RU2250241C2 - Thermally curable binder for composite materials - Google Patents

Abstract

FIELD: polymer materials and composites.

SUBSTANCE: invention relates to epoxide compositions, in particular to preparation of hot-molded thermally curable epoxide compositions used as binders in manufacture of composite materials and products thereof. Binder comprises 60-70% 4,4'-isopropylidenediphenol epoxide resin, amine-type curing agent, and additionally 5-15% aliphatic epoxide resin (DEG-1) and 1-5% phenyl glycidyl ether. Curing agent (utilized in balancing amounts) is aniline-formaldehyde condensation product, condensation being carried out in presence of acid catalyst and giving aminobenzylaniline as main condensation product.

EFFECT: achieved high and stable physicochemical characteristics of glass-plastic articles.

2 tbl, 5 ex

Description

The invention relates to the field of technology of epoxy compositions, in particular to the production of thermosetting hot-formed epoxy compositions used as a binder for the production of composite materials and products from them, for example, reinforced plastics by the pultruded method.

The invention can be used in the construction industry, namely for the manufacture of plastic reinforcing elements for reinforcing building concrete structures, which can also be used in load-bearing prefabricated structures, as a structural material for replacing metal and wooden products. The invention is also intended for use as impregnating compositions, adhesives, coatings, binders for structural fiberglass, also produced by wet winding.

A known binder composition for the manufacture of basalt-plastic reinforcing bars, containing in parts by weight epoxy diane resin, 2,4,6-tris- (dimethylamino) methylphenol (Accelerator UP 606 \ 2) and polymethylene polyphenylpolyamine, which is the product of the interaction of aniline and formaldehyde, and containing 51-57 wt.% diaminodiphenylmethane, mainly 95-97 wt. %, 4,4-isomers.

A known polymer composition comprising an epoxy diane resin, polyepichlorohydrin diglycidyl ether, diethylene glycol diglycidyl ether, a eutectic mixture of aromatic amines and salicylic acid (A.S. N 1014859, class C 08 L 63/02, 1983).

The disadvantage of the composition is its low suitability for the manufacture of fiberglass products by wet winding (especially on an industrial scale) due to the high viscosity at a temperature of 20 ° C (2500 cPa) and, as a consequence, poor-quality impregnation of the reinforcing material (rovings, twisted threads, tapes), negatively affecting the achievement of high and stable physical and mechanical properties of fiberglass products.

Closest to the proposed technical essence is a thermoset composition used for the manufacture of composite materials, including epoxy diane resin, diglycidyl ether of diethylene glycol and a eutectic mixture of aromatic amines, additionally containing a mixture of dioxane alcohols and their high boiling point esters with ionol stabilizer, and as aromatic amines - metaphenylenediamine and 4,4-diaminodiphenylmethane in the following ratio of components, parts by weight: epoxy diane resin 100, digly idilovy ether 25-35, the mixture of dioxane alcohols and their esters with boiling stabilizer ionol 4-12, the eutectic mixture of aromatic amine comprising meta-phenylenediamine and 4,4-diaminodiphenylmethane in a ratio of 35: 65-65: 35: 20-40.

The present invention solves the problem of expanding the range of thermosetting epoxy compositions used for the manufacture of composite materials.

This problem is solved in that the known composition of the thermosetting binder for composite materials, including epoxy diane resin, diethylene glycol diglycidyl ether and amine hardener, additionally contains phenyl glycidyl ether according to the invention, and it contains benzam ABA as a hardener, which is a condensation product of aniline and formaldehyde the presence of an acid catalyst and containing aminobenzylaniline as the main substance, in the following ratio of components s in wt.%

Epoxy Dianan resin 60-70

Diethylene glycol diglycidyl ether 5-15

Phenylglycidyl ether 1-5

Hardener rest

The composition is prepared by mixing the starting components at room temperature and used for the manufacture of reinforced plastics.

Table 1 shows the options for the composition of the proposed composition and its properties. Table 2 shows the test results of reinforcing bars (d 5-6 mm), made of the proposed composition by pultrusion followed by thermosetting.

Table 1 No. p / p The composition in wt. % Composition properties ED DEG-1 FGE Benzam ABA Tensile strength, MPa Modulus of elasticity, MPa Relates. elongation in% 1 60 10 2 28 33.1 230 9.1 2 65 5 2 28 39.0 276 13.0 3 68 2 1 29th 45.3 300 26.0 4 62 3 5 thirty 42,4 280 20.9 5 67 7 3 23 25.5 200 18.1 Note: ED is an epoxy diane resin; in examples 1 and 2, ED-20 resin is used, in the rest of ED-22; DEG-1 - diglycidyl ether of diethylene glycol; PGE-phenyl glycidyl ether. table 2 Composition number The composition of the rod in wt. % Properties of the resulting rods Binder Filler Density, g / cm ³ Tensile Strength MPa (n / mm ² ) Flexural strength MPa (n / mm ² ) Alkali resistance, in% 1. 2. 3. 4. 5. 6. 7. 1 25 75 1.92 1080 740 8.0 2 23 77 1.93 1200 850 3,5 3 thirty 70 1.91 1180 840 3.8 4 twenty 80 1.91 1070 760 7.4 5 25 75 1.92 1230 850 4.2

Note:

1. In examples 1 and 4, fiberglass was used as a filler, in the rest - basalt roving.

2. Alkali resistance - loss of tensile strength after holding the sample in a 4% sodium hydroxide solution at 95 ° C for a day.

Claims (1)

A thermosetting binder for composite materials, including an epoxy Dianova resin and an amine hardener, characterized in that it additionally contains an aliphatic epoxy resin DEG-1 and phenyl glycidyl ether, and as a hardener contains Benzam ABA, which is a condensation product of aniline and formaldehyde in the presence of an acid catalyst containing aminobenzylaniline as the main substance in the following ratio of components, wt.%: Epoxy Dianan resin 60-70 Aliphatic epoxy resin DEG-1 5-15 Phenyl glycidyl ether 1-5 Hardener Else