RU2560370C1 - Hybrid epoxy-triphenol binding agent with application of novolac resin - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: in one version binding agent contains: epoxytriphenol resin ETP, diluents-plasticiser, representing epoxyaliphatic resin DEG-1, curing system, consisting of novolac phenolformaldehyde resin SF-0112 and catalyst 2,4,6-tris(dimethylaminomethyl)phenol(UP-606/2), and solvent - mixture of acetone, ethyl alcohol and toluene. In another version of invention binding agent contains as catalyst complex of boron trifluoride with benzylamine in 50% diethyleneglycol solution (UP-605/3r). Products of binding agent curing - monolith composites - possess improved physical and mechanical, thermophysical and electric properties.

EFFECT: invention makes it possible to obtain organo-, basalt-, carbon-fibreglass with increased heat and thermal resistance, chemical resistance in aggressive and water media with stably high degree of hardening.

2 cl, 1 tbl, 3 ex

Description

The invention relates to heat-erosion-resistant binder based on epoxy resins intended for the manufacture of organo-, basalt-, carbon-, fiberglass products with increased corrosion resistance, thermal stability, as well as products from composite fibrous materials that are operated under conditions of exposure to high-enthalpy high-speed gas flows and under conditions of prolonged exposure to aggressive environments of flue gases, and can be used in the rocket and space industry, aircraft and ships swarming, as well as in a number of other sectors of the national economy: mechanical engineering, railway transport, nuclear, oil and gas and chemical industries.

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 the copyright certificate SU No. 726137, 04/08/1980. 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. When using this binder in composite materials in the process of working with it, the following disadvantages are identified: increased fluidity, porosity, low shear and tear strength, which impede its use for the manufacture of winding plastic products.

The closest analogue and prototype of the invention is a hybrid binder according to ed. St. RU No. 2260022, 09.10.2005. based on ETF epoxy resin, anilinophenol formaldehyde resin SF-340A, epoxyaliphatic resin DEG-1 and an organic solvent - a mixture of acetone, ethyl alcohol, toluene. A significant drawback of this binder is the need to use a long heat treatment mode and high temperatures (190 ÷ 200) ° C in the curing process. If it is not possible to provide a curing process for large-sized winding products made on the basis of a prepreg impregnated with this binder, it is very difficult to obtain composites with a curing degree above 90% at such high temperatures. The insufficient degree of curing of the binder can be explained by the fact that during the curing with prolonged exposure at a temperature of the order of (170 ± 5) ° C, the polymerization reaction proceeds slowly, while the epoxy groups decompose simultaneously with the formation of carbonyl groups C = O and unsaturated double bonds C = C, which in turn react with active methylol groups and methylene ether bridges of resole anilinophenol-formaldehyde resin. As a result of the formation of various by-products of the monomer addition, partial consumption of epoxy groups occurs, which ultimately affects the completeness of curing of the polyepoxide. An increase in the holding temperature during curing of winding products significantly increases energy consumption and complicates the hardware of the heat treatment process.

An object of the invention is the replacement of the hardener - rezol anilinophenol-formaldehyde resin in a binder - a prototype with a curing system, which consists of novolac phenol-formaldehyde resin and a catalyst in order to obtain a new hybrid binder with high reactivity, allowing to cure reinforced plastics at a temperature of (170 ± 5) ° C with a stably high degree of cure 94 ÷ 98% and at the same time provide physical

mechanical, thermophysical, electrostatic (antistatic) and anticorrosion properties of plastics made by winding methods.

Technological difficulties associated with the selection of curing modes can be avoided by replacing the resolved anilinophenol-formaldehyde resin of the SF-340A grade in the binder formulation with the novolac phenol-formaldehyde resin of the SF-0112 brand using curing catalysts. This brand of novolac resin SF-0112 is produced in Russia at several enterprises and has the most stable technological properties. Novolac resin SF-0112 is slow-burning, has a high dropping point (110 ÷ 150) ° C and a low content of free phenol (less than 3%), and phenol is an inhibitor of the polymerization reaction.

The technical result is achieved by the fact that a binder containing a mixture of epoxytriphenol ETF and epoxyaliphatic DEG-1 resins in organic solvents contains, as a curing system, novolac phenol-formaldehyde resin SF-0112 and a 2,4,6-tris (dimethylaminomethyl) phenol catalyst (UP-606) / 2) or a complex of boron trifluoride with benzylamine in a 50% solution of diethylene glycol (UP-605 / 3p), in the following ratio of components, in wt. hours:

ETF epoxytriphenol resin one hundred epoxyaliphatic resin DEG-1 12 novolac phenol-formaldehyde resin SF-0112 34 ÷ 46 acetone 80 ethanol 46 toluene 10 catalyst UP-606/2 0.1 or catalyst UP-605 / 3p 6

A distinctive feature of the proposed technical solution is the high reactivity of the binder on the curing system from novolac phenol-formaldehyde resin and catalyst at a curing temperature of (170 ± 5) ° C, which allows to obtain finished plastic in the manufacture of large-sized winding products with a stably high degree of curing. In addition, when using UP-605 / 3p catalyst in a binder, the pot life is increased.

Thus, the analysis of the prior art allows us to conclude that the proposed hybrid binder meets the criterion of "novelty" and has an essential attribute, allowing to recognize the claimed solution meets the criterion of "inventive step".

The use of a curing system in the form of a novolac phenol-formaldehyde resin and a catalyst in a polymer matrix consisting of a mixture of epoxytriphenol and epoxyaliphatic resins in a new hybrid binder can significantly reduce the temperature and curing time without reducing the thermophysical and deformation-strength characteristics, while creating a more ordered and less defective structure of the mesh polymer of the binder base itself and the reinforced plastic as a whole.

The invention can be demonstrated by specific examples of execution. To confirm the necessary properties of the finished winding composite, it was characterized using standard or generally accepted methods.

Example 1 (prototype). Cooked binder according to the recipe, in wt. hours:

ETF epoxytriphenol resin one hundred epoxyaliphatic resin DEG-1 12 rezol anilinophenol formaldehyde resin SF-340A 34 cetone 80 ethanol 46 toluene 10

fiberglass T-10-14 (92) was impregnated on a vertical impregnation machine and a 50 mm wide glass tape based on VMPS glass fiber was impregnated on the VOL impregnation unit. The impregnated fiberglass fabric was used for winding a cylindrical shell by the PTN method (direct fabric winding), and the impregnated tape was used to wind a similar cylindrical shell by the PTN method (longitudinal-transverse winding). Shells were cured in a polymerization chamber at a holding temperature of (170 ± 5) ° C for 15 hours.

Example 2. Cooked binder according to the recipe, in wt. hours:

  ETF epoxytriphenol resin one hundred  epoxyaliphatic resin DEG-1 12   novolac phenol-formaldehyde resin SF-0112 42   acetone 80   ethanol 46   toluene 10  catalyst UP-606/2 0.1

analogously to example 1 made fiberglass shells.

Example 3. Cooked binder according to the recipe in wt. hours:

 ETF epoxytriphenol resin one hundred   epoxyaliphatic resin DEG-1 12   novolac phenol-formaldehyde resin SF-0112 42   acetone 80  ethanol 46   toluene 10   catalyst UP-605 / 3p 6

analogously to example 1 made fiberglass shells.

From the manufactured fiberglass shells indicated in examples 1, 2, 3, samples were cut for physical, mechanical and physico-chemical tests. The test results are presented in the table.

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 Table end one 2 3 four 5 6 7 8 7 Cracking stress in the axial direction, OST92-1472, MPa 37.3 37.8 33.1 37.9 36.7 36.9 8 Density, OST 92-0903, g / cm ³ 1.75 1.96 1.72 1.99 1.71 2.0 9 Degree of cure binder materials OST 92-0903,% 89.9 92.0 94.0 95.3 94.9 97.2

From the tabular data it can be seen that while maintaining the deformation-strength characteristics of fiberglass, made on the basis of a curing system for hybrid binders specified in examples 2 and 3, they have a higher degree of cure compared to fiberglass based on a hybrid binder specified in the prototype. Windings made of fiberglass with a low degree of cure under conditions of storage and further operation are gradually cured, which leads to a redistribution of residual stresses across the layers, deformation of the products and inter-turn separation.

All other properties of winding plastic based on a hybrid binder, set forth in ed. St. RU No. 2260022 (heat resistance, corrosion resistance, electrical), inherent in composites made using the new hybrid binder proposed in this invention.

The invention allows to obtain organo-, basalt-, coal-, fiberglass with increased heat and heat resistance, chemical resistance in aggressive and aqueous environments with a stably high degree of cure. The invention also allows to reduce energy consumption at the stage of curing reinforced plastic fillers.

Claims (2)

1. Hybrid binder for reinforced plastics based on ETF epoxy resin, DEG-1 epoxy aliphatic resin, hardener and solvents: acetone, ethyl alcohol, oil or coal toluene, characterized in that in order to provide the finished filled plastic, it contains a stably high degree of cure instead of hardener anilinophenol formaldehyde resin SF-340A curing system consisting of novolac phenol formaldehyde resin SF-0112 and a catalyst 2,4,6-tris (dimethylaminomethyl) phenol (UP- 606/2), in the following ratio of components, in wt. hours:
ETF epoxytriphenol resin one hundred epoxyaliphatic resin DEG-1 12 novolac phenol-formaldehyde resin SF-0112 34 ÷ 46 acetone 80 ethanol 46 toluene 10 catalyst UP-606/2 0.1 2. Hybrid binder for reinforced plastics based on ETF epoxy resin, DEG-1 epoxy aliphatic resin, hardener and solvents: acetone, ethyl alcohol, oil or coal toluene, characterized in that it contains a curing system consisting of novolac phenol-formaldehyde resin SF-0112 and catalyst: a complex of boron trifluoride with benzylamine in a 50% solution of diethylene glycol (UP-605 / 3p), in the following ratio of components, in wt. hours:
ETF epoxytriphenol resin one hundred epoxyaliphatic resin DEG-1 12 novolac phenol-formaldehyde resin SF-0112 34 ÷ 46 acetone 80 ethanol 46 toluene 10 catalyst UP-605 / 3p 6