solvents, etc.

In a hybrid binder according to claim 28, carbon-silicon whiskers are introduced to improve the thermophysical, heat-shielding, electrostatic and physico-mechanical properties of plastics based on it and TEMS-k fabrics (p).

Introduction NC carbon silicon in an amount of 2-13 wt.h. in this binder increases the impact strength of plastics based on this binder and fabrics TEMS-k (p) by 20-30% (impact strength - 30-90 kJ / m ² ). The introduction of carbon nanocrystal silicon together with hexachlorobenzene and / or antimony trioxide increases the strength of plastics based on this binder and TEMC-k tissues (p):

- ultimate tensile stress in the direction of the base, MPa - 130-160 (instead of 125-126 MPa without additives NC carbon silicon);

- breaking stress at bending, MPa - 100-110 (instead of 89-90 MPa without additives NC carbon silicon);

- breaking stress during crushing, MPa - 110-120 (instead of 105-106 MPa without additives NC carbon silicon);

- tensile modulus of elasticity, MPa - 2.9-3.2 (instead of 2.8 MPa without additives of carbon nanocrystals);

- breaking stress when separated from the structural plastic SKN-21, MPa - 15-30 (instead of 6-9 MPa without the addition of nanocrystals of carbon silicon);

- destructive stress when separated from the structural plastic SKN-24, MPa - 20-35 (instead of 10-12 MPa without the addition of nanocrystalline carbon silicon).

Table 52
Physical, thermophysical, electrostatic and heat-shielding properties of plastics based on a hybrid binder according to claim 28 with the addition of nanocrystals made of carbon silicon and TEMS-k fabrics (p) Name of indicator Plastic material Flexible based on plastic. communication according to item 28 without additives NC carbon silicon and fabric TEMS-p Flexible based on plastic. communication according to item 28 without additives NC carbon silicon and fabric TEMS-k Flexible based on plastic. communication according to item 28 with additives NC made of carbon silicon and fabric TEMS-p Flexible based on plastic. communication according to item 28 with additives NC made of carbon silicon and fabric TEMS-k Physical and thermophysical properties of plastics Density, g / cm ³ 1.79 1.27 1.8-1.9 1.28-1.3 Water absorption within 24 hours,%, no more 0.4 0.37 0.3 0.25 Pair sliding friction coefficient: heat-proof coating - anti-friction coating 0,093 0,094 0,096 0,097 Thermal conductivity, W / m 0.285 0.239 0.3-0.4 0.27-0.29 Heat capacity, kJ / kg 1.16 1.25 1.2-1.5 1.6-1.9 Thermal diffusivity, m ² / s 1.38 1,53 1.4-1.6 1.55-1.85 Electrostatic properties of plastics The specific volume resistance, · 10 ⁴ , Ohm · cm 5,4 5.9 5.5-5.6 6.1-6.3 Surface resistivity, · 10 ⁵ , Ohm 1.8 2.7 1.9-2.1 2.9-3.1 Thermal protective properties of plastics Heat flow, · 10 ⁵ , W / m ² 3,5 3,5 3,5 3,5 Heat flow rate, m / s 500 500 500 500 Average linear ablation by temperature sensor, mm / s 0.8 0.75 0.72-0.73 0.71-0.72 Thermal resistance, sec / (kg / m ² ) ² 2.29 4.09 2.1-2.2 3.9-4.1 Effective enthalpy, · 10 ⁶ , J / kg 2.6 3.6 2.7-2.8 3.7-3.9 Sublimation temperature, ° С 600 300 700-750 390-420 Oxygen Index,% 54 53 53-54 53.5-54.5

The effectiveness of introducing into a hybrid binder according to claim 28 the whiskers of chromium oxides (CrO ₂ , Cr ₂ O ₃ ).

Chromium oxide whiskers - 2-13 parts by weight are introduced into the hybrid binder according to paragraph 28 of the claims together with flame retardants - hexachlorobenzene and / or antimony trioxide - 12-23 wt.h. for the following purpose:

- to increase the heat resistance, thermal stability, fire resistance and wear resistance of plastics based on this binder and fabrics TEMS-k (p);

- to increase the physical, thermophysical, heat-shielding and physico-mechanical properties of plastics based on this binder and TECS-k fabrics (p);

- to increase their impact strength, hardness and strength, mainly on bending, tearing and shear;

- to improve the anticorrosive and antifriction properties of plastics based on this binder and TEMS-k tissues (p).

CrO ₂ - acid oxide, dark green, refractory, water-insoluble whiskers with a density of 7.1 g / cm ³ , hardness of 8-9 and a melting point of 2163 K (1890 ° C).

The hybrid binder of claim 28 with CrO ₂ and TEMS-k (p) fabrics can be used to produce heat-protective plastics and plastic coatings based on them with high physical, thermophysical, electrostatic, heat-shielding and physico-mechanical characteristics.

Plastics based on a hybrid binder according to claim 27 with chromium oxide (CrO ₂ ) additives can be used to protect glass-boron-carbon-organoplastics from aggressive environments and high-temperature flows of high intensity.

Cr ₂ O ₃ is an amphoteric oxide, dark green, water-insoluble crystals, with a density of 7 g / cm ³ , hardness of 7-8, and a melting point of 2163 K (1890 ° C). The ultimate tensile stress of chromium oxide whiskers is 8.85 GPa, and the elastic modulus is 240 GPa.

Chromium oxide (CrO ₂ ) whiskers can be introduced into a hybrid binder according to claim 27 to increase abrasive properties, and also used as a catalyst in the organic synthesis of a hybrid binder (increases the viability of the hybrid binder without additives in 2-2.5 times).

Chromium oxide (Cr ₂ O ₃ ) whiskers are introduced into the hybrid binder according to claim 28 both as a pigment for coloring plastic products based on this binder in dark green protective tones and as a filler to impart plastics to it based on high antistatic and anti-corrosion properties.

The main properties of plastics based on the hybrid binder according to claim 28 with additives from chromium oxides and TECS-k fabrics (p) are given in Table 53 below.

Table 53
Physical, thermophysical, electrostatic and heat-shielding properties of plastics based on a hybrid binder according to claim 28 with the addition of nanocrystals from chromium oxides and fabrics TEMS-k (p) Name of indicator Plastic material Flexible based on plastic. communication according to item 28 without additives NK from chromium oxides and tissue TEMS-p Flexible based on plastic. communication according to item 28 without additives NK from chromium oxides and tissue TEMC-k Flexible based on plastic. communication according to item 28 with the addition of NK from chromium oxides and tissue TEMS-p Flexible based on plastic. communication according to item 28 with the addition of NK from chromium oxides and tissue TEMS-k Physical and thermophysical properties of plastics Density, g / cm ³ 1.79 1.27 1.85-1.95 1.3-1.45 Water absorption within 24 hours,%, no more 0.4 0.37 0.35 0.3 Pair sliding friction coefficient: heat-proof coating - anti-friction coating 0,093 0,094 0,098 0,099 Thermal conductivity, W / m 0.285 0.239 0.32-0.42 0.28-0.3 Heat capacity, kJ / kg 1.16 1.25 1.24-1.53 1.62-2.0 Thermal diffusivity, m ² / s 1.38 1,53 1.5-1.65 1.6-1.9 Electrostatic properties of plastics The specific volume resistance, · 10 ⁴ , Ohm · cm 5,4 5.9 5.53-5.65 6.12-6.35 Surface resistivity, · 10 ⁵ , Ohm 1.8 2.7 1.95-2.25 2.94-3.15 Thermal protective properties of plastics Heat flow, · 10 ⁵ , W / m ² 3,5 3,5 3,5 3,5 Heat flow rate, m / s 500 500 500 500 Average linear ablation by temperature sensor, mm / s 0.8 0.75 0.75-0.77 0.75-0.76 Thermal resistance, sec / (kg / m ² ) ² 2.29 4.09 2.2-2.3 4.0-4.4 Effective enthalpy, · 10 ⁶ , J / kg 2.6 3.6 2.77-2.86 3.75-3.95 Sublimation temperature, ° С 600 300 720-780 400-450 Oxygen Index,% 54 53 55 55.5 Physico-mechanical properties of plastics Tensile stress in the direction of the base, MPa 125-130 127-132 130-135 140-150 Tensile modulus, GPa 2,8 2.85 2.9 3,1 Breaking stress, MPa 90-95 92-95 94-97 94-98 Breaking stress during crushing, MPa 108 110 110-120 115-125 Destructive separation stresses, GPa 70-150 80-160 75-160 85-170 Destructive shear stress, GPa 7-10 10-12 15-30 16-40

The data in Table 53 show that plastics based on a hybrid binder according to claim 28 with additives of chromium oxide NK provide more reliable protection of glass-boron-carbon-organoplastics from high enthalpy gas flows.

Hybrid binder plastics according to claim 28 with the addition of chromium oxide nanocrystals reliably protect composite fiber materials from the occurrence and accumulation of static charges on their surfaces.

These plastics also have a long-term antistatic effect and retain their antistatic effect for 20 years at temperatures of ± 50 ° C and relative humidity up to 98%.

Plastics of this type are wear-resistant, resistant to the action of light, friction, various solvents, aggressive environments, including aggressive environments DDD and OV.

Flame retardant plastics, and their manufacture meets all the requirements of explosion-fire-vandal safety.

Plastics based on a hybrid binder according to claim 28 with chromium oxide additives have a number of significant drawbacks: they are poorly processed with a conventional cutting tool, a significant amount (from 3 to 7%) of volatile gas products is emitted at temperatures:

20 ± 5 ° С - ethyl alcohol, acetone;

50 ± 5 ° С - ethyl alcohol, acetone, toluene, phenol, aniline, butyl alcohol, formaldehydes, epichlorohydrin.

Nevertheless, such plastics have a great prospect of application in the rocket and space, aviation and other industries.

The efficiency of introducing into the hybrid binder according to claim 28 the claims of whiskers from iron oxides (FeO, Fe ₂ O ₃ , Fe ₃ O ₄ ).

The whiskers of iron oxides are introduced into the hybrid binder according to claim 28 to increase the strength of plastics based on it and TEMC-k (p) fabrics, mainly tear-off, shear and bend. Threadlike crystals of iron are introduced into the hybrid binder according to claim 28 in the form of its oxides - FeO, Fe ₂ O ₃ , Fe ₃ O ₄ .

FeO is the main oxide, black whiskers of iron with a wide homogeneity region, with a dispersion of up to 300 microns, hardness of 7-9, density of 7.85 g / cm ³ ; are introduced into the hybrid binder according to claim 28 of the claims to obtain, on its basis, both TEMC-k (p) fabrics and other ferromagnetic plastics, as well as to modify the properties of other plastics based on it.

Fe ₂ O ₃ - mixed oxide, black refractory crystals; are introduced into the hybrid binder according to claim 27 for improving the physical, thermophysical, electrostatic, heat-shielding and special properties of plastics based on it. The dispersion of nanocrystals from Fe ₂ O ₃ is up to 300 microns, hardness is 6-8, density is 7.8 g / cm ³ .

Fe ₃ O ₄ - amphoteric oxide, whiskers of black or dark gray color; whiskers of this type are introduced into the hybrid binder according to claim 27 to increase the physicomechanical properties of plastics, as well as to improve the physical, thermophysical, electrostatic, heat-shielding and special properties of plastics based on it.

In a finely divided form (up to 100 μm), Fe ₃ O ₄ whiskers can be used both as pigments and as adsorbents — catalysts for the organic synthesis of the hybrid binder according to claim 27.

NK modifications of this type:

- spongy iron, obtained by direct reduction from ores at temperatures below the formation of the liquid phase;

- carbon iron, obtained by thermal decomposition of iron pentocarbonyl, is particularly clean and highly dispersed (up to 10 microns), etc.

In the hybrid binder of claim 28, carbon iron is introduced to produce, on its basis, tissue fillers of particularly pure non-porous plastics.

Plastics based on this hybrid binder with additives of NK from iron oxides have an increased viability of about 2-3 times higher than the viability of the hybrid binder according to claim 28 without NC from iron oxides.

The introduction of nanocrystals from iron oxides into plastics makes it possible to reduce the exothermic effect upon curing, reduce shrinkage, increase the physicomechanical, mainly tear-off, shear, and bend characteristics and improve many physical, thermophysical, electrostatic, and heat-protective characteristics, as well as a number of special properties : resistance to fire, radiation and aging, as well as improved electrical, magnetic and other properties, as well as reduce the cost of plastics.

Properties of iron oxide whiskers introduced into the hybrid binder: melting point - 1813 K (1540 ° С), tensile stress - 13.03 MPa, elastic modulus - 198.8 GPa, hardness - 9-10, dispersion - up to 300 microns.

Whiskers of iron oxides - 2-13 parts by weight are introduced into the hybrid binder according to claim 28 of the claims simultaneously with flame retardants - hexachlorobenzene and / or antimony trioxide - 12-23 wt.h.

NCs from iron oxides are introduced into a hybrid binder according to claim 28 to modify the properties of plastics, mainly based on this binder and TEMS-k (p) fabrics, including their antistatic properties, flame retardants - hexachlorobenzene and antimony trioxide - for increasing the fire resistance of plastics, their fire safety, as well as improving their antifriction properties due to the TEMS-k (p) fabrics and antimony trioxide.

Table 54 below summarizes the main characteristics of plastics based on TEMC-k (p) fabrics and the hybrid binder of claim 28 modified with whiskers of iron oxides.

Table 54
The main characteristics of plastics based on fabrics TEMS-k (p) and a hybrid binder according to claim 28, modified with whiskers of iron oxides

Indicator Name Hybrid based plastic connection according to item 28 with the addition of whiskers from iron oxides and fabrics TEMS-p Hybrid based plastic connection according to item 28 with the addition of whiskers from iron oxides and tissues TEMC-k Physical and thermophysical properties of plastics Density, g / cm ³ 1.8-2.1 1.3-1.5 Water absorption within 24 hours,%, no more 0.4 0.5 Pair sliding friction coefficient: heat-proof coating - anti-friction coating 0,091-0,094 0,092-0,095 Thermal conductivity, W / m 0.25-0.27 0.21-0.24 Heat capacity, kJ / kg 1.2-1.3 1.27-1.36 Thermal diffusivity, m ² / s 0.15-0.2 0.13-0.14 Electrostatic properties of plastics The specific volume resistance, · 10 ⁴ , Ohm · cm 5.4-5.7 5.9-6.3 Surface resistivity, · 10 ⁵ , Ohm 1.8-2.0 2.7-3.0 Thermal protective properties of plastics Heat flow, · 10 ⁵ , W / m ² 3,5 3,5 Heat flow rate, m / s 500 500 Average linear ablation by temperature sensor, mm / s 0.75 0.65 The average speed of ablation by weight loss, mm / s 0.7 0.6 Thermal resistance, sec / (kg / m ² ) ² 2.4-2.8 4.2-4.6 Oxygen Index,% 5,6-5,7 5.4-5.5 Effective enthalpy, · 10 ⁶ , J / kg 2.7-3.0 3.7-4.2 Sublimation temperature, ° С 710-750 410-460 Physico-mechanical properties of plastics Tensile stress in the direction of the base, MPa 140-180 180-210 Tensile modulus, GPa 3.0-3.1 3.1-3.5 Breaking stress, MPa 110-130 130-170 Breaking stress during crushing, MPa 107-110 115-125 Destructive separation stresses, MPa 60-245 (with radial orientation in a magnetic field up to 300) 70-250 (with radial orientation in a magnetic field up to 290) Destructive shear stress, GPa 6-75 10-80 Tear-off voltage from plastic type SKN-21, GPa 15-25 20-30 Tear-off voltage from plastic type SKN-24, GPa 20-35 30-40

The characteristics of plastics based on the hybrid binder according to claim 28 with the addition of nanocrystals from iron oxides and fabrics TEMC-k (p) tend to decrease, below are data on the decrease in the characteristics of plastics during long-term storage (for 10 years) under ± 50 ° С and relative humidity up to 98%:

- physical and mechanical - does not occur, with the exception of a decrease in shear and tear characteristics by 10-20%;

- thermophysical - decrease by 2-5%;

- heat-shielding - reduced by 7-10%;

- electrical - reduced by 10-15%;

- electrostatic - reduced by 15-20%.

Plastics based on a hybrid binder according to claim 28 with additives of iron oxide from iron oxides are resistant to aggressive environments, including DDD and OV agents, lubricants, ointments, hydrocarbon solvents, etc.

Plastics of this type are biostable (from rodents, termites, etc.) and mushroom-resistant, resistant to radiation (γ-radiation with a dose of 0.1 Mrad).

Disadvantages of plastics of this type: plastics are poorly processed with a cutting tool equipped with conventional VK hard alloys; plastics emit a significant amount of gas products (3-7%):

at 20 ± 5 ° С - alcohol, acetone;

at 50 ± 5 ° С - alcohol, acetone, toluene, phenol, aniline, epichlorohydrin, formaldehydes, etc.

The processing methods of the hybrid binder according to claim 28 with the addition of NCs from iron oxides and tissue fillers are conventional (set forth in Tables 14, 15).

Despite the above disadvantages, plastics of this type are highly effective and can be used in many industries. Many performance characteristics of plastics based on a hybrid binder according to claim 28 with the addition of nanocrystals and fabric fillers can be improved by the additional introduction of carbon-graphite mixtures, carbon black, powder metal oxides and nitrides, as well as various types of silicon oxides.

All plastics based on hybrid binders according to claim 28 with additions of nanocrystals and fabric fillers are electrically conductive, with their help the problems of protecting products from composite fibrous materials from the occurrence and accumulation of static electricity charges that occur during their operation are completely solved.

The warranty period of storage and operation of this type of plastics at temperatures ± 50 ° С and relative humidity up to 98% is 20 years.

The effectiveness of the hybrid binder according to claim 29

In the hybrid binder according to claim 29, finely dispersed powder fillers are introduced containing nitrides and / or metal and silicon oxides selected from the group: magnesium oxide - burnt magnesia, aluminum oxides - alumina, titanium oxides - rutile, silicon oxides - silica, nitrides boron or mixtures thereof in various ratios of components.

All of the above powder fillers are introduced into the hybrid binder according to claim 29 in a single component and / or in groups of 2-6 components per group. They are introduced into the hybrid binder in the form of powder fillers in the amount of 7-18 wt.h.

All of the above fillers in a hybrid binder according to claim 29 of the claims are used mainly to modify the physical, thermophysical, electrostatic, heat-shielding, physico-mechanical characteristics of plastics based on this hybrid binder and fabric fillers of different types.

The effectiveness of their single-component incorporation into a hybrid binder according to claim 29 is broadly disclosed in the descriptions to claims 26, 27, 29-33 of the claims. In the description of the effectiveness of using a hybrid binder according to claim 32, the effectiveness of the joint use of aluminum and silicon oxides introduced into the hybrid binder according to claim 32 in ratios from 1: 1 to 1: 0.1 is partially disclosed, and in the description of the effectiveness of use The hybrid binder of claim 33 partially discloses the effectiveness of the joint use of boron nitrides: BN, borazone and borazole.

All other metal and silicon oxides and nitrides introduced into the hybrid binder according to claim 29 (magnesium, titanium, aluminum, silicon oxides, boron nitrides and their modifications) can be introduced into it in groups of 2-6 or more components in group. They can be introduced to improve the many properties of plastics made from this hybrid binder and various types of woven and / or filament fillers.

Unfortunately, the variety of combinations of components from metal and silicon oxides and nitrides introduced into the hybrid binder according to claim 29 of the claims is so great, and their influence on the properties of plastics is so insignificant (within the entered masses of powder fillers - 7-18 parts by weight) that does not allow, within the framework of this description, to conduct a complete analysis of the properties of plastics obtained on the basis of these combinations of materials.

Apparently, this analysis should be done separately in relation to the structural features of composite fiber materials in which the use of these materials is possible and effective.

The effectiveness of the hybrid binder according to claim 30, a method for its preparation

In the hybrid binder according to claim 30, powdered magnesium oxide (MgO) is introduced, which is mainly used to modify the physical properties of composites based on it.

Magnesium oxide - burnt magnesia, is a fine (up to 10 microns) silver-white refractory powder having the properties shown in table 10. Magnesium oxide is introduced into the hybrid binder according to claim 30 as a filler in an amount of 7-18 parts by weight. with the aim of:

- increase the heat resistance and thermal stability of composite plastics made on the basis of this binder and fabrics TEMS-k (p),

- increase the impact strength of glass-carbon-boron-organoplastics formed by winding and / or pressing;

- increasing the specific strength and stiffness of the composites, tensile and shear strengths, as well as improving some of their heat-shielding characteristics.

The increase in the toughness of the hybrid binder composites according to claim 30 depends on:

- the amount and dispersion of the powdered filler of magnesium oxide introduced into them, as well as the uniformity of its distribution;

- humidity of the powdered filler of magnesium oxide introduced into the composites;

- conditions for its pretreatment, that is, on the time and temperature of the heat treatment of powdered magnesium oxide introduced into the composite;

- technological regulations for the processing of a hybrid binder together with the introduced powdered magnesium oxide at various stages of its processing into products, that is, from:

- technologies for the preparation of a hybrid binder;

- modes of obtaining on its basis tissue "prepreg" semi-finished products;

- modes of molding and curing of plastics formed on the basis of these "prepregs".

Note - In order to improve the physicomechanical, thermophysical and some other characteristics of reinforced plastics (for example, their hygroscopicity, hydrophobicity and gas impermeability), powdered magnesium oxides introduced into hybrid binders must be annealed (immediately before introduction into the binder) in a heat chamber at temperatures of 250- 450 ° C for 3-6 hours, and then cooled under vacuum to temperatures of 40-70 ° C.

The introduction of a powdered mass of magnesium oxide into a hybrid binder according to claim 30 is recommended within the following limits:

- for products obtained by pressing methods - up to 30-40% by weight;

- for products obtained by winding methods - up to 20-30%.

Note - The introduction of a powdered mass of magnesium oxide into a hybrid binder according to claim 30 of the claims above 40% is not recommended for products obtained by conventional winding methods, since this leads to an increase in the viscosity of the hybrid binder (up to 1-5 MPa) and, as a result, difficult conditions for its processing, and, therefore, the quality of the products obtained.

Magnesium oxide (burnt magnesia) can also be used as a pigment to impart a specific silver-white color to the hybrid binder and plastics based on it.

It should be borne in mind that the introduction of powdered magnesium oxide into a hybrid binder in large quantities (more than 40%) significantly increases its density, which affects its adhesive characteristics, plastics on such a binder become prone to the formation of large shrinkage, significant internal stresses, warping, cracking pore formation, etc.

A method of obtaining a hybrid binder according to claim 39 of the claims consists in introducing into the hybrid binder according to claim 1, located in the mixing reactor, an additional powdery filler - magnesium oxide in an amount of 7-18 parts by weight and mixing it with a hybrid binder according to claim 1 at temperatures of 40-70 ° C for 3-6 hours based on one ton of the product being prepared and its subsequent cooling to temperatures of 20 ± 1 ° C.

The main properties of plastics based on a hybrid binder according to claim 30 and glass-carbon-boron-organo-fillers are presented in table 54.

Table 54
The main properties of various materials based on a hybrid binder according to claim 30 Name of characteristic Material fiberglass carbon plastics boroplasty organoplasty Density, g / cm ³ 1.6-2.2 1.3-1.9 1.6-1.9 1.2-1.35 Tensile stress, MPa

785-1670 885-1375 785-1480 Shear breaking stress, MPa

Tensile modulus, GPa

118-196 176-265 60-76 Shear modulus, GPa 1.19-20 9.8-15 9.8-13 2,5-15 Elongation at Tension,%

0.4-1 0.3-0.7 2-7 Specific Strength, km 35-110 33-85 75-85 69-120 Specific Stiffness, km 1110-3350 10850-12500 12500-14500 5100-5900 Impact strength, kJ / m ² 20-690 26-85 45-90 160-195 Poisson's ratio

0.22-0.3 0.22-0.25 0.35-0.36 Water absorption,% 0.05-6 0.12-3 0.06-3 3-18 The coefficient of thermal expansion, -10 ⁶ , K ^-1 3,5-30

4-5 0.6-5.5 Specific heat, kJ / (kg · K) 1.7-4.2

1.1-1.2 1.4-2.3 The coefficient of thermal conductivity, W / (m · K) 0.14-0.65

0.5-0.7 0.11-0.37 Thermal diffusivity, · 10 ⁶ , m ² / h 0.3-1.0

0.24-0.58 0.2-0.55 Note - The numerator shows values of the indicator along the direction of reinforcement, and in the denominator - across the direction of reinforcement

The effectiveness of the hybrid binder according to p. 31 of the claims, the method of its production

Titanium oxide (TiO ₂ ) - rutile - is introduced into the hybrid binder according to claim 31 in an amount of 7-18 parts by weight in the form of a white fine powder with a particle size of 1-100 microns and the properties shown in table 10. The effectiveness of its introduction into a hybrid binder is due to several reasons:

- firstly, titanium oxide in an amount of 7-18 parts by weight is introduced into the hybrid binder according to claim 31 to increase the toughness of plastics formed on its basis, while the toughness of the composites based on a binder according to claim 1 with powder additives of rutile can be increased by 50-70%;

- secondly, titanium oxide increases some physico-mechanical characteristics of plastics formed on the basis of a hybrid binder according to claim 31, in particular, characteristics of plastics such as:

- resistance to cracking;

- resistance to heat and light flux;

- specific strength and stiffness of plastics;

- hardness of plastics to local loads;

- thirdly, titanium oxide increases the corrosion resistance of plastics formed on the basis of a hybrid binder according to claim 31, therefore, a hybrid binder with titanium oxide additives can be used for:

- Creation of power structures for aerospace engineering;

- education on the basis of this binder heat-protective plastic anti-corrosion coatings of mines and smoke trunks;

- giving the composites a specific color;

- giving the composites some specific properties, such as: resistance to cracking, adhesion to fibers, vibration resistance, etc.

Although a hybrid binder with titanium oxide additives in plastics carries no more than 5% of the total load, it is in a difficult stress state, since its main role is to redistribute the load between the fibers. Only when stretching unidirectional plastics, the conditions for the deformation of the filler and the cured binder (polymer matrix) are approximately the same.

Fibers that do not coincide in direction with the acting force cause a significant concentration of stresses in the binder, the level of which is determined by the ratio of the elastic moduli of the components.

Moreover, the destruction in the layers with transverse reinforcement occurs during deformations that are significantly smaller than the tensile strains of the hybrid binder according to claim 1. The formation of microcracks during loading of the composition is a consequence of stress concentrations due to both the nature of the reinforcement and the presence of point microdefects in the structure, the less dispersion of the introduced rutile powder, the less point defects in the structure of plastics based on a hybrid binder according to claim 31 of the formula inventions.

The process of microcrack formation begins at a certain level of stress, called the fracture toughness limit of the composite material. For example, for fiberglass based on a hybrid binder according to claim 31 and T-10/2 fiberglass, the tensile crack resistance limit is 85-92% of its tensile strength and varies depending on the ratio of components (binder, filler and finely divided additive titanium oxide).

The shear strength of the binder plays a significant role in creating critical structures. It should be at least not lower than the adhesion strength of the binder to the fiber. With sufficient accuracy for practice, the shear strength of fiberglass based on a hybrid binder according to paragraph 31 of the claims can be considered equal to 55-75% of their tensile strength.

In real conditions, when selecting components of a hybrid binder, attention was paid to the adhesion strength to the fiber. It is known that poor adhesion leads not only to the destruction of the most loaded fibers, but is also accompanied by a significant increase in the stress concentration in the cured hybrid binder, which ultimately reduces the bearing capacity of structures based on it.

The mechanism of adhesive bonding of the binder with reinforcing fibers includes physical, chemical, electrical phenomena, friction of the fibers on the polymer matrix during their mechanical compression in the composition. The high level of the specific surface area of the used fibers (0.2-2.3 m ³ / g), compliance with the conditions of their critical length (0.12-1 mm) and the optimal dispersion of the rutile additives introduced into the hybrid binder (1-10 μm) are determinants of the adhesive strength of the composite material.

An important role is given to chemical adhesion, which depends on the type of polar groups that make up the molecules of substances in contact with each other. In this regard, the hybrid binder used in accordance with claim 31 compares favorably with other types of binders, since it allows for substantially equal cohesive strengths to achieve a significant increase in the specific strength of plastics.

Unfortunately, at present, a generalized criterion of requirements for binders has not yet been developed, which would combine the strength and deformation properties of fibrous fillers with reinforcement patterns and the nature of the loading of the composition, physico-mechanical and thermophysical properties of the latter, and also take into account the technological features of molding methods, sizes and form designs, economic indicators. The same can be said about fillers. So far, the development of new types of binders and plastic structures based on them is associated with a large amount of experimental research, especially time-consuming and expensive, when testing the design of the product and the technology for its manufacture is carried out on full-scale samples and / or products.

Unfortunately, due to the large volume of experimental studies, as well as their complexity, duration of reproduction, and expensiveness, it is not possible to reveal the whole range of issues related to the production of plastics based on a hybrid binder according to claim 31 with additives of titanium oxide and fabric fillers of different structures.

After all, additives introduced into a hybrid binder change a wide range of properties of plastics, therefore, this description will focus only on the main effects created by additives introduced into the binder (and composites based on it).

For example, the introduced additives from titanium oxides and soot (or carbon-graphite mixtures) significantly (except for the main strength, thermophysical and antistatic properties) increase the quality and operational reliability of plastics from the action of aggressive media, such as:

- the effect of aggressive media gases and vapors of substances;

- the action of solutions of alkalis and basic salts;

- the effect of neutral and acid salts;

- the effect of solutions of sulfuric, nitric and other acids.

All plastics based on a hybrid binder with additives of titanium oxide and soot (and / or carbon-graphite mixtures) have increased heat resistance and thermal stability (by 20-50% in comparison with plastics based on a hybrid binder according to claim 1). Plastics based on a hybrid binder according to claim 31 and glass-carbon-boron-organo-fillers withstand long-term (up to 1000 hours) temperatures - 180-300 ° C.

All plastics based on a hybrid binder according to paragraph 31 of the claims are suitable for long-term operation (up to 10 years without repair) in a mildly cold climate at temperatures of the working zone of ± 50 ° C and humidity up to 98%, while maintaining high anti-corrosion and antistatic properties in for 10 years.

Table 55 below shows the main properties of various materials based on a hybrid binder according to claim 31.

Table 55
The main properties of various materials based on a hybrid binder according to p. 31 claims Name of characteristic Material fiberglass carbon plastics boroplasty organoplasty Density, g / cm ³ 1.7-2.3 1.4-2.0 1.7-1.9 1.3-1.45 Tensile stress, MPa

790-1675 890-1400 790-1490 Shear breaking stress, MPa

Tensile modulus, GPa

120-200 180-270 65-81 Shear modulus, GPa 1,2-21 9.9-16 9.9-13.5 2.6-15.4 Elongation at Tension,%

0.3-0.8 0.2-0.6 1,5-5 Specific Strength, km 40-120 35-89 79-90 73-125 Specific Stiffness, km 1120-3400 10900-13000 13000-15000 5200-6000 Impact strength, kJ / m ² 25-695 27-89 50-95 165-200 Poisson's ratio

0.23-0.3 0.23-0.26 0.36-0.37 Water absorption,% 0.045-5.5 0.13-3.1 0.07-3.1 3.1-18.1 The coefficient of thermal expansion, · 10 ⁶ , K ^-1 3.6-30.1

4.1-5.1 0.61-5.6 Specific heat, kJ / (kg · K) 1.8-4.3

1.2-1.3 1.5-2.5 The coefficient of thermal conductivity, W / (m · K) 0.15-0.66

0.6-0.8 0.12-0.39 Thermal diffusivity, · 10 ⁶ , m ² / h 0.4-1.1

0.25-0.6 0.25-0.59 Note - The numerator shows values of the indicator along the direction of reinforcement, and in the denominator - across the direction of reinforcement

A method of obtaining a hybrid binder according to claim 31 of the claims consists in introducing into the hybrid binder according to claim 1, located in the mixing reactor, an additional finely divided filler - titanium oxide in an amount of 7-18 parts by weight and mixing it with a hybrid binder according to claim 1 at temperatures of 40-70 ° C for 3-6 hours based on one ton of the product being prepared and its subsequent cooling to temperatures of 20 ± 1 ° C.

The effectiveness of the hybrid binder according to claim 32

In a hybrid binder according to claim 32, the oxides of aluminum and / or silicon oxides in the amount of 7-18 parts by weight are used as finely divided fillers.

Alumina (Al ₂ O ₃ ) - alumina - amphoteric oxide capable of entering into chemical compounds with binder components and exhibiting both acidic and alkaline properties with them.

Alumina can have several powder and crystalline modifications: aluminosilicates, aluminates, as well as water-insoluble feldspars, mica, etc., and can be used in a hybrid binder in an amount of 7-18 wt.h. for:

- increase heat resistance, thermal stability and fire resistance of composites based on it;

- increase the impact strength of composites based on it;

- increase the physicomechanical properties of composites and, in particular, to increase their strength during interlayer shear and separation, and especially to increase the transversal strength and stiffness of composites;

- as an adsorbent, that is, as a component on the surface of which adsorption occurs - the concentration of certain substances from the volume of phases on the interface: as an agent that slows down the rate of chemical reactions that occur in the binder during its curing, and increases the viability of the binder;

- as a silver-white pigment that allows you to change the color of the composites.

Alumina can be introduced into the hybrid binder in the form of several modifications:

- in the form of aluminum oxide (Al ₂ O ₃ ) - alumina silver-white refractory powder with a dispersion of crystals of 1-100 microns in an amount of 7-18 wt.h. to the mass of the hybrid binder according to claim 32 of the claims with the properties shown in table 10;

- in the form of aluminosilicates, that is, groups of chemical compounds based on silicates (SiO ₂ + Al ₂ O ₃ , SiO ₄ + AlO ₄ , etc.).

In the first embodiment, powdered alumina can be used to improve the physical, thermophysical, electrostatic, heat-shielding, and physicomechanical characteristics of plastics (introduced into the hybrid binder in the form of a powder mass up to 40% by weight of the binder).

Alumina mainly increases the impact strength of plastic - from 10 to 50% (depending on the amount of introduced mass and its dispersion: the higher the dispersion, the higher the impact strength of plastic, the higher the tensile, shear and tear strength of plastic, the higher and transversal characteristics of cylindrical plastics from composite fibrous materials, in particular, their transversal strength and stiffness).

In the second embodiment, aluminum oxide is introduced into the hybrid binder according to claim 32 of the claims, together with silicon oxides in the form of particulate fillers to 5-10% by weight of binder administered dimensions in hybrid binder particulate fillers _of Al ₂ O, AlO ₄ and SiO _2, SiO ₄ can range from 1 to 300 microns.

The introduction of finely dispersed fillers from Al ₂ O ₃ , AlO ₄ , SiO ₂ , SiO _4, and others into the composition of plastics makes it possible to reduce the exothermic effect during curing of the binder, reduce shrinkage, reduce the entrainment of plastic from the effects of high-speed highly enthalpy gas-dynamic flows, and also improve mechanical and some thermophysical characteristics of plastics, as well as a number of their special properties - radiation and aging, electrical, electrostatic, magnetic, etc.

The introduction of fine powder fillers of aluminum and silicon oxides into a hybrid binder according to claim 32 of the claims makes it possible to significantly reduce the cost of plastics formed on its basis.

The introduction of aluminum and silicon oxides (Al ₂ O ₃ , AlO ₄ , SiO ₂ , SiO ₄ , etc.) into this hybrid binder can be used both as fillers, and as thickeners, and as retardants for curing the hybrid binder according to claim 32.

In particular, aluminum oxides (Al ₂ O ₃ , AlO ₄ , etc.) together with silicon oxides (SiO ₂ , SiO ₄ , etc.) can also be used to increase the viability of the hybrid binder. In this embodiment, aluminum and silicon oxides can be used in the form of molecular sieves capable of adsorbing various components of the hybrid binder, including the components of its hardener - resin SF-340A.

The use of aluminum oxides in crystalline sodium aluminosilicates (claims 13-18) or pure aluminosilicates in the form of zeolites is recommended as molecular sieves.

Their introduction into a hybrid binder according to claim 32 of the claims may be carried out by several methods:

- directly by mixing with a hardener - resin SF-340A at various stages of its preparation;

- pre-saturation of the hybrid binder with pairs of adsorbed hardener;

- introducing into the binder in the form of Na zeolites, that is, sodium aluminosilicates in the form of solid particles with a regular porous structure and dispersion up to 10-15 microns.

Introduced (up to 5-10% by weight of the hybrid binder) molecular sieves such as Na zeolite (or sodium aluminosilicates) can increase the viability of the hybrid binder according to claim 32 by a factor of 2-3.5 and simultaneously reduce the shrinkage of plastics based on it, and consequently, to reduce the formation of internal stresses in such plastics, which are most significant at the phase boundary.

It should be noted that the magnitude of the internal stresses in plastics, and, therefore, their transversal strength, largely depends on:

- type of reinforcing filler, its composition, structure and technology of its processing;

- the presence of lubricants and / or dressings applied to it;

- coefficients of thermal expansion of the materials of the composite and mandrel;

- wall thickness of the composite;

- geometric dimensions and shapes of the composite;

- the degree and speed of curing of the hybrid binder and other parameters.

All of the above parameters and their analysis cannot be disclosed in the materials of this application, since they are beyond the scope of the claims of this patent.

However, they cannot be ignored, since the most significant drawback of all plastics is their low strength at interlayer separation - 59-245 MPa (transverse strength) and low strength at interlayer shear - 5.9-78.5 MPa.

In concluding the description of this section, we can conclude that the introduction into a hybrid binder according to claim 32 of the claims of heterogeneous porous substances based on aluminum and silicon oxides significantly (by 200-300%) increases the viability of these binders, and also increases the toughness of the composites on them basis (by 20-50%) and transversal strength (by 30-40%).

Note - All of the above parameter values significantly depend on the methods of manufacturing structural composites and fillers used for their formation. So, for example, it is practically impossible to obtain unidirectional material containing less than 55% filler by winding and drawing, in pressed plastics the content of fibrous filler can vary from 40 to 65%, and composites obtained by the method of dry impregnation of filler in closed form are usually characterized filler content from 30 to 50%. The maximum filling of the composition when spraying a binder does not exceed 30%.

For plastics containing powder fillers from aluminum and silicon oxides, the relationship of the properties of the starting components and their ratios (binder, filler and additives) with the properties of the finished composition has not yet been established.

In this invention, for the first time, an attempt was made to evaluate the strength properties of composites depending on the binder and filler, critical sizes — fiber lengths, shape and size of filler particles, their orientation, etc.

In general, predicting certain properties of plastics based on a hybrid binder according to claim 32, it should be noted that if the deformative properties of composites can be estimated based on an analysis of their macrostructure, then their physical, thermophysical, electrostatic, heat-shielding and other properties - only by test methods taking into account the mechanisms of their destruction.

The effectiveness of the hybrid binder according to claim 33

In a hybrid binder according to claim 33, boron nitrides, borazon (BN) and borazole (B ₃ N ₃ H ₆ ) in the amount of 7-18 parts by weight are used as fillers.

Borazon is one of the crystalline forms of boron nitride, crystals with a particle size of up to 100 microns, not inferior to diamond in hardness, but more heat-resistant and durable; is introduced into the hybrid binder according to paragraph 33 of the claims to obtain, on its basis, and filament woven fillers of superhard abrasive plastics, which can be used to create:

- elastic-flexible tape spirals made of composite fibrous materials;

- visco-elastic tape spirals with "elastic memory";

- heat-resistant plastics with high heat and flame retardant properties and erosion resistance;

- to obtain boroplastics - reinforced plastics containing as filler monofilament or woven and / or nonwoven materials from boron fiber.

Boroplasty with borazon additives can be used:

- for the manufacture of highly loaded plastic structures;

- for hardening metal structures;

- to improve the properties of GRP formed mainly based aluminoborosilicate yarns or fabrics having in its composition up to 10% boron oxide (B ₂ O _3), up to 54% of silicon oxide (SiO ₂₎ and to 7-25% of aluminum oxide ( Al ₂ About ₃ ) and 7-25% of iron oxides (Fe ₂ About ₃ ) (table 3).

Fiberglass based on the specified glass filler and a hybrid binder according to paragraph 33 of the claims can also be used for the manufacture of structures of space rocket and aviation equipment.

The main properties of the powdered filler of boron nitride (BN) are presented in table 10:

- molecular weight - 24.8;

- density, g / cm ³ - 2.27;

- melting point, K - 3023;

- boiling point, K - 3273;

- specific heat, kJ / (kg · K) - 0.92;

- coefficient of thermal conductivity, W / (m · K) - 14.3.

In addition, the borazon additives introduced with the above properties can be used to modify the properties of the hybrid binder based composites according to claim 33. It is proposed to introduce finely dispersed borazon powder (up to 100 μm) in the amount of 7-18 parts by weight of this hybrid binder. The borazon introduced in this amount significantly increases the impact strength of plastics, which is, kJ / m ² :

- for fiberglass - 25-750;

- for carbon plastics - 30.5-90.3;

- for boroplastics - 55-98;

- for organoplastics - 170.8-210.1.

At the same time, the modified borazon plastics have rather high and other characteristics of plastics, for example, water absorption, with the exception of organoplastics, in which water absorption is in the range of 3-18%, while for fiberglass, boroplastics and carbon plastics it is in the following limits,%:

- for fiberglass - 0.05-6;

- for carbon plastics - 0.12-3;

- for boroplastics - 0.06-3.

One of the crystalline modifications of boron nitride is white graphite, a white, talc-like powder; is introduced into the hybrid binder according to claim 33 as an additive in an amount of 7-18 parts by weight to obtain on its basis refractory plastics with high fire-erosion resistance.

In addition, plastics based on a hybrid binder according to claim 33 and TEMS-k (p) fabrics can be used as anti-friction wear-resistant materials with high sublimation and antistatic properties.

Plastics with graphite additives in an amount of 7-18 parts by weight or other carbonated products, for example, carbon black, carbon-graphite mixtures, carbon silicon, etc. - as antifriction electrically conductive materials that can be widely used in electrical engineering, mechanical engineering, nuclear energy, etc., for example, to create plastic retarders in nuclear reactors, for creation of solid lubricants from composites, as well as for modification of a number of thermophysical and special properties of plastics, and in combination with flame retardants and metal oxides - resistance to fire, radiation aging, vibration resistance, and to improve the electrical, electrostatic, electromagnetic, semiconductor, and other properties.

The hybrid binder according to claim 33 has a number of significant drawbacks: plastics based on it with the introduction of more than 18 parts by weight of them. boron nitride has a low water resistance (in fiberglass plastics, water absorption within 24 hours is 0.05-6%, in boroplastics - 0.06-3%, in carbon plastics - 0.12-3%, and the highest water absorption in organoplastics is 3- 18%), which significantly reduces the operational capabilities of such plastics under conditions of exposure to aggressive environments and high-temperature gas flows - (3.5-4) · 10 ⁶ W / m ² and flow rates - 500-600 m / s.

In plastics based on a hybrid binder according to claim 33, finely divided fillers of boron and borazon nitrides can also cause undesirable effects such as a change in their hygroscopicity and gas permeability.

With the introduction of boron nitrides into the hybrid binder according to claim 32 of the claims above 18 parts by weight there is a significant increase in its viscosity (up to 1-5 Pa · s), which impairs the impregnation of such hybrid binder compositions under atmospheric pressure.

Therefore, for the effectiveness of the impregnation of hybrid binder fillers with such compositions, it is recommended that they be impregnated under vacuum, and / or under pressure, and / or under the influence of ultrasonic waves, or under the influence of a magnetic field with a strength of 120-1100 E.

The aforementioned drawbacks in the impregnation of tissue fillers with a hybrid binder according to claim 33 are easily eliminated if, instead of borazon, borazole - B ₃ N ₃ H _{6 is} introduced from the composition of these binders.

Borazole is no longer a powder filler, but an inorganic cyclic compound, a low boiling and volatile liquid. Borazole is a high-tech additive for a hybrid binder according to claim 33, which can be used to produce heat-resistant polymer plastics.

Firstly, its introduction into a hybrid binder according to claim 33 in an amount of 7-18 parts by weight lowers its viscosity from 0.1 to 1 Pa · s (when controlling viscosity with a VZ-4 viscometer, this corresponds to 15-85 s), and it is these viscosity of the binder that are more effective for impregnating complex tissue structures.

Secondly, a hybrid binder with borazole additives 7-18 wt.h. with a viscosity of 0.1 to 1 Pa · s, it easily penetrates the interstitial spaces of tissue fillers and fills pores with a diameter of 5-15 microns, and in large-tonnage mass production of plastic products, fibers with a diameter of 5-15 microns are mainly used.

The most common technological recommendations for using a hybrid binder according to claim 33 are as follows: it is more expedient to use fibers with a diameter of 5-10 microns with a predominance of phenol-formaldehyde fractions, and fibers with a diameter of 11-15 microns with a predominance of epoxy fractions. The hybrid binder according to claim 33 with borazole additives can be impregnated with woven and / or filler fillers with any lubricants and finishes, including straight ones, which include substances with high adhesive and hydrophobic properties.

Direct lubricants increase not only the adhesion strength of the fibers, but also their weather and water resistance. At the same time, these lubricants, the basis of which are most often made up of organosilicon compounds (diethylaminomethyltriethoxylan, epoxypropylethoxylan, etc.), can limit the viability of the hybrid binder according to claim 33 to within 3 days, and in this case, the composition of this binder with borazole additives it is necessary to additionally introduce crystalline aluminosilicates and / or molecular sieves such as Na zeolite, which contribute to an increase in the viability of this binder by 2-3.5 times.

The most effective use of boron nitrides in the creation of boroplastics. With a density of boroplastics of 1.65-1.95 g / cm ³ they have the following properties:

- ultimate tensile stress, MPa - 885-1390;

- breaking stress at shear, MPa -

- modulus of tensile elasticity, GPa - 180-270;

- shear modulus, GPa - 10.5-15.5;

- elongation,% - 0.2-0.5;

- specific strength, km - 75-95;

- specific stiffness, km - 12500-15500;

- impact strength, kJ / m ² - 45-95.

Note - In the numerator are given the values of the indicator along the direction of reinforcement, and in the denominator - across this direction.

The effectiveness of the hybrid binder according to clause 34 of the claims

In a hybrid binder according to claim 34, discrete additives are introduced in the form of monolithic or hollow whiskers made of aluminum, chromium, iron and carbon silicon oxides.

All of the aforementioned fillers are introduced into the hybrid binder according to claim 34 in a single component and / or in groups of 2-3 components in a group. They are introduced into the hybrid binder in the form of whiskers in an amount of 2-18 wt.h.

All of the above whiskers are introduced into the hybrid binder according to claim 34, mainly to increase the physicomechanical characteristics of plastics based on this binder and fabric or filament fillers, as well as to modify the physical, thermophysical, electrostatic, heat-shielding, physico-mechanical characteristics of plastics on the basis of this hybrid binder and tissue fillers of various types.

The effectiveness of their one-component introduction into a hybrid binder according to claim 34 is widely disclosed in the descriptions to claims 28, 35-38 of the claims.

All of the above whiskers can be introduced into the hybrid binder according to claim 34 and in groups of 2-3 or more components in the group. They are introduced to increase the physicomechanical characteristics of plastics, mainly tear-off, shear and bend, as well as to modify some properties of plastics based on this hybrid binder and woven and / or filamentous fillers.

Unfortunately, the variety of combinations of whiskers introduced into the hybrid binder according to claim 34 is quite large, and their influence on the properties of plastics is so insignificant (within the introduced masses of whiskers - 2-18 parts by weight) that it does not This description to conduct a complete analysis of the properties of plastics obtained on the basis of these combinations of whiskers.

Apparently, this analysis should be done separately in relation to the structural features of composite fibrous materials in which the use of these whiskers is possible and effective.

The effectiveness of the hybrid binder according to clause 35 of the claims

The hybrid binder according to claim 35 of the claims contains in its composition whiskers of aluminum oxide in an amount of 2-18 parts by weight

Alumina (Al ₂ O ₃ ) whiskers are introduced into the hybrid binder according to claim 35 in order to increase the strength of the composites based on it, including during interlayer shear and bending, providing the composites with high physical and mechanical characteristics, especially transverse ( tear-off) strength.

Alumina - amphoteric oxide, refractory whiskers of silver-white color. They are introduced into the hybrid binder according to claim 35 in an amount of 2-18 parts by weight. as:

- filler (base) of ultralight composites used in aerospace engineering;

- hybrid binder catalyst;

- an adsorbent to slow down the curing of the hybrid binder according to claim 35, increasing the viability of the binder by 2-3.5 times.

Alumina whiskers are capable of exhibiting both basic and acidic properties depending on the nature of the hybrid binder reactants that interact with it.

Alumina in nature exists in the form of several crystalline modifications - feldspars, clays, mica, etc. Alumina whiskers can be introduced as a filler into a hybrid binder to create refractory plastics based on it, which simultaneously have high heat-fire-erosion properties.

The most effective use of aluminum oxide is in the composition of aluminosilicates - groups of chemical compounds based on silicates, in which aluminum is also present in the form of aluminates. Such groups of aluminates (for example, Al ₂ O ₃ + SiO ₂ , AlO ₄ + SiO ₄ , etc.) can be used as part of a hybrid binder according to claim 35 both as fillers, and as catalysts, and as adsorbents.

Table 56 below shows the properties of whiskers of aluminum oxides in comparison with a powder filler of aluminum oxides.

Table 56
Properties of Alumina Filaments Compared to Alumina Powder Filler Name of material Density, g / cm ³ Melting point, K Tensile stress, GPa Modulus of elasticity, GPa Specific heat, kJ / (kg · K) The coefficient of thermal conductivity, W / (m · K) Alumina whiskers 3.94-3.96 2313 20.58-275.3 413.6-507.6 1.05 29.5 Powdered Alumina (Alumina) 3.97-3.98 2288 20-225 395-450 1.09 30,2

Whiskers of aluminum oxides are introduced into the hybrid binder according to claim 35 to increase the mechanical strength of plastics based on it: rupture, shear, shear, bending and bending strength, including interlayer shear and tear strength.

For example, the introduction of whiskers of aluminum oxide in an amount of 2-18 wt.h. in a hybrid binder according to claim 35, it is possible to increase the shear strength of plastics based on it and TEMS-k (p) fabrics by 20-30%, and the transverse by 25-40%.

The introduction into the hybrid binder according to claim 35 of the formula of the invention simultaneously and whiskers of aluminum oxide in an amount of 2-18 wt.h. and powdered aluminum oxide (alumina) in an amount of 2-18 wt.h. in a ratio of 1: 1 to 1: 0.1 increases both the impact strength of plastics (by 5-10%), and mechanical strength, mainly bending strength (by 10-15%), shear (by 15-20%) and separation (25-35%).

Alumina whiskers can be introduced into the hybrid binder according to claim 35 as a molecular sieve, they are usually introduced into the hybrid binder in the form of crystalline aluminosilicates (AlO ₄ + SiO ₄ ). Their introduction into a hybrid binder can be carried out both by direct mixing with a hardener - resin SF-340A, and by pre-saturation of ETF and DEG-1 resins with pairs of an adsorbing hardener.

For example, molecular sieves such as Na zeolite (or sodium aluminosilicate) increase the viability of the hybrid binder by 2.5-3.5 times. It is noted that plastics based on a hybrid binder according to claim 35 and the TEMS-k (p) fabrics have: both high thermal conductivity (0.23-0.24 W / m · deg) and high heat capacity (1.16- 1.25 kJ / kg · deg), and high thermal diffusivity ((1.38-1.55) · 10 ³ m ² / s).

In addition, plastics based on a hybrid binder according to claim 35 have high electrostatic characteristics (specific volume resistivity (5.4-5.9) · 10 ⁴ Ohm · cm, specific surface resistance (1.8-2.8 ) · 10 ⁵ Ohms), and high heat-shielding and antistatic characteristics (effective enthalpy for plastics based on a hybrid binder according to claim 35 and TEMS-k fabrics (p) - (3.26-4.35) · 10 ⁶ J / kg, the average linear ablation plastic with gas flow velocity 500 m / sec and a heat flux of 3.5 x 10 ⁶ W / m ² - 0,5-0,75 mm / sec) and the high sublimation temperature (350-450 ° C - for fabrics of type TEMS-k, 650-850 ° C - for fabrics of type TEMS-p), and high fire resistance (oxygen index: KI ≈ 55-56% - for fabrics of TEMS-k, KI ≈ 56-57% - for TEMS-p tissues).

In this case, plastics based on a hybrid binder according to claim 35 of the invention prevent the occurrence and accumulation of static charges on their surfaces during operation and, in addition, have a long-term antistatic effect, while maintaining an antistatic effect under various operating conditions: atmospheric and aggressive environments of flue gases, various hydrocarbon solvents, acids and alkalis, sea water, oils, lubricants, as well as means of degassing, decontamination and disinfection tion.

In addition, plastics based on a hybrid binder according to claim 35 and TEMS-k (p) fabrics can be guaranteed to be used at temperatures of ± 50 ° C and relative humidity up to 98% for 20 years, without reducing their physical and mechanical and thermophysical characteristics (with the exception of a decrease in tear strength - by 10-20%, as well as heat-shielding - by 5-10% and electrostatic - by 15-20% of characteristics).

The effectiveness of the hybrid binder according to clause 36 of the claims

36 to the hybrid binder according to claim 36, whiskers of carbon silicon (SiC) are introduced in an amount of 2-18 parts by weight

Silicon carbon - dark gray with a metallic luster whiskers, are introduced into the hybrid binder according to claim 36 to form a large group of heat-erosion-flame retardant plastics used in aerospace engineering based on it.

The following are the main properties of carbon-silicon whiskers:

- density, g / cm ³ - 3.16-3.2;

- melting point, K - 2963 (2690 ° С)

- destructive stress, GPa - 10.97-20.58;

- modulus of elasticity, GPa - 480-485.

Plastics based on a hybrid binder according to claim 36 with additives of whiskers of carbon silicon in an amount of 2-18 parts by weight possess high specific strength and rigidity and, in addition, have high heat-fire-erosion resistance; are used in hybrid binder formulations according to claim 36 to obtain plastics with high bending, shear and tear-off heat resistance, as well as to obtain plastics having a number of specific properties: resistance to fire, radiation, aging, electrostatic, electrical, magnetic and other properties .

The hybrid binder according to claim 36 increases the heat resistance of plastics based on it, mainly with interlayer separation and shear. The addition of whiskers of carbon silicon in an amount of 2-18 wt.h. into a hybrid binder allows to obtain plastics based on it with the following interlayer characteristics:

- according to the interlayer shift, MPa - 10-90;

- by interlayer separation, MPa - 80-300.

Hybrid binder-based plastics according to claim 36 when operating under conditions of high temperatures have the lowest temperature stresses and they are the best of all of the above plastics to resist warping, especially when exposed to high-temperature high-speed gas flows (heat flows (3.5- 4,5) · 10 ⁶ W / m ³ , high-speed flows - 500-600 m / s).

Heat-protective plastics based on a hybrid binder according to clause 36 of the claims and TEMS-k (p) fabrics have high thermophysical, heat-shielding and electrostatic characteristics (Table 59). These plastics have high impact strength, especially plastics formed on the basis of aluminoborosilicate fibers, in which the impact strength is 25-750 kJ / m ² .

In addition, plastics based on the hybrid binder according to clause 36 of the claims and carbon and / or boron fibers (strands or bundles) have increased specific strength and stiffness and increased heat-shielding characteristics (Tables 57, 58).

Table 57
The strength of plastics based on a hybrid binder according to claim 36 and fillers of glass, carbon, boron and organic fabrics Materials Density, g / cm ³ Specific Strength, km Specific Stiffness, km Destructive stress, MPa Elastic modulus E, GPa Shear modulus G, GPa Relative extension, % tensile on shift SKN 1.6-2.2 35-100 1100-3350 350-1850 6.5-63.5 13-20 1,2-21 1.5-2.9 UKN 1.3-1.9 33-85 10800-12000

10-45 117-196 10-15 0.9-4.5 BKN 1.6-1.9 75-85 12500-15000 885-1400

174-265 10-13 0.3-0.7 OKN 1.2-1.4 67-115 5000-6000 785-1500

60-77.5 3-15 2-7 Note - The numerator shows values of the indicator along the direction of reinforcement, in the denominator - across the direction of reinforcement Table 58
Thermal protective properties of reinforced plastics based on a hybrid binder according to claim 36 and glass-carbon-boron-organic fillers Material Water absorption The coefficient of thermal expansion, × 10 ⁶ , K ^-1 Specific heat, kJ / kg · K The coefficient of thermal conductivity, W / (m · K) Thermal diffusivity × 10 ³ , m ² / hour SKN 0.05-6 3,5-30 1.8-4.5 0.15-0.66 0.3-1 UKN 0.12-3

BKN 0.06-3 4-5 1.1-1.15 0.5-0.8 0.24-0.58 OKN 3-18 0.6-5.5 1.4-2.5 0.11-0.38 0.2-0.55 Note - The numerator shows values of the indicator along the direction of reinforcement, in the denominator - across the direction of reinforcement

Table 59
Thermophysical and heat-shielding properties of plastics based on a hybrid binder according to claim 36 of the claims and TEMS-k fabrics (p) Material Heat flow, W / m ² Effective enthalpy, J / kg Thermal resistance, sec / (kg / m ² ) ² Sublimation temperature, ° С The average speed of ablation by weight loss, mm / s Surface resistivity, Ohm Volume resistivity, Ohm · cm Oxygen Index,% The hybrid binder of claim 35 + TEMS-p 3,510 ⁶ 2.510 ⁶ 0.5 · 10 ⁶ 750-800 0.8 (1.7-2) · 10 ⁵ (5-5.3) 10 ⁴ 45-53 The hybrid binder of claim 35 + TEMS-k 3,510 ⁶ 3,510 ⁶ 4.210 ⁶ 350-450 0.7 (2-2.6) · 10 ⁵ (5.3-6) 10 ⁴ 53-56 Note - The above data show that all plastics (except heat-shielding) based on a hybrid binder according to claim 36 have high physical and mechanical characteristics, and heat-shielding plastics based on TEMS-k (p) fabrics also have high sublimation (effective enthalpy (2.5-3.5) · 10 ⁶ J / kg) and electrostatic (specific surface resistance (1.7-2.6) · 10 ⁵ Ohm, specific volume resistance (5-6) · 10 ³ Ohm · cm) properties

All plastics (and construction ones - glass-carbon-boron-organoplastics, and heat-shielding based on TEMS-k (p) fabrics and a hybrid binder according to claim 36 of the claims) are technologically advanced in manufacture, can be produced by dry winding methods; the thicknesses of the layers of the products (both structural and heat-shielding) are reproduced with high accuracy (0.1-0.25) ± 0.1 mm, since they are provided only by the dimensions of the fabric fillers and the geometry of the equipment on which they are made.

In addition, heat-protective plastics based on a hybrid binder according to claim 36 and TEMS-k (p) fabrics have a long-term antistatic effect and have a water absorption of no more than 0.4% within 24 hours. In addition, plastics are highly resistant to virtually all known aggressive environments, including the effects of aggressive environments of flue gases, acids, alkalis, sea water, oils, lubricants, hydrocarbon solvents, as well as detergents and DDD (degassing, decontamination and disinfection).

Water absorption in heat-shielding plastics of this class can be reduced to 0.1-0.3% due to the operation of calcination of whiskers of carbon silicon introduced into the hybrid binder according to claim 36.

Recommended annealing modes of carbon-silicon silicon whiskers: 200-800 ° С without air for 3-6 hours, followed by uniform cooling of heat chambers with carbon-silicon whiskers in them.

Note - The physico-mechanical characteristics of heat-shielding plastics based on a hybrid binder according to claim 36 and TEMS-k (p) fabrics are low, 2-5 times lower than structural plastics based on glass-carbon-boron-organofillers.

The description of the physicomechanical properties of plastics based on hybrid binders according to claim 36 and TEMS-k (p) fabrics is given below in the description text:

- ultimate tensile stress in the direction of the base, MPa - 152-160;

- destructive stress during bending, MPa - 89-100;

- destructive stress during crushing, MPa - 110-130;

- destructive separation (transverse) stresses, GPa:

from structural fiberglass SKN-21 - 15-20;

from structural fiberglass SKN-24 - 20-30.

In addition, plastics based on a hybrid binder according to claim 36 and TEMS-k (p) fabrics practically do not reduce their physical, mechanical and thermophysical properties during 10 years of operation at temperatures of ± 50 ° C and relative humidity up to 98%.

The heat-shielding properties of such plastics during long-term operation (10 years) are reduced by 10-15%, and electrical and electrostatic - by 15-25%. The greatest decrease in the strength properties of such plastics during long-term operation is observed for transverse (tear-off) stresses, the decrease of which reaches 20-30% from SKN-21 fiberglass and up to 10-15% from SKN-24 fiberglass.

Plastics based on a hybrid binder according to claim 36 and TEMC-k (p) fabrics have a significant drawback - they emit gaseous products during operation: at temperatures of 20 ± 5 ° C - ethyl alcohol, acetone, toluene; at temperatures of 50 ± 5 ° С - ethyl alcohol, acetone, toluene, phenol, butyl alcohol, formaldehydes, and when burning also ammonia, carbon dioxide, phosphoric and chlorine anhydrides, water vapor and other volatile gas emissions.

The effectiveness of the hybrid binder according to clause 37 of the claims

In a hybrid binder according to claim 37, whiskers of chromium and its oxides are introduced in an amount of 2-18 parts by weight.

The chromium whiskers have a gray-steel color, have very high heat resistance and hardness (with a density of 7.18 g / cm ² , a melting point of 1903 ° C and a hardness of 9-10). In its pure form, the introduction into a hybrid binder according to claim 37 of the claims as an additive for crystals of pure chromium is difficult due to technological difficulties in obtaining its discrete compositions.

As additives to the hybrid binder according to claim 37, chromium oxides — Cr ₂ O ₃ and / or CrO ₃ can be introduced.

Cr ₂ O ₃ is an amphoteric oxide, dark green refractory, water-insoluble whiskers. Depending on the nature of the reactants of the hybrid binder, Cr ₂ O ₃ may exhibit both acidic and basic properties. In the hybrid binder of claim 37, Cr ₂ O ₃ can be used for several purposes:

- as a component of heat-protective plastics based on a hybrid binder according to claim 37 and TEMS-k (p) fabrics for protecting plastics like SKN and others from the effects of aggressive flue gas environments and high temperatures (from 180 to 300 ° C);

- as a filler for structural plastics with increased wear resistance;

- as a catalyst in the organic synthesis of a hybrid binder according to claim 37;

- as a pigment for plastics, dyeing them in a dark green color.

CrO ₃ - acid oxide, dark red crystals soluble in organic solvents and water. CrO ₃ is used in a hybrid binder according to claim 37 as:

- an oxidizing agent of organic compounds in a hybrid binder (during chemical interaction with them, CrO ₃ exhibits acidic properties);

- filler type SKN plastics formed on the basis of a hybrid binder according to clause 37 of the claims and fiberglass fabrics of various structures and linear densities;

- a component introduced into the hybrid binder according to clause 37 of the claims to obtain chrome heat-protective coatings or heat-protective plastics based on it, used to increase the corrosion resistance of structural plastics such as SKN.

Chromium oxide whiskers are introduced into a hybrid binder according to claim 37 to create plastics based on it with high corrosion resistance, as well as the formation of protective coatings based on these plastics for applying them to metal-plastic surfaces, as well as to increase the impact strength of plastics and their tensile strength, compression, bending, tearing and shear. Chromium whiskers have the following characteristics:

- density, g / cm ³ - 7.1-7.2;

- melting point, K - 2160-2170;

- ultimate tensile stress, GPa - 8.85-9.5;

- modulus of elasticity, GPa - 240-250.

In a hybrid binder according to clause 37 of the claims simultaneously with whiskers in an amount of 2-18 wt.h. aniline is also introduced (2-5 parts by weight); it is introduced into a hybrid binder in the composition of phenol-formaldehyde resin SF-340A to bind free formaldehyde.

Due to this selection of the composition of the hybrid binder plastic based on it and the TEMC-k (p) fabrics, an insignificant amount of gas is released during the operation of the products.

The gas evolution products of such plastics are as follows:

- at operating temperatures of 20 ± 5 ° C - ethyl alcohol, acetone, toluene;

- at operating temperatures of 50 ± 5 ° C - ethyl alcohol, butyl alcohol, acetone, phenol, aniline, formaldehyde and epichlorohydride.

Based on the hybrid binder according to claim 37 and boron fillers, plastics with high abrasive properties are obtained; the friction coefficient of such plastics with a metal counterbody is in the range of 0.094-0.096. Such plastics have high wear resistance and are corrosion resistant even under prolonged exposure to aggressive environments of flue gases, as well as acids, alkalis, hydrocarbon solvents, etc.

Such plastics are biostable (from fungal formations, termites, rodents and other bio-effects). Such plastics are also resistant to the effects of radiation (γ-radiation, dose 0.1 Mrad), as well as ultraviolet, electromagnetic, ultrasonic and microwave radiation.

Structural plastics such as SKN (winding fiberglass), BKN (winding boroplastics), UKN (winding carbon plastics) and OKN (winding organoplastics) have the following characteristics:

- impact strength, kJ / m ² - SKN - 21-685, BKN - 44-88, UKN - 26-82, OKN - 157-192;

- specific strength, km - SKN - 30-100, BKN - 75-90, UKN - 35-85, OKN - 67-120;

- specific stiffness, km - SKN - 1150-3350, BKN - 13000-15000, UKN - 10900-12500, OKN - 5500-6000.

Destructive stresses, moduli of elasticity and shear of plastics based on a hybrid binder according to claim 37 of the claims and glass-boron-carbon-fillers are presented in table 60.

Table 60
Destructive stresses, moduli of elasticity and shear of plastics based on a hybrid binder according to claim 37 of the claims and glass-boron-carbon-organo-fillers Name of materials Destructive stress, MPa Elastic modulus E, GPa Shear modulus G, GPa σ _p σ _sd σ _neg tensile on shift at separation tensile SKN 345-1770 6.5-60.5 50.5-250 13-70 1,2-19,7 BKN 885-1375

61.5-270 176.5-265 10.1-13.2 UKN 785-1670

50.9-260

10,1-15 OKN 785-1500

60.1-255 59-77 2,5-15 Ceramics 137-372 30-295 - 89-490 0.98-19.6 Polymers 0.98-343 1.96-59 - 0.5-17.6 0.76-2.45

Thermophysical properties of plastics based on a hybrid binder according to clause 37 of the claims and glass-boron-charcoal-fillers are presented in table 61.

Table 61
Thermophysical properties of plastics based on a hybrid binder according to claim 37 and glass-boron-carbon-organo-fillers

Name of material The coefficient of thermal expansion × 10 ⁶ , K ^-1 Specific heat, kJ / (kg · K) The coefficient of thermal conductivity, W / (m · K) Thermal diffusivity × 10 ³ , m ² / h SKN 3,5-30 1.7-4.2 0.14-0.65 0.3-1 BKN 4-5 1.1-1.3 0.5-0.7 0.25-0.6 UKN

OKN 0.6-5.3 1.4-2.3 0.19-0.37 0.2-0.55 Ceramics 0,1-48 0.01-4.2 0.11-208 0.85-38 Polymers 4-550 0.5-2.9 0.09-1.1 0.1-15 Metals 1,5-32 0.1-2.3 16-418 36-460 Note - In the tables in the numerator are the values of the indicator along the direction of reinforcement, and in the denominator - across this reinforcement

The ranges of values given in the tables of characteristics of materials on a hybrid binder according to claim 37 are determined by the influence of various factors, starting with the features of the reinforcement and the hybrid binder and ending with the differences in the technological parameters of manufacture, there are a lot of these differences.

For example, the use of non-twisted threads instead of twisted ones increases the strength and stiffness of plastics by 10-15%, and the use of fibers with direct sizing instead of paraffin emulsion - by another 5-7%. It affects the strength and stiffness of plastics and the content of pores in them, which can vary over a wide range (from 0.5 to 30%) depending on the technological factors of plastic molding processes.

For example, only the surface layer of the hybrid binder according to claim 37 with a thickness of 0.1-0.3 mm on the wound product has a porosity of 0.6-1.5%. Porosity significantly affects the strength properties of plastics, for example, an increase in porosity from 1 to 10% reduces the strength of plastics by 1.5-2 times, especially bending strength and, to a lesser extent, strength in interlayer bending and tearing.

The remarks given in this paragraph are true for almost all plastics based on hybrid binders according to claims 1-38 of the claims, to a lesser extent - for plastics based on hybrid binders according to claims 1 to 18, and to a greater extent - for plastics based on hybrid binders according to claims 19-38.

Heat-protective plastics, for example, based on a hybrid binder according to clause 37 of the claims and TEMS-k fabrics (p) (especially pressed according to the regimes presented in Table 11), have higher sublimation (effective enthalpy (2.6-4, 5) -10 ⁶ J / kg, KI oxygen index - 45-60%) and electrostatic (specific surface resistance (1.8-3.6) · 10 ⁵ Ohm, specific volume resistance (5.4-6.1) · 10 ⁴ Ohm · cm) properties. In addition, heat-protective plastics based on a hybrid binder according to claim 37 and TEMS-k (p) fabrics have higher (in comparison with glass-boron-carbon-organoplastics) heat-shielding and electrostatic characteristics:

- thermal conductivity, W / m · deg - 0.24-0.3;

- heat capacity, kJ / kg · deg - 1.16-1.26;

- thermal diffusivity, m ² / s - 1.4-1.55;

- specific volume resistance, Ohm · m (Ohm · cm) - 1.2 (0.12 · 10 ³ );

- oxygen index,% - 45-60;

- specific volume resistance, Ohm · cm - (5.2-5.9) · 10 ⁴ ;

- specific surface resistance, Ohm - (1.6-2.9) · 10 ⁵ ;

- thermal resistance, sec (kg / m ² ) ² - 2.2-4.2;

- sublimation temperature, ° С - 350-850;

- the average rate of ablation by weight loss with a heat flux of 3.6 · 10 ⁶ W / m ² and a gas flow velocity of 600 m / s, mm / s - 0.5-0.7.

All heat-protective plastics based on a hybrid binder according to claim 37 of the claims and TECS-k fabrics (p) are biostable materials; these materials are mainly intended for the manufacture of structural products (chimneys, elastic-flexible tape spirals, components and parts of rocket and space technology, etc.) and coatings for them in order to protect their internal and external surfaces from high-temperature gas-dynamic heating, exposure to aggressive environments and the accumulation of static electricity.

Guaranteed shelf life of heat-protective plastics based on a hybrid binder according to claim 37 and TEMS-k (p) fabrics at temperatures ± 50 ° C and relative humidity up to 98% - 20 years.

Physical and thermophysical properties of plastics based on a hybrid binder according to claim 37 of the claims and TEMS-k fabrics (p):

- water absorption within 24 hours, not more than 0.4%;

- slip coefficient of friction of a pair: a heat-resistant coating based on a hybrid binder according to clause 37 of the claims and TEMS-k fabrics (p) - anti-friction coating - 0.093-0.095;

- density, g / cm ³ - 1.2-1.8;

- coefficient of thermal conductivity, W / m · K - 0.2-0.25;

- coefficient of thermal diffusivity, · 10 ⁶ , m ² / s - 0.15-0.19;

- specific heat, kJ / kg · K - 1.1-1.5.

Physico-mechanical characteristics of plastics based on a hybrid binder according to claim 37 of the claims and TEMS-k fabrics (p):

- ultimate tensile stress in the direction of the base, MPa - 130-150;

- modulus of elasticity in the direction of the base, GPa - 3-3.5;

- destructive stress during bending, MPa - 90-120;

- destructive stress during crushing, MPa - 110-120;

- breaking stress at separation, MPa, not less than:

from structural fiberglass type SKN-21 (OST 3-485-77), plain fiberglass T13 + epoxy adhesive EP-5122 - 7-10;

from structural fiberglass type SKN-24 (OST 3-483-77), TSU 8/3-VM-78 satin fiberglass + EP-5122-11-15 epoxy binder.

Thermal protective plastics of this type do not reduce their operational characteristics for 10 years (in conditions of storage of a heated room) and for 3 years (in conditions of storage of an unheated warehouse). Such plastics do not lose their properties (and do not corrode) under atmospheric conditions, a decrease in breaking stresses at separation is noted by 10-30%, and at shear by 7-10%.

Thermal protective plastics of this class are resistant to the effects of solutions of acids and alkalis, sea water, hydrocarbon solvents (gasoline, acetone, toluene, alcohol, etc.), as well as radiation (γ-radiation, dose 0.1 Mrad), the effects of lubricants, oils, DDD (degassing, decontamination and disinfection) and OV.

The disadvantages of the hybrid binder according to clause 37 of the claims: plastics based on it are not waterproof enough and hygroscopic, and at temperatures of 50 ± 5 ° C ethanol, acetone, toluene, phenol, aniline, butyl alcohol, formaldehyde, epichlorohydrin are isolated, and when burning, and ammonia, carbon dioxide, water vapor, phosphoric and chloride anhydrides, etc.

With the introduction of discrete whiskers of Cr, and / or Cr ₂ About ₃ , and / or CrO ₃ more than 18 wt.h. the hybrid binder according to claim 37 of the claims becomes non-technological during processing, when it is cured, a lot of pores are formed (up to 25-30%), which sharply affects the performance of plastics based on it.

Plastics based on a hybrid binder according to claim 37 with additives of chromium oxides introduced in small quantities (up to 2 parts by weight) do not provide improvement in the physicomechanical and thermophysical properties of plastics within the required limits.

In addition, the introduction of a hybrid binder according to clause 37 of the claims in amounts of more than 18 parts by weight NC made of chromium oxides significantly accelerates the curing of the binder and increases its viscosity, which leads to significant technological difficulties in its processing into “prepregs” and further into structural products based on it.

The effectiveness of the hybrid binder according to § 38 of the claims

The whiskers of iron (Fe) and its oxides (FeO, Fe ₂ O ₃ , Fe ₃ O ₄ ) are introduced into the hybrid binder according to claim 38 in an amount of 2-18 parts by weight with the aim of obtaining on its basis and woven fillers of plastics with special properties:

- obtaining ferritic plastics and / or coatings for them, used as magnetic materials used in electronics, radio engineering, radar and other industries; for these purposes, whiskers of iron oxide Fe ₂ O ₃ are introduced into the hybrid binder of claim 38.

Fe ₂ O ₃ is an amphoteric oxide, exists in the form of several crystalline modifications: sponge iron, carbonyl iron, etc. They are introduced into the hybrid binder according to claim 38, usually together with other metal oxides and / or metal nitrides and silicon oxides.

At the same time, whiskers of iron oxide Fe ₂ O ₃ can be introduced into the hybrid binder according to claim 38 and in order to increase the strength and stiffness of plastics based on it, mainly vibration strength, tensile and compressive strength, and especially bending strength, interlayer shift and separation.

At the same time, finely dispersed whiskers of Fe ₂ O ₃ can be used in the hybrid binder according to claim 37 as pigments to obtain black plastics on its basis, and in combination with chromium oxides Cr ₂ O ₃ - dark green, and in combination with CrO ₃ oxides - dark red.

At the same time, the hybrid binder according to claim 38 with the addition of chromium oxides can be used to create iron-chromium coatings used to increase the heat resistance and thermal stability of structural composites used in the manufacture of chimney trunks, launch containers and other products.

For these purposes, it is most effective to use whiskers of carbonyl iron obtained by thermal decomposition of iron pentocarbonide; this iron is very clean and highly dispersed (up to 10 microns).

The use of these whiskers is especially effective for the production of plastic cores of electromagnets and for the manufacture of plastics with special properties: for example, high resistance to radiation and aging, as well as high electrical, electrostatic, electromagnetic and other characteristics.

Fe ₃ O ₄ - mixed oxide, black refractory whiskers with sizes up to 300 microns; the most effective is their introduction into a hybrid binder according to claim 38 to obtain polyphene (or kapron) fabrics of the type TEMS-k (p) heat-protective plastics having high physical, thermophysical, electrostatic, heat-shielding and physico-mechanical characteristics, and at the same time resistant to aggressive environments: any hydrocarbon solvents, oils, greases, DDD, SIO and other aggressive environments.

In addition, plastics based on the hybrid binder according to claim 38 with the addition of Fe ₃ O ₄ whiskers and TEMC-k (p) fabrics have high shear, tear-off, and bend characteristics, and do not accumulate static charges on their surfaces, i.e. are good antistatic agents with antistatic effect for 20 years.

FeO - basic iron oxide, black whiskers with a dispersion of up to 100 microns with a wide homogeneity region; are introduced into the hybrid binder according to claim 38 of the claims to obtain, on its basis, tissue fillers TEMS-k (p) heat-protective plastics with a high homogeneous structure (without pores, cracks, swellings and other defects) that have simultaneously high sublimation, heat and fire-retardant , antistatic and physico-mechanical characteristics, especially shear and transverse strength.

The main properties of whiskers of iron oxides have the following characteristics:

- density, g / cm ³ - 7.85;

- melting point, K - 1813;

- destructive stress during bending, GPa - 13.05;

- modulus of elasticity, GPa - 199-200;

- hardness - 9-10.

Even in small doses (2-5 parts by weight), whiskers of iron oxides can play the role of catalytically active structure-forming agents in a hybrid binder according to claim 38; whiskers of iron oxides during curing of the hybrid binder regulate the size and number of the formed elements of the supramolecular structure of the hybrid binder and thereby improve the physical, thermophysical, heat-shielding, electrostatic, physico-mechanical and other characteristics based on it.

At the same time, the introduction into the hybrid binder according to claim 38 of the invention of whiskers of iron oxides can increase the viability of the hybrid binder and "prepregs" based on it by 2-3.5 times, which contributes to the manufacturability and economy of the production of plastics based on these "prepregs "

The hybrid binder according to claim 38 of the claims allows several types of curing:

- thermochemical curing of plastics, which is usually carried out by convectively heating them in thermal furnaces, most often electric, autoclaves, by contact heating in molds, etc .;

- induction high-frequency curing;

- curing the hybrid binder by passing an electric current through it;

- radiation curing, which allows it to be cured at sub-zero temperatures, in water, in vacuum (for example, in space); the process of radiation curing a hybrid binder can be performed at low temperatures and does not require heating; the energy level required for radiation curing the hybrid binder is 3-4 times lower than for conventional thermochemical; in particular, in the radiation curing of a hybrid binder according to claim 38, the energy costs are only 21-27 kJ / mol.

High-intensity exposure during radiation curing makes it possible to more fully and at a new qualitative level (densely crosslinked, the formation of chemical and other adhesive bonds of the hybrid binder with other components) structure the polymer and improve its properties, for example, to obtain non-porous plastics of high purity.

For curing the hybrid binder according to claim 38, a dose of 0.6-1.8 MGy is required.

The radiation-polymerization of the hybrid binder is significantly affected by the DEG-1 resin plasticizer and additives — whiskers from iron oxides, as well as the SF-340A resin hardener.

The behavior of the hybrid binder according to claim 38 of the claims during its radiation curing is influenced by the types of fiberglass and other fillers, as well as the types of their lubricants and sizing.

For example, the boron oxides and nitrides in their compositions are capable of absorbing large doses of radiation energy (about 1.5-3 MGy), as a result of which the doses of irradiation of the hybrid binder with such fillers increase sharply by 3.5 times.

This complicates the curing process, and also requires the introduction of stabilizing additives into the hybrid binder, which reduce the level of radiation doses, and at the same time worsens a number of physicomechanical (mainly shear, tear-off, and bend) properties of the cured composite.

For aluminum-borosilicate alkali-free glass of the ABS brand (Table 3), which incorporates up to 10% boron oxide (Br ₂ O ₃ ), intended for the manufacture of critical structures made of fiberglass type SKN, as well as acid-resistant glass E grades (US formulations) containing boron oxide up to 7-8%, the radiation curing of the hybrid binder according to claim 38 is not practical, since under more intense irradiation, the destruction of plastics based on it begins, and as a result, the properties of plastics deteriorate.

The most effective is the use of a hybrid binder according to claim 38 of the claims to obtain plastics based on TEMC-k tissues (p). They have (in comparison with other fillers) higher thermophysical, electrostatic and heat-shielding characteristics (Tables 62-64).

Table 62
Thermophysical properties of plastics based on a hybrid binder according to claim 38 of the claims and TEMS-k fabrics (p) Plastic material Density, g / cm ³ Thermal conductivity, W / m Heat capacity, kJ / kg Thermal diffusivity, · 10 ³ , m ² / hour The hybrid binder according to claim 38 of the claims (40-50 parts by weight) + TEMS-p fabric (50-60 parts by weight) 1.8-1.9 0.3-0.35 1.2-1.25 1.4-1.41 The hybrid binder according to claim 38 of the claims (40-50 parts by weight) + TEMS-k fabric (50-60 parts by weight) 1.3-1.45 0.24-0.25 1.26-1.28 1.55-1.8

Table 63
The electrostatic properties of plastics based on a hybrid binder according to claim 38 of the claims and TEMS-k fabrics (p) Plastic material Surface resistivity, · 10 ⁵ , Ohm The specific volume resistance, · 10 ⁴ , Ohm · cm The hybrid binder according to claim 37 of the claims (40-50 parts by weight) + TEMS-p fabric (50-60 parts by weight) 1.8-1.85 5.2-5.5 The hybrid binder according to claim 37 of the claims (40-50 parts by weight) + TEMS-k fabric (50-60 parts by weight) 2.7-2.8 5.9-6.1

Table 64
Thermal protective properties of plastics based on a hybrid binder according to claim 38 of the claims and TEMS-k fabrics (p) Plastic material Heat flux, · 10 ⁶ , W / m ² Heat flow rate, mm / s Average ablation of material by a temperature sensor, mm / s The average ablation of material by weight loss, mm / sec Thermal resistance, sec / (kg / m ² ) ² Effective enthalpy, · 10 ⁶ , J / kg Sublimation temperature, ° С The hybrid binder according to claim 38 of the claims (40-50 parts by weight) + TEMS-p fabric (50-60 parts by weight) 3,5 500 0.7 0.65 2,5 3,1 650-750 The hybrid binder according to claim 38 of the claims (40-50 parts by weight) + TEMS-k fabric (50-60 parts by weight) 3,5 500 0.5 0.5 4.3 4,5 350-450

Plastics based on a hybrid binder according to claim 38 of the claims and TEMS-k fabrics (p) have other advantages (in comparison with prototype plastic):

- water absorption within 24 hours,% - 0.2-0.3;

- slip coefficient of friction of the pair: heat-resistant coating - antifriction coating of the same composition, but with the addition of antimony oxide - 0,091-0,095;

- radiation resistance during γ-irradiation with a dose of 0.1 Mrad (with the exception of plastics based on boron-containing fibers - boron, aluminoborosilicate (type ABS), American glass fibers of composition E and other boron-containing fibers (Table 3).

The plastics based on the hybrid binder according to claim 38 of the formula of the invention undergo aging: during aging under long-term storage conditions at temperatures of ± 50 ° C and humidity up to 98%, the following characteristics of plastics decrease:

- physical and mechanical - by 5-10%;

- thermophysical - by 10-15%;

- heat-shielding - by 15-20%;

- electrical and electrostatic - by 20-30%;

- interlayer shear and separation characteristics - by 20-40%.

Plastics based on a hybrid binder according to claim 38 and TEMS-k (p) fabrics are well processed into structural products by any winding methods: PN, PPN, SN, KPPN and combined winding methods.

The processing modes of the hybrid binder according to claim 38 of the claims into “prepregs” from TECS-k (p) fabrics and then by winding into structural products are identical to the modes shown in Table 14. Plastics based on a hybrid binder according to claim 38 of the claims and TEMS-k (p) fabrics can also be manufactured by pressing in the following mode:

- recommended pressing pressure, MPa - 3-3.5;

- the pressing pressure should be created when the plates reach the temperature, ° С - 80-130;

- the rate of temperature rise from 70 to 180-200 ° C, min - 3-5;

- pressing temperature, ° С - 160-200;

- the exposure time of the plastic bag at pressing temperatures, min:

up to 1 mm thick, not less than 25,

more than 1 mm thick, not less than 20 per 1 mm of thickness.

The plastics based on the hybrid binder according to claim 38 and the TEMS-k (p) fabrics have a sufficiently high strength with an interlayer separation of 60-300 MPa and a shear of 10-80 MPa, while other physical and mechanical characteristics of plastics of this type have underestimated characteristics (in comparison with power glass-carbon-boron-organoplastics):

- ultimate tensile stress in the direction of reinforcement, MPa - 140-160;

- destructive stress during bending, MPa - 110-140;

- destructive stress during crushing, MPa - 130-140;

- breaking stress at separation, GPa, not less than:

from fiberglass type SKN-21 - 20-25;

from fiberglass type SKN-24 - 30-45.

The above data on the properties of plastics based on a hybrid binder according to claim 38 and TEMS-k (p) fabrics show that they can be used as heat-protective coatings for glass-carbon-boron-organoplastics products from high-temperature gas-dynamic heating, and antistatic to protect the surfaces of products from the occurrence and accumulation of charges of static electricity.

All plastics based on hybrid binders according to claims 1-38 of the claims and TEMS-k (p) fabrics can be subjected to the following machining: turning, grinding, drilling, cutting with tools equipped with VK hard alloys, etc.

The above studies of the properties of hybrid binders according to claims 1-38 of the claims have shown that their characteristics depend not only on the composition and amount of the constituent components and the additives introduced into them - flame retardant, carbon-graphite, powder from metal oxides and nitrides, discrete , from whiskers and their mixtures, but also from the methods of their preparation, as well as from the methods of their processing by impregnation methods into "prepreg" fillers and from methods of processing "prepreg" fillers by winding methods into product items.

In some cases, for example, based on hybrid binders according to claims 1-8 and tissue fillers, plastics with enhanced thermal and heat-shielding characteristics are obtained (in comparison with a prototype plastic based on a hybrid binder according to author certificate No. 1036730A )

In other cases, for example, based on hybrid binders according to claims 9-12 and tissue fillers, plastics with improved electrical and electrostatic (antistatic) characteristics are obtained with high heat resistance and heat resistance.

In third cases, for example, based on the hybrid binder according to claim 13 of the claims and tissue fillers, plastics with increased viability are obtained (Table 65).

Table 65
Hybrid binder viability versus temperature and excipients used Name of indicator Hybrid Binder Performance Values Temperature, K 293 313 353 393 413 423 Temperature ° C twenty 40 80 120 140 160 The viability of the hybrid binder according to claim 1 5-6 days 3 days 120 minutes 150 minutes 8 minutes 4 minutes The viability of the hybrid binder according to claims 2-8 5 days 2 days 90 minutes 9 minutes 4-5 minutes 3 minutes The viability of the hybrid binder according to claim 9 6 days 4 days 150 minutes 180 minutes 12 minutes 10 minutes The viability of the hybrid binder according to claim 10 8 days 5 days 180 minutes 210 minutes 15 minutes 13 minutes The viability of the hybrid binder according to claims 11-12 5-6 days 4 days 130 minutes 160 minutes 12 minutes 8 minutes The viability of the hybrid binder according to claims 13-18 20-25 days 9-10 days 300-360 minutes 40-45 minutes 20-24 minutes 10-12 minutes The viability of the hybrid binder according to claims 19-24 5-5.5 days 2-2.5 days 100-110 minutes 10-12 minutes 5-7 minutes 3-3.5 minutes The viability of the hybrid binder according to claim 25 5.5 days 3.5 days 95 minutes 9.5 minutes 6 minutes 4 minutes The viability of the hybrid binder according to PP.26-27 6-7 days 3-4 days 150 minutes 20 minutes 15 minutes 10 minutes The viability of the hybrid binder according to claim 28 8-9 days 5-6 days 200 minutes 30 minutes 20 minutes 15 minutes The viability of the hybrid binder according to claim 29 5-6 days 3.5-4.5 days 160 minutes 30 minutes 20 minutes 15 minutes The viability of the hybrid binder according to claim 30 4,5 days 3-4 days 120 minutes 25 minutes 18 minutes 13 minutes The viability of the hybrid binder according to claim 31 4.6 days 3.5-4.5 days 115 minutes 20 minutes 17 minutes 12 minutes The viability of the hybrid binder according to claim 32 25-30 days 10-12 days 360-420 minutes 45-50 minutes 24-26 minutes 15-20 minutes The viability of the hybrid binder according to claim 33 5-6 days 4-5 days 130 minutes 30 minutes 20-25 minutes 13-18 minutes The viability of the hybrid binder according to claim 34 7-8 days 5-6 days 140 minutes 35-40 minutes 25-30 minutes 20-25 minutes The viability of the hybrid binder according to claim 35 8-9 days 5-6 days 200 minutes 40-45 minutes 35-40 minutes 30-35 minutes The viability of the hybrid binder according to claim 36 5-6 days 2-3 days 115-120 minutes 12-15 minutes 7-9 minutes 4-5 minutes The viability of the hybrid binder according to claim 37 6.5 days 4 days 125 minutes 20 minutes 10 minutes 7 minutes The viability of the hybrid binder according to claim 38 8-12 days 5-8 days 250 minutes 50-60 minutes 40-50 minutes 35-40 minutes

In other cases, for example, based on hybrid binders according to claims 14 to 18 of the claims and tissue fillers, plastics with increased viability and fire resistance with sufficiently high heat-shielding characteristics are obtained.

In the fourth cases, for example, based on the hybrid binder according to claim 19 and tissue fillers, plastics with high electrical, antistatic and heat-shielding properties are obtained.

In the fifth cases, for example, on the basis of hybrid binders according to claims 20-24 of the claims and tissue fillers of the type TEMS-k (p), heat-protective plastics with increased antistatic and electrical characteristics are obtained with increased fire resistance and heat resistance.

In six cases, for example, based on the hybrid binder according to claim 25 of the claims and tissue fillers of the type TEMS-k (p), plastics with high wear resistance are obtained at high fire and fire resistance indices.

In the seventh cases, for example, based on hybrid binders according to items 26-29 of the claims and tissue fillers, plastics with high vibration resistance and high interlayer characteristics — transverse and shear strength with increased heat resistance and thermal stability are obtained.

In eighth cases, for example, based on hybrid binders according to claims 29-33 and tissue fillers, plastics with high impact strength and interlayer strength, as well as with high antistatic and heat-protective properties and wear resistance, are obtained.

In ninth cases, for example, based on hybrid binders according to claims 34-38 and tissue fillers, plastics with high heat resistance, thermal stability and impact strength, as well as with high shear, tear and bend strength, are obtained.

All of the hybrid binders presented in this description according to claims 1-38 of the claims are highly versatile and adaptable: they can be used to impregnate any filament, woven, and combined fillers (Table 66), with any weave structures in woven fillers and any currently known coupling agents, lubricants and copolymers, and any flame retardants, and antistatic additives of metal oxides and metal nitrides and silicon compounds (SiQ _2, SiC, etc.) as well as soot and uglerodografitovymi mixtures.

In combination with various fillers, for example, glass-organoplastic (Table 66), hybrid binders according to claims 1-38 of the claims can be used for the manufacture of any plastic structural products using any winding and / or pressing methods, including the number of combined with the use of combinations of wet and dry windings, as well as their varieties: direct fabric winding (PTN), spiral winding (SN), longitudinally-transverse winding (PPN), oblique-longitudinally-transverse winding (KPPN) oblique spiral winding (SPL) and any combination thereof.

Table 66
Physico-mechanical characteristics of combined glass-organoplastics based on "prepreg" glass-organotissue of T-42-78 brand and hybrid binder according to claim 1 at a temperature of 20 ± 1 ° C Feature Name The average value of the characteristic The coefficient of variation, % The tensile strength of the plastic material in the weft, kgf / mm ² 42.6 4.8 The tensile strength of the plastic material on the basis, kgf / mm ² 69.5 5,4 The elastic modulus of the plastic material in the weft, kgf / mm ² 2075 4.1 The elastic modulus of the plastic material based, kgf / mm ² 3075 5.3 The tensile strength of the plastic material in compression by weft, kgf / mm ² 24.5 5,4 The tensile strength of the plastic material in compression on the basis, kgf / mm ² 25.1 6.8 The tensile strength of the plastic material when bending along the weft, kgf / mm ² 28.1 3.9 The tensile strength of the plastic material in bending on the basis, kgf / mm ² 50.9 4.7 The tensile strength of the plastic material during crushing by weft, kgf / mm ² 30.6 7.4 The tensile strength of the plastic material during crushing on the basis, kgf / mm ² 30.1 8.1 The tensile strength of the plastic material when cut by a duck, kgf / mm ² 19.9 7.1 The tensile strength of the plastic material when cutting on the basis, kgf / mm ² 13,2 6.8 The tensile strength of the plastic material when cleaved by a duck, kgf / mm ² 3.0 8.3 The tensile strength of the plastic material when cleaved on the basis, kgf / mm ² 3.3 6.5 The tensile strength of the plastic material with interlayer separation, MPa 75 6.3 The tensile strength of the plastic material at the interlayer shear along the weft, MPa 45 6.4 The tensile strength of the plastic material at the interlayer shear on the basis, MPa 45 6.3 Shear modulus, kgf / mm ² 395 6.2 Poisson's ratio 0,086 5,4 Density, g / cm ³ 1,56 4.3

The methods for producing hybrid binders according to claims 1-38 of the claims, the methods for their processing into “prepreg” fillers and the methods for producing plastic construction products made from “prepregs” made by winding and / or pressing methods can differ significantly from each other: and in terms of temperature and speed regimes of impregnation and winding, and in terms of tension and overlap of layers of woven fillers, and in terms of contact pressures of their rolling, and in terms of temperature regimes of impregnation and drying of "prepreg" fillers, and in part p presses and curing processes of hybrid binders in pretreatment portion of the individual components - additives added to the binding of the hybrid p.p.1-38 claims.

In the scope of one patent, it is not possible to characterize even all preferred variants of methods for producing hybrid binders according to claims 1-38 of the claims and methods for their processing into “prepregs” and further into structural products from them.

Below are given several preferred variants of the methods for producing hybrid binders presented in the description and claims.

Option 1. The method of obtaining hybrid binders according to claims 39-44 of the claims

The method involves sequential mixing and dissolving in each other epoxytriphenol (ETF), epoxyaliphatic (DEG-1) and rezol phenol-formaldehyde (SF-340A) resins at elevated temperatures.

The preparation of resins (ETF, DEG-1 and SF-340A) for mixing is carried out in several technological processes connected in series with each other. First, prepare a mixture of epoxy resins ETF and DEG-1, having the parameters shown in table.7.

Both of these resins are ETF (97-103 parts by weight) and DEG-1 (9-15 parts by weight) are fed sequentially or simultaneously to the reactor-mixer and mixed there with each other and with an acetone-alcohol-toluene mixture (acetone - 87 -93 parts by weight, ethyl alcohol - 43-49 parts by weight, oil and / or coal toluene - 7-13 parts by weight).

Both resins (ETF and DEG-1) are heated separately up to 180-200 ° С in special melting chambers before loading into the reactor-mixer separately and with different heating rates. ETF epoxytriphenol resin is heated at heating rates of 20-30 ° C / hour. Epoxyaliphatic resin DEG-1 is heated with heating rates of 90-100 ° C / hour. Then both the heated resin are fed into the reactor-mixer and mixed with each other at temperatures of 40-70 ° C. Mixing and dissolving between each other ETF and DEG-1 resins is carried out by means of acetone, ethyl alcohol and oil and / or coal toluene, sequentially loaded into the reactor-mixer in the following ratio of components, in parts by weight:

- epoxytriphenol resin ETF - 97-103;

- epoxyaliphatic resin DEG-1 - 9-15;

- acetone - 87-93;

- ethyl alcohol - 43-49;

- toluene oil and / or coal - 7-13.

Mixing all of the above components is carried out in a reactor-mixer at temperatures of 40-70 ° C for 3-6 hours per ton of the prepared composition.

At the next stage, the ETF and DEG-1 resins dissolved in the reactor-mixer and the organic acetone-alcohol-toluene solvent resins SF-340A are used as hardener in the amount of 31-37 wt.h. in the form of a powder mass with a particle size of up to 3 mm. Resin SF-340A introduced into the reactor-mixer must comply with the parameters specified in Table 7.

After introducing the SF-340A resin into the reactor-mixer, it is mixed with ETF and DEG-1 resins and an organic solvent at temperatures of 40-70 ° С for 3-6 hours based on one ton of the resulting binder composition.

At the next stage, an alcohol-acetone solvent with a component ratio of 1: 2 is additionally introduced into the binder composition obtained and located in the reactor-mixer and the newly obtained consistency of the hybrid binder is mixed at temperatures of 40-70 ° С for 30-60 minutes per ton of newly obtained composition bringing its density to 0.95-1.1 g / cm ³ . Then, the prepared binder composition is filtered with the removal of all insoluble components from it by means of a filter and / or rarefied fabric of the "Excelsior" type, followed by cooling to 20 ± 1 ° С and packaging in a special container with sealing means or by pouring it into an impregnation bath machines (figure 1).

Thus, the implementation of the method for producing a hybrid binder according to claim 1 is carried out. This binder is well compatible with various filament and woven glass-carbon-boron-organofillers of various structures. The average characteristics of plastics based on the above fillers and a hybrid binder according to claim 1 of the claims are given in tables 16-18.

The hybrid binder obtained by the above method according to claim 1 of the claims is well compatible with both caproamide and polyphene tissue fillers of the type TEMC-k (p).

The properties of plastics based on these tissue fillers and hybrid binder according to claim 1 of the claims are given in table 16-18 of this description.

The hybrid binder according to claim 1 is well compatible with the additives presented in claims 2-38 of the claims.

Hybrid binders according to claims 2-38 of the claims have a wide range of modified properties:

- high fire resistance (PP.2-8 of the claims);

- high electrical conductivity and heat resistance (paragraph 9 of the claims);

- high shear and transverse strength (paragraph 10 of the claims);

- high electrostatic characteristics (claims 11-12 of the claims);

- high viability (paragraph 13 of the claims);

- high viability and fire resistance (PP-18 claims);

- high electrical, electrostatic and heat-shielding properties (p. 19 claims);

- high electrical, electrostatic, heat-shielding properties at high fire-and-fire resistance (claims 20-24);

- high fire-resistance and fire safety (p.25 claims);

- high vibration resistance and fire resistance with a sufficiently high heat resistance and thermal stability (PP.26-27 of the claims);

- high shear, tear-off and bending heat resistance with a sufficiently high fire resistance (paragraph 28 of the claims);

- high thermophysical, electrostatic, heat-shielding and dynamic properties (paragraphs.29-33 of the claims);

- high heat resistance and thermal stability, as well as high anticorrosive, antistatic, heat-shielding, shear, tear-off and bending characteristics (items 34-38).

Option 2. A method for producing hybrid binders according to claims 45-50 of the claims

The method involves obtaining hybrid binders according to claims 1-38 of the claims by sequentially dissolving ETF, DEG-1 and SF-340A resins in two stages: first, together with an acetone-alcohol-toluene solvent with a component ratio of 1: (0.5 -0.6) :( 0.1-0.2), and then still together with an alcohol-acetone solvent with a component ratio of 1: 2.

Using this method, mixtures of two ETF and DEG-1 resins, similar in composition, are prepared, containing from 13 to 30% epoxy groups, from 0.015 to 0.04% mass fractions of chlorine ions, from 0.02 to 0.05 mass% fractions of saponified chlorine, up to 4% of the mass fractions of aniline and phenol and up to 1-1.5% of the mass fractions of volatile substances (Table 7).

The process of dissolution of epoxy resins ETF and DEG-1 is carried out in several stages:

- at the first stage, they are prepared for mixing with each other, for this, both resins are separately heated to a temperature of 180-200 ° C with different heating rates: 20-30 ° C / hour - for ETF resin and 90-100 ° C / hour - for resin DEG-1;

- at the second stage, they are poured into the reactor-mixer (together or sequentially) with components of an organo-aromatic solvent (acetone-alcohol-toluene) with the following ratio of components, in parts by weight:

- epoxytriphenol resin ETF - 97-103;

- epoxyaliphatic resin DEG-1 - 9-15;

- acetone - 87-93;

- ethyl alcohol - 43-49;

- toluene oil and / or coal - 7-13

and carry out their joint mixing in the reactor-mixer and dissolving together with the solvent at temperatures of 40-70 ° C for 3-6 hours per ton of the prepared consistency of the hybrid binder,

- at the third stage, crystalline sodium aluminosilicate in the amount of 7-13 parts by weight is introduced into the thus prepared consistency of ETF and DEG-1 resins and mixed in a reactor-mixer together with the consistency of ETF, DEG-1 resins and solvent at temperatures of 40-70 ° C for 3-6 hours per ton of product being prepared;

- at the fourth stage, a powdered piece of resole phenol-formaldehyde resin SF-340A is introduced into the product thus prepared and the introduced resin is mixed and dissolved together with the previously introduced components of ETF and DEG-1 epoxy resins at temperatures of 40-70 ° C for 3- 6 hours per ton of product being prepared;

- at the fifth stage of preparation of the hybrid binder, it is filtered to remove all insoluble components and the density of the hybrid binder is checked by the "density" indicator, which should be in the range of 0.95-1.1 g / cm ³ , and in cases where the "density" indicator is too high "more than 1.1 g / cm ³ an organic alcohol-acetone solvent is additionally introduced into it in a ratio of 1: 2 (≈20-30 kg per ton of the product to be prepared) and additionally mixed and dissolved with the previously prepared hybrid consistency the binder for 30-60 minutes at temperatures of 40-70 ° C, followed by cooling and filtering, and in cases of underestimation of the "density" of the hybrid binder (less than 0.95 g / cm ³ ), an additional 2-5 wt. hours powder mass of resin SF-340A and mix and dissolve it with a previously prepared mass of ETF, DEG-1 resins and solvents at temperatures of 40-70 ° C for 3-6 hours, followed by cooling and filtration.

In such a sequence of technological operations, methods for producing hybrid binders according to claims 32, 35, 38 of the claims are also carried out. These hybrid binders have a higher viability, 2-3 times higher than the viability of the hybrid binder according to claim 1.

Option 2 of the method of obtaining a hybrid binder according to item 13 of the claims may have several sub-options.

Sub-option 2a. According to this method, in each of the ETF and DEG-1 epoxy resins taken in the ratio 1: (0.1-0.2), crystalline sodium aluminosilicates are added in an amount of 7-13 parts by weight, introduced into ETF and DEG-resins 1 in the same proportions, then ETF and DEG-1 resins together with aluminosilicates are separately heated to temperatures of 180-200 ° С, and the mixture of ETF resins with aluminosilicates is heated to these temperatures with heating rates of 20-30 ° С / h, and the resin mixture DEG-1 with aluminosilicates is heated to temperatures of 180-200 ° C with heating rates of 90-100 ° C / h, then prepared in this way m of a mixture of ETF and DEG-1 resins together with aluminosilicates are placed in a mixing reactor and mixed with each other and with an organo-aromatic solvent of the composition: acetone - 87-93 parts by weight, ethyl alcohol - 43-49 parts by weight, petroleum toluene and / or coal - 7-13 parts by weight until completely dissolved in each other at temperatures of 40-70 ° C for 3-6 hours per ton of the product being prepared, at the next stage, into a hybrid semi-finished product of ETF, DEG-1 resins with aluminosilicates prepared in this way, located in the mixing reactor, enter powdered rezol phenol-formaldehyde resin SF-340A in an amount of 31-37 wt.h. and carry out its mixing and dissolution with other components of the resins and solvents at temperatures of 40-70 ° C for 3-6 hours, followed by removal from it of all insoluble components by filtration.

Thus prepared hybrid binder - semi-finished product is checked by the "density" indicator (norm 0.95-1.1 g / cm ³ ) and if the "density" indicator (more than 1.1 g / cm ³ ) is overestimated, alcohol is additionally introduced into it an acetone mixture with a component ratio of 1: 2 and this indicator is brought to normal due to the introduced mixture, and in cases of underestimation of the "density" indicator (below 0.95 g / cm ³ ), the powder mass of SF-340A resin is additionally introduced into the hybrid binder in an amount 2-5 parts by weight and it is mixed and dissolved with ETF, DEG-1 resins and solvents located in the mixing reactor for 3-6 hours at temperatures of 40-70 ° C, followed by cooling and removal of all insoluble particles by filtration.

Subvariant 2b. Obtaining a hybrid binder according to item 13 of the claims in this embodiment of the method is carried out in the following sequence of technological operations:

- at the first stage, ETF and DEG-1 epoxy resins are heated separately to 180-200 ° С with different heating rates: ETF resins - with a heating speed of 20-30 ° С / h, DEG-1 resins - with a heating speed of 90-100 ° C / hour;

- at the second stage, the heated resins ETF and DEG-1 are poured into the reactor-mixer and mixed and dissolved in each other together with an acetone-alcohol-toluene solvent (acetone - 87-93 parts by weight, ethyl alcohol - 43-49 parts by weight, oil and / or coal toluene - 7-13 parts by weight) at temperatures of 40-70 ° C for 3-6 hours per ton of the prepared binder-semi-finished product;

- at the third stage, 31-37 parts by weight are introduced into the binder-semi-finished product. the powder mass of resin SF-340A and mix it with a binder-prefabricated product for 3-6 hours at temperatures of 40-70 ° C for 3-6 hours per ton of the product obtained, followed by cooling and filtering through a filter;

- at the fourth stage (if it is necessary to give the hybrid binder one or another property), it is additionally introduced flame retardant (hexachlorobenzene, carbon tetrachloride, trichloroethyl phosphate, antimony trioxide, chladone, claims 2-8 of the claims) component-wise or in groups, antistatic ( copper phthalcyanines, nickel chlorine compounds, Sigbol and / or ASP-1 additives, soot and / or carbon-graphite mixtures - claims 9-12, 19-24 of the claims) and shockproof (metal oxides and nitrides, silicon oxide and whiskers - pp. 28-38 f Formulas of the invention) additives in various combinations and ratios;

- at the fifth stage, the above additives introduced are mixed in the reactor-mixer with the hybrid binder semi-finished product there at temperatures of 40-70 ° C for 3-6 hours, followed by uniform cooling of the obtained hybrid binder to temperatures of 20 ± 1 ° C.

In accordance with this method, hybrid binders are prepared according to 2-12, 19-38 of the claims.

The order of introduction of these additives in the above binders can be different, that is, they can be introduced into their compositions in any sequence; some of the additives, for example, flame retardants introduced into hybrid binders according to claims 2-8, can be microencapsulated, and some, for example, crystalline aluminosilicates (claims 13-18, 32) introduced into hybrid binders in the form of molecular sieves such as Na zeolites and / or with their preliminary saturation with pairs of adsorbed hardener. Molecular sieves such as Na zeolite (or sodium aluminosilicates) increase the viability of the above hybrid hot curing binders by 2-3.5 times.

Subvariant 2c. The simplest way to obtain hybrid binders according to claims 1-38 of the claims may be carried out in the following sequence of technological operations:

- at the first stage, 80-82 parts by weight are fed to the reactor-mixer. acetone (80% of its calculated amount);

- at the second stage, for example, by means of a vacuum pump, the calculated amount of ETF resin (97-103 parts by weight), heated in the melting chamber of the reactor-mixer to a temperature of 180-200 ° С with a heating rate of 20-30, is loaded into the reactor-mixer ° C / hour;

- at the third stage, the calculated amount of DEG-1 resin (9-15 parts by weight) heated in the melting chamber of the reactor-mixer to 180-200 ° C with a heating rate of 90-100 ° C / hour is loaded into the mixer reactor;

- at the fourth stage, the remaining calculated amount of acetone (8-10 parts by weight) is poured into the reactor-mixer and all introduced components are mixed at temperatures of 40-70 ° C for 30-60 minutes based on one ton of the product being prepared;

- at the fifth stage, for example, by means of centrifugal pumps, the calculated amount of ethyl alcohol (43-49 parts by weight) and oil and / or coal toluene (7-13 parts by weight) are fed into the reactor-mixer and the prepared consistency is additionally mixed at temperatures of 40-70 ° C for 30-60 minutes based on one ton of the prepared product;

- at the sixth stage, the calculated amount of SF-340A powder resin (31-37 parts by weight) is loaded into the mixer-reactor and mixed in the mixer-reactor together with other components introduced at temperatures of 40-70 ° С for 3-6 hours from calculation for one ton of the prepared product;

- at the seventh stage of obtaining a hybrid binder, samples are taken from it for indicators: "density" (norm 0.95-1.1 g / cm ³ ), "mass fraction" (norm 55-63%), "gelatinization time" (norm 3-6 days);

- at the eighth stage, when the “density” and “mass fraction” of the hybrid binder are obtained above the norm, an additional alcohol-acetone mixture with a component ratio of 1: 2 with a mixture density at temperatures of 20 ± 1 ° С is 0.75-1 g / cm ³ ;

- at the ninth stage, upon receipt of the indicator "gelation time" above the specified norm, an additional 3 parts by weight are added to the hybrid binder. resins SF-340A;

- at the tenth stage, the added SF-340A resin additives are mixed and dissolved in the mixer reactor with the previously introduced components and mixed at temperatures of 40-70 ° C for 3-6 hours based on one ton of the product to be prepared, followed by removal of all insoluble from it components by means of a filter and / or sparse fabric type "Excelsior";

- at the eleventh stage (if it is necessary to change certain properties of the obtained product), flame retardant, carbon-graphite, powder, filiform and other additives are introduced into it and mixed together with the consistency of the finished hybrid binder at temperatures of 40-70 ° C for 3-6 hours based on one ton of the prepared product;

- at the twelfth stage (if it is necessary to increase the viability of the obtained product), it is saturated with pairs of adsorbable hardener such as Na zeolite and / or pairs of aluminosilicates.

Note - The mixing time of the components of the prepared hybrid binders at temperatures below 40 ° C is excluded from the cycles of obtaining hybrid binders and the processes of mixing and dissolution of their components are accordingly extended by this time.

The list of equipment necessary to obtain hybrid binders according to claims 1-38 of the claims is presented in table 67.

Table 67
The list of equipment necessary for obtaining hybrid binders according to claims 1-38 of the claims Name of equipment Characteristic Appointment Apparatus with mechanical stirrer Sernv 1-2-12-01 volume 1 m ³ for the preparation of solvent mixtures Apparatus with a mechanical stirrer X18N10T volume 6.3 m ³ to obtain hybrid binders according to claims 1-38 Mernik scale 1 class volume 0.75 m ³ for alcohol dosage Mernik weight A1-684-00 volume 0.7 m ³ for acetone dosage Scales are platform, GOST 23711-79, GOST 23676-79 weight limit 100-2000 kg for weighing components Pumps TsG 50 / 50-15-1 productivity is 50 l / min for pumping alcohol, acetone Vacuum pump RLP-01 productivity 1200 m / h for loading ETF resin Crusher inv. 0804201 productivity 1000 kg / h for grinding resin SF-340A Electric Truck EK-2 load capacity 1500 kg for transportation of raw materials Electric lift EB 426-1 load capacity 800 kg for raising resin SF-340A Nitrogen ramp, damn. P3-9 No. 01.000 30 balloons for purging equipment with nitrogen Reducer oxygen ramp RDV-1 P _y = 16.2 MPa (P _y = 165 kgf / cm ² ) to reduce pressure in the pipeline Cylinders with nitrogen, GOST 949-73 volume 0.04 m ³ P = 15 MPa for purging equipment Sampler, damn. SPR 5310 volume of 100-200 ml (P _y = 150 kgf / cm ² ) for sampling

Figure 1-2 of this description shows a schematic diagram of a reactor-mixer for producing hybrid binders according to claims 1-38 of the claims prepared in the conditions of mass production of FSUE Avangard.

Figure 3 shows the conventions for figure 1, 2.

The reactor-mixer (figure 1, 2) contains: containers for storing acetone 1, ethyl alcohol 2, toluene oil and / or coal 3; containers for storing flammable liquids and solids - for resin SF-340A 4, for resin ETF 5, for resin DEG-1 6; resin crushing plant SF-340A 7; scales for weighing resins: resins SF-340A 8, resins ETF 9, resins DEG-1 10; measuring devices: for resin SF-340A 11, for resin ETF 12, for resin DEG-1 13; heat chambers: for heating the ETF 14 resin, for heating the DEG-1 15 resin.

The reactor-mixer through a pipe 16 is connected to the tray 22 of the impregnation machine, equipped with guides 17, squeeze 18 and impregnation 19 rollers, through which under tension stretches the fabric filler 20 (before impregnation) and 21 (after impregnation with a binder 23 located in the tray 22 of the impregnation machine )

The housing 24 of the reactor-mixer has two bottoms: the top 26, equipped with several necks:

25 - for manual loading of resin SF-340A,

27 - for joint automatic loading of resins ETF and DEG-1,

28 - for separate automatic loading of resin DEG-1,

29 - for automatic air supply on line 30,

31 - for automatic loading of acetone along line 32,

33 - for automatic loading of ethyl alcohol through line 34,

35 - for automatic loading of toluene oil and / or coal on line 36,

and the bottom bottom 37, is equipped with a neck 38 with a filter 39 for draining and filtering the finished products of hybrid binders according to claims 1-3, of the claims.

The reactor-mixer has an additional purge line 40 for purging the lines of acetone 32, ethyl alcohol 34 and toluene oil and / or coal 36 with liquid nitrogen. Line 40 is equipped with a valve 41 and a valve 42 (figure 2).

The reactor-mixer is additionally equipped with three measuring tanks:

43 - measuring device of ethyl alcohol,

44 - measuring device of toluene oil and / or coal,

45 - measurer of acetone,

and four pumps:

46, 47 - vacuum pumps,

48, 49 - centrifugal pumps.

The reactor-mixer additionally has three pipelines for loading ETF, DEG-1 and SF-340A resins into its internal cavity:

50 - pipeline loading line resin DEG-1,

51 - pipeline loading line ETF resin,

52 - pipeline resin loading line SF-340A.

The mixing reactor is also equipped with three collecting batchers:

53 - drive dispenser resin DEG-1,

54 - drive metering resin ETF,

55 - accumulator-dispenser resin SF-340A,

as well as valves 56 of the feed line of acetone, alcohol, toluene and ETF, DEG-1, SF-340A resins, shut-off valves 58 and fire arresters 59, as well as plugs 60, valves 61 of the DEG-1 resin loading line 50 and air purge line 30.

The operation of the reactor-mixer and its systems in accordance with the methods set forth in paragraphs 39-50 of the claims

Acetone, alcohol and toluene in ratios 1: (0.5-0.6) :( 0.1-0.2) in a total amount of 137-155 parts by weight from tanks 1-3 by means of weight measuring devices 43-45 they are fed into the internal cavity of the reactor-mixer 24 through the mouths 31, 33, 35 of the upper bottom 26, where they are mixed by means of a mixer for 30-60 minutes at temperatures of 40-70 ° C from calculation per ton of product being prepared.

At the same time (or after that) in another reactor-mixer of a similar type with a volume of 1 m ³ (Table 67), an alcohol-acetone mixture is prepared with a ratio of components 1: 2 with a density of 0.7-1.0 g / cm ³ in the amount of 2-5 parts by weight and mix it at temperatures of 40-70 ° C for 30 minutes.

Note - Alcohol-acetone mixture (≈20-30 kg per ton of the product being prepared) is a reserve solvent, it is additionally prepared for introduction into the main reactor-mixer with a volume of 6.3 m ³ (Table 67) in order to bring the density indicator to the norm of 0.95-1.1 g / cm ^{3 of the} prepared hybrid binders according to claims 1-38 of the claims in cases when their "density" indicators are overestimated; it is fed into the reactor-mixer through the upper neck 25 when the supply of resin SF-340A and the mixer of the reactor-mixer are turned off.

Then, through the accumulators of dispensers 53-55 (Fig. 1), 9-15 parts by weight are fed sequentially into the reactor-mixer 26. resin DEG-1, 97-103 wt.h. ETF resin and 31-37 parts by weight resins SF-340A, where they are mixed and dissolved by means of a mixer at temperatures of 40-70 ° C for 3-6 hours per one ton of product being prepared.

Notes

1. ETF and DEG-1 resins are fed to the reactor mixer in a form heated to temperatures of 180-200 ° C, heated in melting chambers 12, 13 (Fig. 1) with different heating rates: for an ETF resin, the heating speed is 20-30 ° C / hour, for DEG-1 resin - heating rate of 90-100 ° C / hour.

2. It is allowed to supply DEG-1 resin to the reactor-mixer without heating at a viscosity index of less than 0.1 Pa · s.

Next, the obtained hybrid binders are cooled to 20 ± 1 ° C and through the necks of 25 or 38 (Figs. 1, 2), samples of 100-200 ml are taken with a special sampler (Table 67) to determine the following indicators:

- "density" is the norm of 0.95-1.1 g / cm ³ ,

- "mass fraction" - the norm is 55-63%,

- "vitality" - the norm of 15 days.

In cases of overestimation of standards in terms of "density" or "mass fraction" of a hybrid binder, 2-5 parts by weight are added to its semi-finished product. previously prepared reserve alcohol-acetone mixture with a component ratio of 1: 2, the temperature is raised to 40-70 ° C and the mixture is mixed with the semi-finished product for 30-60 minutes at these temperatures based on one ton of the finished product.

Thus, the hybrid binder is prepared according to claim 1 of the claims (one of the sub-options of the method for its preparation) and hybrid binders according to claims 2-12.

In cases of underestimation of standards in terms of "density" or "mass fraction" of a hybrid binder, 2-5 parts by weight are added to it. powder resin SF-340A and carry out its mixing and dissolution with the components of the binder at temperatures of 40-70 ° C for 3-6 hours based on one ton of the finished product, followed by its filtration and cooling to a temperature of 20 ± 1 ° C.

Thus, the hybrid binder according to claim 1 of the claims (one of the sub-options of the method for its preparation) and hybrid binders according to claims 2-12 are also prepared.

In cases of underestimation of the viability indicator, additional sodium aluminosilicates or zeolites (AlO ₄ + SiO ₄ or Al ₂ O ₃ + Si ₂ O ₃ ) are added to the hybrid binder in an amount of 7-13 parts by weight. and mix them with it at temperatures of 40-70 ° C for 3-6 hours based on one ton of the finished product with its subsequent filtration (or without filtration) and cooling to temperatures of 20 ± 1 ° C.

Thus, the hybrid binder according to claim 13 is prepared.

To obtain hybrid binders according to claims 2-12, 14-38 of the claims, the hybrid binders according to claim 1 or claim 13 are formulated with fire-retardant components or groups (claims 2-8, 14-18), antistatic (items 9-12, 19-28) and anti-shock (items 26-38) additives in different ratios and combinations and mix them with hybrid binders according to claim 1 or 13 at temperatures 40-70 ° C for 3-6 hours based on one ton of the finished product.

Notes

1. The introduction of additives into hybrid binders according to claims 2-38 of the claims in any sequence of operations for their introduction is allowed.

2. All powder and filamentary fillers must be subjected to heat treatment at temperatures of 200-850 ° C for 2-3 hours before being introduced into hybrid binders (with the exception of SF-340A powder resin) (to remove excess moisture and volatile substances).

3. It is recommended to reduce the explosion and fire safety of technological operations for the production of hybrid binders according to claims 1-38 of the invention introducing chalk powder (up to 10%), calcium sulfate (up to 20%), and resin granules into the powder mass of the resin and zeolites moisten with water (up to 25%).

Almost all compositions of hybrid binders (with and without fillers) can be cured by various methods: thermochemical (the main method of curing hybrid binders according to claims 1-38 of the claims), high-frequency induction, curing by passing electric current through the hybrid binders, microwave curing in an alternating electric field (frequency 15-17 MHz for 10-60 seconds), radiation, etc.

All of the above curing methods (especially thermochemical) can be intensified by short-term exposure to hybrid binders of a magnetic field with a strength of 120-1100 E.

Methods for microwave and radiation curing of hybrid binders are quite complex and expensive; both methods require the use of special equipment and protective devices.

The most effective method of curing hybrid binders according to claims 1-38 of the claims is the combined one: thermochemical with intensification of the curing process by evacuation of the cured product. This combined method allows to improve not only the properties of the obtained plastics (increase the strength by 10-12%, reduce the dispersion of strength values by 40-50%, reduce porosity by 2–3 times, for example, for plastics based on hybrid binders according to 9-10 of the claims, but also to improve their technological characteristics: reduce the curing temperature by 50-100 ° C, reduce the duration of curing processes by 0.5-10 hours or more, reduce the amount of released volatile products).

All the above curing methods are carried out at high temperatures (160-200 ° C); these methods are explosive and fire hazard and therefore must be carried out in compliance with safety regulations with the use of fire arresters (figure 1, 2).

Almost all hybrid binders (with the exception of hybrid binders according to claims 1 to 8, 13 of the claims) are electrically conductive and have high electrostatic properties, and plastics based on them are antistatic and retain their antistatic properties under various operating conditions: friction, solvents , means DDD, OV, acids, alkalis and various types of radiation.

To accelerate the curing of hybrid binders, nitrogen-containing, for example, dimethylaniline, and metal-containing, for example, nickel (claim 10 of the claims), cobolt and vanadium accelerators can be introduced into them. For example, the introduction of the latest initiating additives reduces the consumption of these additives by several times and increases the gelation and curing rates of hybrid binders by several times.

All of the above confirms the universality of properties and the high quality of hybrid binders according to claims 1-38 of the claims and plastics based on them.

The proposed technical solutions - hybrid binders according to claims 1-38 of the claims and methods for their preparation give a great direct economic effect. This economic effect, depending on the volume of production of hybrid binders and products based on them, can reach from several hundred million to several billion rubles.

The economic effect of the proposed technical solutions can be manifested both at various technological stages of obtaining hybrid binders, and during their processing into “prepregs” and further into structural products from them, as well as at various stages of operation of the products in terms of: increasing the duration of their operation, increasing quality and operational reliability, etc.

The scope of the proposed inventions should be understood broader than specifically described in the materials descriptions and claims of technical solutions.

It should be borne in mind that in the description materials are presented only some possible preferred options for their implementation. And other embodiments of the inventions may be presented with respect to the compositions of hybrid binders, methods for their preparation and processing methods, for example, in terms of methods for impregnating tissue fillers with them, obtaining “prepregs” from them, and then obtaining “prepregs” of structural products based on them .

The proposed technical solutions for their technical performance are new, high-tech and highly efficient in comparison with the prior art.

The proposed technical solutions can be practically used in any sectors of the national economy: in rocket and space technology, aircraft engineering, mechanical engineering, energy, construction equipment, agriculture, as well as the oil and gas industry and medicine, for example, in the manufacture of elastic flexible tape spirals, smoke trunks of boiler rooms, launch tubes and pipelines of various classes and purposes, that is, where there is a need to use their strength, stiffness, thermal, electrical, electrical ktrostaticheskih, electromagnetic and other properties.

New technical solutions in the proposed combination of new and known existing features meet the criteria of patentability: the criteria of "novelty", "industrial utility" and "applicability", that is, the level of inventions.

Claims (50)

1. Hybrid binder for reinforced plastics based on ETF epoxy resin, hardener and solvent, characterized in that it additionally contains a plasticizer diluent, which is an epoxyaliphatic resin DEG-1, while the hardener is a resol phenol-formaldehyde resin SF-340A, and the solvent - a mixture of acetone, ethyl alcohol and toluene oil and / or coal, in the following ratio, wt.h .: Epoxytriphenol resin ETF 97-103 Epoxyaliphatic resin DEG-1 9-15 Hardener 31-37 Acetone 87-93 Ethyl alcohol 43-49 Toluene oil and / or coal 7-13 2. The binder according to claim 1, characterized in that it further comprises a flame retardant additive - 7-18 wt.h. trichloroethyl phosphate. 3. The binder according to claim 1, characterized in that it further comprises a flame retardant additive - 7-18 wt.h. carbon tetrachloride. 4. The binder according to claim 1, characterized in that it further comprises a flame retardant additive - 7-18 wt.h. freon. 5. The binder according to claim 1, characterized in that it further comprises a flame retardant additive - 7-18 wt.h. hexachlorobenzene. 6. The binder according to claim 1, characterized in that it further comprises flame retardant additives: 2-13 wt.h. freon, 2-13 parts by weight hexachlorobenzene and 2-13 parts by weight antimony trioxide. 7. The binder according to claim 1, characterized in that it further comprises flame retardant additives: 12-23 wt.h. trichloroethyl phosphate and 12-23 parts by weight hexachlorobenzene and / or carbon tetrachloride. 8. The binder according to claim 1, characterized in that it further comprises flame retardants: 12-23 wt.h. trichloroethyl phosphate, 12-23 parts by weight hexachlorobenzene, 12-23 parts by weight carbon tetrachloride, 12-23 wt.h. antimony trioxide and 12-23 wt.h. freon. 9. The binder according to claim 1, characterized in that it further comprises an additive - 1-1.5 wt.h. copper phthalcyanine. 10. The binder according to claim 1, characterized in that it further comprises an additive - 1-6 parts by weight in the form of a chlorine-containing nickel compound. 11. The binder according to claim 1, characterized in that it further comprises 0.001-0.003 parts by weight antistatic additives in the form of additives "Sigbol" containing a conductive solution of metal compounds of organic acids and a polymer component in toluene. 12. The binder according to claim 1, characterized in that it further comprises 0.001-0.005 parts by weight antistatic additives such as ASP-1 from a solution of chromium salts in synthetic fatty acids. 13. A hybrid binder for reinforced plastics based on ETF epoxy resin, hardener and solvent, characterized in that it additionally contains a plasticizer diluent, which is an epoxyaliphatic resin DEG-1, and an additive - crystalline sodium aluminosilicate, while the hardener is a resol phenol-formaldehyde resin resin SF-340A, and the solvent is a mixture of acetone, ethyl alcohol and toluene oil and / or coal, in the following ratio, wt.h .: Epoxytriphenol resin ETF 97-103 Epoxyaliphatic resin DEG-1 9-15 Hardener 31-37 Acetone 87-93 Ethyl alcohol 43-49 Toluene oil and / or coal 7-13 Crystalline Sodium Aluminosilicate 7-13 14. The binder according to item 13, characterized in that it further comprises a flame retardant additive - 7-23 wt.h. antimony trioxide. 15. The binder according to item 13, characterized in that it further comprises a flame retardant additive - 7-23 wt.h. hexachlorobenzene. 16. The binder according to item 13, characterized in that it additionally contains additives: 7-23 wt.h. carbon tetrachloride and / or freon. 17. The binder according to item 13, characterized in that it further comprises a flame retardant additive - 7-23 wt.h. trichloroethyl phosphate. 18. The binder according to item 13, characterized in that it further comprises flame retardant additives: 2-13 wt.h. trichloroethyl phosphate, 2-13 parts by weight antimony trioxide and 2-13 parts by weight freon. 19. A hybrid binder for reinforced plastics based on ETF epoxy resin, hardener and solvent, characterized in that it additionally contains a plasticizer diluent, which is an epoxyaliphatic resin DEG-1, and an antistatic additive - carbon black and / or carbon-graphite mixture in the ratio of carbon and graphite from 1: 1 to 1: 0.1, while the hardener is a resol phenol-formaldehyde resin SF-340A, and the solvent is a mixture of acetone, ethyl alcohol and toluene oil and / or coal tar at the following ratio of components, parts by weight: Epoxytriphenol resin ETF 97-103 Epoxyaliphatic resin DEG-1 9-15 Hardener 31-37 Acetone 87-93 Ethyl alcohol 43-49 Toluene oil and / or coal 7-13 Antistatic additive 7-18 20. The binder according to claim 19, characterized in that it further comprises a flame retardant additive - 7-18 wt.h. hexachlorobenzene and / or antimony trioxide. 21. The binder according to claim 19, characterized in that it further comprises a flame retardant additive - 7-18 wt.h. trichloroethyl phosphate. 22. The binder according to claim 19, characterized in that it further comprises a flame retardant additive - 7-18 wt.h. carbon tetrachloride and / or freon. 23. The binder according to claim 19, characterized in that it further comprises flame retardant additives: 2-13 wt.h. trichloroethyl phosphate, 2-13 parts by weight carbon tetrachloride and 2-13 parts by weight freon. 24. The binder according to claim 19, characterized in that it further comprises flame retardant additives: 2-13 wt.h. hexachlorobenzene, 2-13 parts by weight antimony trioxide, 2-13 parts by weight trichloroethyl phosphate, 2-13 parts by weight carbon tetrachloride and 2-13 parts by weight freon. 25. Hybrid binder for reinforced plastics based on ETF epoxy resin, hardener and solvent, characterized in that it additionally contains a plasticizer diluent, which is an epoxyaliphatic resin DEG-1, and flame retardants - antimony trioxide and hexachlorobenzene in a ratio of 1: 1 to 1: 0.1, while the hardener is a resol phenol-formaldehyde resin SF-340A, and the solvent is a mixture of acetone, ethyl alcohol and toluene oil and / or coal, in the following ratio components, parts by weight: Epoxytriphenol resin ETF 97-103 Epoxyaliphatic resin DEG-1 9-15 Hardener 31-37 Acetone 87-93 Ethyl alcohol 43-49 Toluene oil and / or coal 7-13 Fire Supplement 12-23 26. Binder according A.25, characterized in that it further comprises 2-13 parts by weight powder fillers in the form of monolithic, hollow, scaly and fibrous particles of metal oxides and / or nitrides and silicon oxide. 27. Binder according A.25, characterized in that it further comprises 2-13 parts by weight silica powder fillers. 28. Binder according A.25, characterized in that it further comprises 2-13 parts by weight discrete fillers in the form of whiskers - alumina and / or carbon silicon and / or chromium oxide and / or iron oxide. 29. A hybrid binder for reinforced plastics based on ETF epoxy resin, hardener and solvent, characterized in that it further comprises a plasticizer diluent, which is an epoxyaliphatic resin DEG-1, and a finely divided filler containing nitrides and / or metal and silicon oxides, selected from the group magnesium oxide — burnt magnesia, aluminum oxide — alumina, titanium oxide — rutile, silicon oxide — silica (aerosil), boron nitride (BN), or mixtures thereof, wherein the hardener is a resol soy phenol-formaldehyde resin SF-340A, and the solvent is a mixture of acetone, ethyl alcohol and toluene oil and / or coal, in the following ratio, wt.h .: Epoxytriphenol resin ETF 97-103 Epoxyaliphatic resin DEG-1 9-15 Hardener 31-37 Acetone 87-93 Ethyl alcohol 43-49 Toluene oil and / or coal 7-13 Filler 7-18 30. The binder according to clause 29, characterized in that magnesium oxide - burnt magnesia is used as a finely divided filler. 31. The binder according to clause 29, characterized in that titanium oxide - rutile is used as a finely divided filler. 32. The binder according to clause 29, characterized in that as a fine filler used alumina - alumina and / or silicon oxide - silica. 33. The binder according to clause 29, wherein boron nitride (BN) is used as a finely divided powder filler. 34. Hybrid binder for reinforced plastics based on ETF epoxy resin, hardener and solvent, characterized in that it additionally contains a plasticizer diluent, which is an epoxyaliphatic resin DEG-1, and a discrete additive in the form of monolithic or hollow whiskers, while the hardener represents a phenol-formaldehyde resin SF-340A, and the solvent is a mixture of acetone, ethyl alcohol and toluene oil and / or coal, in the following ratio of components, ma S.ch .: Epoxytriphenol resin ETF 97-103 Epoxyaliphatic resin DEG-1 9-15 Hardener 31-37 Acetone 87-93 Ethyl alcohol 43-49 Toluene oil and / or coal 7-13 Whiskers 2-18 35. The binder according to claim 34, characterized in that it contains 2-18 parts by weight of whiskers. whiskers of alumina. 36. The binder according to claim 34, characterized in that it contains 2-18 parts by weight of whiskers. whiskers of carbon silicon. 37. The binder according to clause 34, characterized in that as a whisker contains 2-18 wt.h. whiskers of chromium and / or its oxides. 38. The binder according to clause 34, characterized in that as a whisker contains 2-18 wt.h. whiskers of iron and / or its oxides. 39. A method of obtaining a hybrid binder for reinforced plastics based on epoxytriphenol, epoxyaliphatic and phenol-formaldehyde resins by sequentially dissolving them together in the presence of a solvent at elevated temperatures, characterized in that the hybrid binder is prepared according to one of claims 1-38, while separately heating up to temperatures of 180-200 ^о С ETF and DEG-1 resins: ETF resin - with a uniform heating rate of 20-30 ^о С / h, DEG-1 resin - with a uniform heating rate of 90-100 ^о С / h, after which the resins are mixed in pr isutstvii solvent - acetone, ethyl alcohol and toluene, petroleum and / or coal in a reactor-mixer at a temperature of 40-70 ^{° C} for 3-6 hours based on one ton of the obtained product is then added ground hardener - phenol-formaldehyde resole resin SF- 340A and stirred at temperatures of 40-70 ^about C for 3-6 hours based on one ton of the resulting composition, followed by its filtration. 40. The method according to § 39, wherein the filtration is carried out by means of a filter and / or several layers of rarefied tissue with mesh sizes from 0.1-0.1 to 1-1mm. 41. The method according to § 39 or 40, characterized in that after filtering to bring the density of the resulting composition to 0.95-1.1 g / cm ³ , a solvent containing a mixture of ethyl alcohol and acetone in a ratio of 1: 2 is introduced into the hybrid binder and mixed at temperatures of 35-60 ^about C for 30-60 minutes based on one ton of the resulting composition. 42. The method according to paragraph 41, characterized in that after filtration, the indicator "gelation time" of the hybrid binder is monitored, with its values above 3-6 minutes, the milled hardener - resol phenol-formaldehyde resin SF-340F is added in an amount of up to 3 parts by weight and carry out additional mixing at temperatures of 35-60 ^about C for 1-3 hours based on one ton of the obtained product, after which the finished product is filtered to remove insoluble solid components. 43. The method according to § 39 or 42, characterized in that the additives are introduced into the hybrid binder located in the reactor-mixer, component or group and mixed at temperatures of 35-60 ^about C for 3-6 hours 44. The method according to item 43, wherein the obtained hybrid binder compositions are additionally saturated with pairs of an adsorbing hardener such as Na zeolite and / or sodium aluminosilicate. 45. A method of obtaining a hybrid binder for reinforced plastics based on epoxytriphenol, epoxyaliphatic and phenol-formaldehyde resins by sequentially dissolving them together in the presence of a solvent at elevated temperatures, characterized in that the hybrid binder is prepared according to one of claims. 1-38, at the same time, ETF and DEG-1 resins are heated separately to temperatures of 180-200 ^о С: ETF resin - at a speed of 20-30 ^о С / h, DEG-1 resin - at a speed of 90-100 ^о С / h, then fed to the reactor-mixer acetone in an amount of 80-82 wt.h. and a heated ETF epoxytriphenol resin in an amount of 97-103 parts by weight, the remaining calculated amount of acetone is introduced into the mixing reactor 7-11 parts by weight. and stirred for 30-60 minutes at temperatures of 40-70 ^about With the calculation of one ton of the prepared final product, then ethanol is subsequently fed into the reactor-mixer in an amount of 43-49 wt.h. toluene and petroleum and / or coal in an amount of 7-13 parts by weight, the resulting mixture was stirred at 40-70 ^{° C} for 3-6 hours based on one ton of the obtained product, then charged into a reactor-mixer preheated epoksialifaticheskuyu DEG resin-1 and curing agent, the ground - resol phenol-formaldehyde resin SF-340A, and stirred at a temperature of 40-70 ^{° C} for 3-6 h per one ton of finished product, followed by its filtration. 46. The method according to item 45, wherein the filtering of the finished product is carried out by means of a filter and / or rarefied fiber glass "Excelsior". 47. The method according to one of claims 45 or 46, characterized in that after filtering the finished product to bring its density to 0.95-1.1 g / cm ³ , a solvent containing a mixture of ethyl alcohol and acetone in a ratio of 1: 2, and stirred at temperatures of 40-70 ^about C for 30-60 minutes based on one ton of the finished product. 48. The method according to item 45, characterized in that after filtration, the indicator "gelatinization time" of the hybrid binder is monitored, with its values above 3-6 minutes, the ground hardener - resol phenol-formaldehyde resin SF-340A is added in an amount of up to 3 wt. .h. and carry out additional mixing at temperatures of 35-60 ^about C for 1-3 hours based on one ton of the obtained product, after which the finished product is filtered to remove insoluble components. 49. The method according to item 45 or 48, characterized in that the additives are introduced into the hybrid binder located in the reactor-mixer, component or group and mixed at temperatures of 40-70 ^about C for 3-6 hours, component or group. 50. The method according to 49, characterized in that the obtained hybrid binder compositions are further saturated with pairs of an adsorbing hardener such as Na zeolite and / or aluminosilicates.

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