RU2495892C2 - Polymer binder for composite reinforcement - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to epoxy binder for composite plastic and can be used in production of reinforcement with a composite periodic profile. The binder contains the following (pts. wt): epoxy-diane resin with weight ratio of epoxy groups of 20.0-24.0 - 100, aromatically conjugated hydroxy phenylene, combined with isomethyl tetrahydrophthalic anhydride in ratio of 9:1 - 85-90, diglycidyl ether of oligooxypropylene glycol with weight ratio of epoxy groups of 16-18% - 10-12, amine-type polymerisation accelerator - tridimethyl aminomethyl phenol or 2-methylimidazole or ethyl-2-methylimidazole - 0.3-3.0.

EFFECT: invention enables to obtain an article with high strength, elasticity and chemical resistance.

1 tbl, 3 ex

Description

The invention relates to epoxy binders for composite plastics - in particular, as a polymer matrix for unidirectional fiberglass plastic in combination with rovings made of glass, basalt fibers and can be used in the production of composite periodic reinforcement used for hardening concrete with a bond of asphalt, gypsum, polymer and cement, as well as in the form of independent products and structures.

A known rod for concrete reinforcement (RU 2220049, publ. 12/27/2003, B32B 17/04, E04C 5/07), in which the bearing part of the rod and the windings of fiberglass, is impregnated alternately with a binder containing epoxy-diane resin (base), isomethyl tetrahydrophthalic anhydride - i-MTHFA - (hardener) and triethanolamine (accelerator) with the ratio of components in the rod together with the winding, wt.%: reinforcing filler 60-80; binding rest. After glass roasting is impregnated with a broach through a bath with a liquid binder and winding is applied, the binder is cured by a broach through cameras with infrared emitters and through a thermostatic chamber for 180-240 s.

The specified rod for reinforcing concrete has insufficient: tensile strength - 1090 MPa and elasticity, which is determined by the parameters of its manufacture and the composition of the binder.

There is also a technical solution according to the patent for the invention (SU 1761903, Е04С 5/07), where the rod is made of a roving bundle and a braid fastened with a polymer binder. The polymer binder is formed from epoxy resin with a hardener and a curing accelerator at a ratio of components in reinforced plastic, mass. parts: - basalt threads 40.5-69.2: epoxy resin ED-20 - 9-10; hardener IMTGFA 6-7; accelerator UP 606/2 - 0.3-0.4. The formed bundle of threads is subjected to heat treatment in the annealing chamber; impregnated with a binder; curing of the connecting rod is carried out when passing through eight heat chambers with IR emitters in the mode of stepwise heating and cooling.

The resulting rod has a tensile strength of 1060 MPa and a degree of polymerization of 82.3 wt.%, Which are insufficient values for reinforcing cement concrete in an alkaline environment, especially when steaming products and structures.

There is also known a technical solution for a utility model patent (RU 77309, Е04С 5/07, published on October 20, 2008 Bull. No. 29), which is closest to the proposed technical solution, according to which (in an independent claim) for concrete reinforcement, it contains a support rod made of a fibrous filler impregnated with a polymeric binder based on epoxy resin, a hardener, a polymerization accelerator and a winding, characterized in that the support rod is reinforced with at least one additional bundle twisted from at least one fiber th filler impregnated with a polymer binder, and the mass fraction of reinforcing ropes does not exceed 30% of the total mass of the fibrous filler.

The polymer binder according to the closest analogue contains the product of the interaction of the TEG-1 epoxy aliphatic resin with urethane rubber in the following ratio of components,% mass:

Fibrous filler - 49.8-69.13;

Epoxy resin ED-20 - 17.1-27.6;

Hardener iso-MTHFA - 13.6-22.1;

The interaction product of the TEG-1 epoxy aliphatic resin with urethane rubber - 0.12-0.42;

Accelerator - UP 606/2 - 0.05-0.08.

As a filler, filaments of basalt and glass fibers are used, which are subjected to annealing in a special chamber before impregnation, impregnated and cured in a heat chamber.

A disadvantage of the known utility model for the closest analogue is the low mechanical strength in terms of temporary tensile strength of 1200-1300 MPa and an elastic modulus of 55000-71000 MPa. These drawbacks are associated with the imperfection of the structure of the reinforcing bar both in the composition of the polymer binder and its redistribution and polymerization — in the structuring of the polymer matrix in the composition of the reinforcement with the formation of a polymer film on the surface. The use of a binder isomethyltetrahydrophthalic anhydride (IMTFA) in the curing system also has a negative effect on the properties of the core. It is capable of crystallizing during preparation and impregnation and liquefying, draining and evaporating at a high-speed polymerization temperature of more than 200 ° C.

The technical task of the invention is to increase the operational characteristics of composite products based on the inventive polymer binder.

The technical result consists in increasing the strength, elasticity and chemical resistance of composite reinforcement made using the inventive polymer binder.

The technical result is achieved by the fact that in the polymer binder for composite reinforcement containing epoxy resin, the hardener is methyl tetrahydrophthalic anhydride, an amine-type polymerization accelerator, an epoxy-containing elasticizing modifier according to the invention, additionally contains diglycidoxyphenyl-ethylene-phenylene oligo oligo oligo combined with isomethyl tetrahydrophthalic anhydride in elations 9: 1, respectively, at the following component ratio, mass.ch .:

- epoxy resin with a mass fraction of epoxy groups of 20.0-24.0 one hundred - aromatically conjugated hydroxyphenylene combined with isomethyl tetrahydrophthalic anhydride 85-90 - diglycidyl ether of oligooxypropylene glycol with a mass fraction of epoxy groups of 16-18% 10-12 - an amine type accelerator - tridimethylaminomethylphenol, or 2,4,6-trisdimethylaminomethylphenol, or 2-methylimidazole, or ethyl, 2-methylimidazole, or 2-methylimidazole, or 4-ethyl, 2-methylimidazole 0.3-3.0

The technical result is ensured by the fact that the inventive polymer binder contains a crosslinking aromatically conjugated hydroxyphenylene combined with isomethyl tetrahydrophthalic anhydride (IMTFA). It was experimentally established that IMTHFA combined with aromatically conjugated hydroxyphenylene does not evaporate, does not leak and does not crystallize for a long time after preparation of the binder and during the operation of composite products based on it, thereby improving the performance characteristics of composite fittings based on the inventive polymer binder. When using a binder epoxy resin with a mass fraction of epoxy groups of more than 24.3%, the binder may contain crystals of individual diglycidyl ether diphenyl propane, which is not technologically advanced; when the content of epoxy groups is less than 20%, the viscosity becomes increased, which requires heating the binder during preparation and impregnation, increases the number of air inclusions in the mass, which reduces the performance and strength and water resistance of the reinforcement. The amount of the mixture of the oligomer of aromatically conjugated hydroxyphenylene with IMTFA in the curing system in the range of 85-90 parts by weight selected experimentally by gelation time at 180 ° C until the desired reactivity is achieved. The ratio of 1 to 9 components in a mixture of an oligomer of aromatically conjugated hydroxyphenylene with IMTHA was established based on the sufficiency of the structural effect of the oligomer on self-healing of defective zones and chemical resistance, as well as compatibility with IMTHA, which determines the absence of crystallization of the latter without heating. The epoxy-containing elasticizing component is oligoxypropylene glycol diglycidyl ether at less than 10 parts by weight. the content does not provide elongation in tension of the cured binder of at least 4%, with more than 12 parts by weight requires an increase in the number of functional groups of curing agents or accelerator, or manufacturing conditions, which is not desirable. Amine-type curing accelerators are selected, like all accelerators of this type, empirically. Imidazoles - 2-methylimidazole, ethyl, 2-methylimidazole, 4-ethyl, 2-methylimidazole - are selected in the range of 0.3-0.5 parts by weight, and tridimethylaminomethylphenol or 2,4,6-trisdimethylaminomethylphenol - 2.0- 3.0 when starting reinforcement in production on prototypes. In special cases, the combined use of accelerators is allowed.

A polymer binder is prepared as follows:

To make the binder base, the calculated amount of an epoxy diane resin, for example ED-20, an epoxy-containing elastic modifier - oligoxypropylene glycol diglycidyl ether, for example, BF-2 laproxide brand, is loaded and closed with a stirrer. The components are mixed at a temperature of 60 ° C for 60 minutes. Then the contents of the reactor are naturally cooled. A sample is taken to determine the following parameters: viscosity, mass fraction of non-volatiles, the content of epoxy groups, their values are recorded in the passport for this batch of resin.

For the manufacture of a hardener for a binder, a calculated amount of structuring aromatically conjugated gyroxyphenylene, for example, ARGOF 3 and isomethyltetrahydrophthalic anhydride (IMTFA), is loaded into a vacuum reactor, closed and a stirrer is turned on. The components are mixed at a temperature of 20 ° C for 60 minutes. Then the contents of the reactor are defended for 60 minutes. A sample is taken to determine the following parameters: viscosity, mass fraction of non-volatile substances, their values are recorded in the passport for this batch of hardener.

Then the base of the binder and hardener are combined in the calculated amount, mixed thoroughly, held for 20-30 minutes until the air inclusions are removed, the finished binder is transferred to the production of composite products.

The technological process of manufacturing composite reinforcement based on a polymer binder consists in impregnating a bundle of mineral or carbon fibers in a polymer binder and then curing the binder at a temperature of 160-280 ° C.

To obtain the inventive polymer binder, for example, the following starting materials can be used:

- epoxy resin ED-20 according to GOST 10587-84 or resin DER-330 (Germany);

- Isomethyltetrahydrophthalic anhydride (IMTGFA) - TU 2418-399-05842324-2004 (Russia):

- K-54 brand tridimethylaminomethylphenol;

- 2,4,6-trisdimethylaminomethylphenol - the company "Air products" (England);

- 2-methylimidazole - the company "Ciba-Geigi" (Switzerland), Zd. Sverdlov, Dzerzhinsk, Nizhny Novgorod Region .;

4-ethyl, 2-methylimidazole - the company "Air products" (England);

Epoxy-containing elasticizing modifier, brand BF-2; production of LLC Mikrodin Vladimir;

As the structuring agent of aromatically conjugated hydroxyphenylene, it is most expedient to use the ARGOF 3 oligomer.

ARGOF-3 oligomer is aromatically conjugated hydroxyphenylene with a number average molecular weight of 300 and 400 cu, respectively. The ARGOF-3 oligomer is the oxidative condensation products of diatomic phenols or their alkyl substituted homologs. ARGOF 3 is obtained, for example, by condensation of alkylresorcinol at 240-250 ° C in the presence of concentrated sulfuric acid for 3-4 hours with distillation of 10% of the mass. water.

Diglycidyl ether of oligooxypropylene glycol with a mass fraction of epoxy groups of 16-18% can be used with Laproxide BF brands (TU 2225-065-10488057-2011).

For example, the following compositions of the inventive polymer binder, parts by weight:

the composition of the binder 1

epoxy resin - one hundred modifier - eleven

aromatically conjugated hydroxyphenylene,

combined with isomethyl tetrahydrophthaliev

anhydride - 87.8 polymerization accelerator - 1.2.

the composition of the binder 2

epoxy resin - one hundred; modifier - 10;

aromatically conjugated hydroxyphenylene,

combined with isomethyl tetrahydrophthaliev

anhydride - 89; polymerization accelerator - 1.0.

the composition of the binder 3

epoxy resin - one hundred; modifier - 10.4;

aromatically conjugated hydroxyphenylene,

combined with isomethyl tetrahydrophthaliev

anhydride - 88.8; polymerization accelerator - 0.8.

Physico-mechanical, chemical and technological parameters of composite reinforcement made on the basis of the inventive polymer binder are shown in the table.

Table Name of indicator Composite reinforcement made on the basis of polymer binder The composition of 1 binder The composition of the 2 binder The composition of the 3 binder 1 Physical and mechanical: 1.1 The modulus of elasticity during static bending across the fibers, MPa 1100 1200 1150 1.2 Tensile modulus 1449 1500 1470 1.3 Relative elongation under tension before deformation,% 2.2 2.2 2.2 1.4 Modulus of elasticity in bending, MPa 60,000 75,000 65,000 1.5 Impact strength across the fibers, kJ / m2 340 350 340 1.6 Resistance to heating within 24 hours, ° C 200 200 200 2 Chemical: 2.1 Water absorption,% 0.2 0.2 0.28 2.2 Alkalinity (10% sodium hydroxide solution),% 4.96 4.96 5.00 2.3 Resistance to sulfuric acid,% 0.28 0.2 0.28 2.4 Resistance to sea water,% 0.6 0.5 0.9 3 Technological: 3.1 Speed drawing (curing), m / min 3.8 4.2 4.4

According to the data given in the table, it can be concluded that composite reinforcement made on the basis of the inventive binder has high strength, elasticity and chemical resistance.

Thus, the claimed invention improves the performance of products based on a polymer binder, in particular, to increase their strength, elasticity and chemical resistance.

Claims (1)

A polymer binder for composite reinforcement containing an epoxy resin, a hardener is methyltetrahydrophthalic anhydride, an amine type polymerization accelerator, an epoxy-containing elastic modifier, characterized in that it contains oligoxyoxypropylene-phenylenethenylene-glycene aromatic, an additional oligoxyoxypropylene-phenylenethenylene 9: 1 in the following ratio of components s, parts by weight .:
epoxy resin with a mass fraction of epoxy groups of 20.0-24.0 one hundred aromatically conjugated hydroxyphenylene combined with isomethyl tetrahydrophthalic anhydride 85-90 oligoxypropylene glycol diglycidyl ether with a mass fraction of epoxy groups of 16-18% 10-12 amine type accelerator - tridimethylaminomethylphenol or 2-methylimidazole or ethyl, 2-methylimidazole 0.3-3.0