RU2506291C2 - Polymer composition - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: present invention relates to production of polymer compositions based on epoxy resins and modified amine curing agents, intended for producing high-strength composite materials with high resistance to thermal deformation. Described is a polymer composition based on epoxy resin, active epoxy diluents and nitrogen-containing curing agents intended for producing high-strength composite materials with high resistance to thermal deformation, characterised by that the curing agent is a product of reaction of an amine component with monocarboxylic acids, using as the amine component a mixture consisting of a primary aromatic amine or a mixture of aromatic amines (A), a secondary aliphatic amino alcohol (B) and a tertiary aliphatic amino alcohol (C) in weight ratio A:B:C from 98:0.2:1.8 to 80:5:15, and a monocarboxylic acid (D) is added in form of a 25-80% solution to the monoatomic aliphatic or aromatic alcohol, or ester thereof with a mono- or dicarboxylic acid, in ratio (A+B+C):D from 90:10 to 60:40 per 100% acid, followed by reaction by mixing in a reactor at temperature ranging from 50 to 130°C for 20 to 120 minutes and mixer speed of 100 to 3000 rpm, and additionally contains a thickener, a pigment or a dye, wherein the composition contains the following in pts.wt: epoxy resin - 100, active epoxy diluent - 5-130, curing agent - 15-110, thickener - 5-50, pigment and dye - 0.5-25.

EFFECT: obtaining compositions having a long life during processing, having in a cured state high resistance to thermal deformation and improved dielectric properties.

2 tbl, 7 ex

Description

The invention relates to the field of producing polymer compositions based on epoxy resins and modified amine hardeners with various target additives and can be used for high-strength composite materials with high deformation heat resistance.

The closest prototype of the claimed invention is a series of polymer compositions based on epoxy resins, active diluents and modified amine hardeners (see Handbook of Plastics, Volume II, edited by Kataev V.M. et al. M. Publishing House "Chemistry", 1975 )

A disadvantage of the known compositions is the mismatch of technological properties with the new requirements for the industrial use of composite materials, such as the adjustable rheological properties that ensure their use in the formation of large-sized products with vertical surfaces, the presence of high viability, the possibility of curing in a wide temperature range while achieving high deformation heat resistance and improved dielectric indicators that persist after od temporary exposure to elevated temperatures and 100% humidity.

The aim of the invention is to achieve a set of technological properties of a family of polymer compositions, ensuring their high viability during processing, curing in the temperature range from -10 ° C to + 60 ° C at 100% humidity and under water, the possibility of using prepregs based on them on vertical surfaces and the achievement in the cured state of increased deformation heat resistance and improved dielectric properties that persist after exposure to 100% humidity and increased ennyh temperatures.

This goal is achieved in that the composition based on epoxy resin and an active epoxy diluent contains a hardener obtained by the interaction of amines with monocarboxylic acids using, as an amine component, a mixture consisting of a primary aromatic amine or a mixture of aromatic amines (A), a secondary aliphatic amino alcohol ( B) and a tertiary aliphatic amino alcohol (B) in a mass ratio of A: B: C from 98: 0.2: 1.8 to 80: 5: 15, and monocarboxylic acid (D) is introduced as a 25 ÷ 80% solution in a monoatomic alif tritic or aromatic alcohol, or their ester with mono- or dicarboxylic acid, in the ratio (A + B + C): D from 90:10 to 60:40 in terms of 100% acid, while the interaction process is carried out by stirring in a reactor at a temperature of from 50 ° C to 130 ° C for 20 to 120 minutes and a stirrer speed of 100 to 3000 rpm, as well as a thickener, dye or pigment, the composition contains in parts by weight

epoxy resin -one hundred active epoxy diluent -5 ÷ 130 hardener -15 ÷ 110 thickener -5 ÷ 50 pigment or dye -0.5 ÷ 25

Example 1

Obtaining hardener

In a reactor equipped with heating, cooling and a high-speed stirrer, 3 ingredients included in the amine component are alternately loaded - metaphenylenediamine (A), secondary amino alcohol - diisopropanolamine (B) and tertiary amino alcohol - N, N 'diisopropanylethanolamine (C) in a mass ratio A : B: C = 88: 2.6: 9.4. The mixture is stirred at 100 ° C for 5 minutes at 1500 rpm of the working mixer. Then, butyric acid (G) is added to the reactor in the form of a 50% solution in ethanol in the ratio (A + B + C): G = 75: 25 in terms of 100% acid and maintaining the temperature at 100 ° C, when the stirrer is working, they interact for 60 minutes.

The obtained hardener is used to prepare a polymer composition.

Preparation of polymer composition

In another reactor load 100 wt.h. epoxy Dianova resin brand ED-20 and 70 parts by weight active epoxy diluent - diglycidyl ether polyepichlorohydrin brand E-181. The temperature in the reactor was raised to 70 ° C and stirred for 10 minutes at 500 rpm / min, after which 27 wt.h. thickener - oxypropylated starch and 12 parts by weight dye - phthalocyanine blue. The temperature in the reactor is reduced to + 25 ° C, load 60 wt.h. hardener and mix at the same speed for 15 minutes. The resulting composition is sent for processing.

Examples 2 ÷ 8 are carried out analogously to example 1 with a change in parameters and components in accordance with table 1.

The properties of the obtained composition according to examples 1-8 are presented in table 2, which shows its advantages over the known technical solutions.

table 2 The properties of the inventive polymer composition according to examples 1] -7 No. p / p Name of indicator The value of the indicator for examples 1-7 and prototype one 2 3 four 5 6 7 prototype one The curing time of the composition At -10 ° C, day 3 one 2 2 one 3 3 Not cured At + 60 ° С, min thirty twenty 25 25 twenty thirty thirty thirty At + 20 ° С, hour under water eighteen 10 12 12 10 eighteen eighteen Not cured 2 Composition viability At 20 ° C, min 120 one hundred 110 110 one hundred 120 120 50-60 At 40 ° C, min 40 thirty 35 35 thirty 40 40 20-60 3 The indicators of the cured compositions in the cold state; tensile strength σ-tensile, MPa; 105 one hundred 120 one hundred 105 130 one hundred 80 σ-under compression, MPa; 150 250 200 220 160 165 165 148 - specific volume electric resistance, Ohm · cm 8 · 10 ¹⁴ 7 · 10 ¹⁴ 9 · 10 ¹⁵ 8.510 ¹⁴ 9 · 10 ¹⁴ 8 · 10 ¹⁴ 6 · 10 ¹⁴ 6 · 10 ¹⁴ - dielectric loss tangent 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 four Cured compositions after 30 days of exposure to T = 80 ° C and 100% humidity: - in tension, MPa; 9288 105 96 105 94 96 98

- under compression, MPa 160 165 170 165 170 160 158

- specific volume electric resistance, Ohm / cm 6 · 10 ¹⁴ 5 · 10 ¹⁴ 4 · 10 ¹⁴ 5 · 10 ¹⁴ 2 · 10 ¹⁴ 6 · 10 ¹⁴ 8 · 10 ¹⁴ 6 · 10 ¹³ - dielectric loss tangent 0,022 0,026 0,020 0,021 0,022 0,020 0.02 0.16

Claims (1)

A polymer composition based on epoxy resin, active epoxy diluents and nitrogen-containing hardeners, intended for the manufacture of high-strength composite materials with increased deformation resistance, characterized in that it contains the product of the interaction of the amine component with monocarboxylic acids as a hardener, using a mixture as the amine component, consisting of a primary aromatic amine or a mixture of aromatic amines (A), a secondary aliphatic amine mouth (B) and tertiary aliphatic amino alcohol (C) in a mass ratio of A: B: C from 98: 0.2: 1.8 to 80: 5: 15, and monocarboxylic acid (G) is administered in the form of - 25 ÷ 80% a solution in a monohydric aliphatic or aromatic alcohol, or their ether with mono- or dicarboxylic acid, in the ratio (A + B + C): D from 90:10 to 60:40 in terms of 100% acid, followed by interaction by stirring in the reactor at a temperature of from 50 to 130 ° C for 20 to 120 min and a stirrer speed of 100 to 3000 rpm, and further comprises a thickener, pigment or dye, while the composition contains in parts by weight:
Epoxy resin one hundred Active Epoxy Thinner 5 ÷ 130 Hardener 15 ÷ 110 Thickener 5 ÷ 50 Pigment or dye 0.5 ÷ 25