SU1740386A1 - Binding agent for glass plastics - Google Patents

Abstract

The invention relates to a binder for glass-reinforced plastics, in particular unidirectional electrical-grade glass-reinforced plastics. The invention makes it possible to create low-viscosity, low-toxic impregnating binders for obtaining nonstop durable glass plastics with reduced water absorption, due to the fact that the binder containing diallyl phthalate monomer and oligomer, an oligo ether maleinate resin, peroxide initiators, additionally combi ts ecuts, and in addition, the combination of in-target networks will be added to the system by combining short-circuiting sources, complementary initiators; fiberglass insulation and structural designation, in particular unidirectional profile fiberglass obtained by the method of continuous stretching. A low viscous binder is described. epoxy and carboxyl groups 2: 1: 1. The composition of the binder components are in the following ratio, wt.%: Diallyl phthalate 64.7- 68.8; Diallyl phthalate oligomer 2.1-13.7, diallyl phthalate copolymer with maleic anhydride 8.1-15.5, condensation product of epoxy oligomer with maleic acid maleoyl ester and stearic acid 2.6-4.4; epoxy oligomer 2.6-6.9; benzoyl peroxide 0.8-1.3; tert-butyl perbenzoate 0.8 to 1.8; cumyl peroxide 0.9-1.8. Filling samples based on the binder have the following physicomechanical properties: flexural stress of 94.9-120.0 MPa. Martens heat resistance is 120-140 ° C, Brinell hardness is 168-183 MPa and water absorption is 0.50- 0.85% per 24 h (L C VJ N O CO 00 ON materials with high mechanical strength and heat resistance. This is consisting of: Oligomerama.d.mas.% Dialylylphthalate 10.8-19.6 10.5-18.7 Oligomermate with terminal allyl monomer groups 30-1029, 3-9.5 Diallylphthalate 59.2-70, 4 57.7-67.0

Description

Benzoyl peroxide, 5-10.5-1.0

Kumil peroxide1, 0-2.01.0-1.9

Tri-butylper

benzoate1.0-2.01.0-1.9

as the closest to the technical essence and the achieved effect, selected for the prototype. The binder prototype is distinguished by its high technological characteristics, low viscosity, low toxicity. Polymeric materials based on it have high physicomechanical and dielectric properties.

The disadvantage of the prototype binder is the relatively high water absorption of fiberglass based on it (up to

2%).

The aim of the invention is to improve the water resistance of fiberglass. The goal is achieved by the fact that the binder containing diallyl phthalate, diallyl phthalate oligomer, oligoequamide manate resin, peroxide initiator as the oligoethermalate resin takes the product of the interaction of epoxyoligomer with a stearic acid and a body, a heart, a body, an object, a body, a red graphed body, a body, a heart, a red graphome, an object, a body, a heart, an object, a heart, a red graphed, a heart and a body, a red graphed object, a heart, a red graphed body, a heart, a red graphole, a heart and a body, a red graphed object, a heart pattern, a red graphed object, a red graphed object, a red graphole, a heart pattern, an object, a red graphed object, a heart pattern, an air line, a red graphed object, a heart pattern, an air line, a heart pattern, an air line, a heart pattern, an air line, a heart pattern, an air line, a heart pattern, an air line, an object and a body. the ratio of epoxy and carboxyl groups is 2: 1: 1, respectively, and the epoxy oligomer and copolymer of diallyl phthalate with maleic anhydride are additionally introduced. The components are taken in the following ratio, wt.%: Diallyl phthalate 64,7-68,8

Diallyl phthalate oligomer 2 .1-13.7 Malely anhydride diallyl phthalate copolymer8.1-15.5 Epoxy polymer condensation product with stearic acid and monoallyl acid

maleic ester

acids 2.6-4.4

Epoxy oligomer 2.6-6.9

Peroxide initiator2, 5-4.9 Copolymer DAP with MA and oligomer DAP are obtained by copolymerization of DAP monomer with MA in the presence of 0.1-0.25 wt.% Benzoyl peroxide at a temperature of (90 ± 2) ° C to 20-25 % conversion. The resulting polymer is a solution of oligomer DAP and copolymer DAP with MA in DAP monomer of the following composition, wt.%: DAP monomer 75-80 Oligomer DAP 15.7-2.5 DAP copolymer with MA 3.3-17.5

The polymer is used to prepare a binder without isolating the DAP oligomer and DAP / MA copolymer from it. The condensation product of epoxy oligomer with stearic acid and MAM is obtained in two stages. In the first stage, by reacting epoxy oligomer ED-20 with stearic acid at a ratio of 2: 1 epoxy and carboxyl groups, a mono-adduct is obtained. In the second stage, by reacting the mono-adduct with the MAM at a 1: 1 ratio of epoxy and carboxyl groups, an oligo ester maleate resin is obtained. The product obtained as a result of the synthesis is a light brown solid resin with a softening temperature range of 60-70 ° C; acid number 2-27 mg KOH / 1 g of the product, epoxy number 0.2-0.7%. Without further purification, it is used to prepare binders.

Epoxy oligomer is an epoxy-dianin ED-20 resin based on diphenylolpropane and epichlorohydrin (GOST 10587-84), which is a viscous, resinous, light brown product with the following characteristics: Dynamic viscosity at 25 ° С12–25 Pa –s with gel time with a velter of 4–8 h Massov

chlorine ions0.003-0.006%

A mixture of benzoyl peroxides, cumyl, tert-butyl perbenzoate in the amount of (0.8-1.3) (0.8-1.8) (0.9-1.8), respectively, is used as polymerization initiators. Benzoyl peroxide GOST 14888-78; cumyl peroxide TU 38-4030-77; required perbenzoate TU 6-01-461 / 79.

The initiators are injected into the binder in advance or immediately before use. If necessary, long-term storage in the composition of the initiated binder is introduced 0: 0.5-0.5% of the inhibitor. Binders are prepared by dissolving the epoxy oligomer, the condensation product, and the peroxide initiators in the polymer. Binders obtained in this way for a long time under normal conditions retain low viscosity (conditional viscosity of prepared binders according to VZ-4 at 20 ° C for 50–200 s) and quickly harden at 150–200 ° C. toxic and volatile components, not fire hazardous. In the cured state, the binders have the following physicomechanical indicators: flexural stress 94.9-120 MPa; Martens heat resistance 120-140 ° C; Brinell hardness 168-183 MPa. The unidirectional profile glass-reinforced plastics obtained on the basis of the claimed binder have the following physicomechanical indicators, the fracture stress during bending of fiberglass profiles 1153-1415 MPa, water absorption 0.5-0.7%. The positive effect of the claimed binder is to increase the mechanical strength and reduce the water absorption of glass-reinforced plastics based on it compared to glass-based plastics based on the binder-prototype, In Table. Figure 1 shows the physicomechanical properties of the casting specimens and core unidirectional glass-reinforced plastics based on the claimed and known binders.

Given in Table. 1, the data indicate that potting specimens and glass-reinforced plastics based on the claimed binder have a breaking stress on bending (17.7-19.8)%, (28.1- 13.2)%, respectively, higher than samples based on the binder prototype. Compared to the epoxy binders used at present for the manufacture of core fiberglass plastics, the inventive binder is non-toxic, non-flammable, has low viscosity and high curing speed at temperatures of 150-200 ° C, greater viability under processing conditions , which reduces the number of scrap, its use allows to increase productivity and improve working conditions.

PRI me R 1. Obtaining polymerizate. 76 kg (94.8 wt.%) DAF, 4 kg (5 wt.%) MA and 0.16 kg (0.2 wt.%) PB are loaded into a reactor with a capacity of 100 l with a stirrer, a thermocouple and a reflux condenser. They are heated with stirring to (90 ± 2) ° C and are copolymerized, controlling the process by changing the refractive index until the difference between the final and initial measurement is 0.01. The contents of the reactor are cooled to room temperature. The resulting solution contains, wt%:

DAP copolymer with MA17,5

DAP-oligomer4,8

DAP monomer77,7

It has the following properties: conditional viscosity at 25 ° С according to VZ-4 120 s. p20 1.5299.

Copolymerisates with a different ratio of DAP and MA are prepared as described in Example 1. The results are shown in Table 2.

PRI me R 5. Obtaining a condensation product.

In a three-neck flask with a capacity of 1 l with a stirrer and reflux condenser load 215 g (0.5 mol) of an epoxy-diane resin with an epoxy content of 20% and 150 ml of toluene. The contents of the flask are heated with stirring to (90 ± 5) ° C, 142.2 g (0.5 mol) of stearic acid, 2 g of pack-606 / 2-2.4.6 tris (dimethylaminomethyl) phenol are loaded into the flask. , (TU 6-05-4136-75). The reaction mass is heated to (120 ± 5) ° C and the process is carried out at this temperature to an acid number of 4.7 mg KOH / 1 g of substance.

Next, 78 g (0.5 mol) of monoallyl maleate with an acid number of 360 mg KOH / 1 g of powder is loaded into the flask and carried out at a temperature of (120 ± 5) ° C to an acid number of the reaction mass of 25.4 mg KOH / 1 g of the substance .

Then from the reaction mass is distilled

volatile components at a temperature of (100- ± 10) ° C and a residual pressure of 19.6-29.4 KPa. 430 g of a solid, light brown, resinous product were obtained with the following characteristics: acid number 27.4 mg KOH / 1 va, epoxy number 0.7%.

PRI me R 6. Preparation of the binder.

In a three-neck flask with a capacity of 1 l with a stirrer and reflux condenser, the polymerizate obtained in example 1-4, the condensation product obtained in example b, and the epoxy oligomer ED20 with an epoxy number of 20% are loaded. PB, MPC, TBPB Heated to (45 ± 5) ° C and stirred until a homogeneous mass. The binder thus prepared is used to make potting.

samples and profile fiberglass.

Curing of the casting samples is carried out in a stepwise temperature mode of 70-160 ° C for 20 h.

Preparation of binder compounds

is carried out according to Example 6. The formulation of the binder and the physicomechanical properties of the casting samples and profile glass-based plastics based on them are given in Table 3, Examples 6-18.

PRI me R 19. Obtaining unidirectional profile fiberglass.

Glass band RBN 10-25-20-78 is passed through an impregnating bath with a temperature of 25-30 ° C filled with a binder,

prepared according to example 6-18.

Impregnated glass fiber is formed and cured in a continuous manner in dies at 190-200 ° C. The drawing speed is 970-1500 mm / min.

Claims (1)

Invention Formula Binder for fiberglass plastics, including diallyl phthalate, diallyl phthalate oligomer, oligo ester maleate gum, peroxide initiator, characterized in that, in order to improve the water resistance of fiberglass on its basis, it contains as a oligo metal sulfate gum from the template, it contains the product of the effec- acid and maleic acid ester of maleic acid, obtained at a ratio of 2: 1: 1 epoxy and carboxyl groups, respectively, and additionally contains an epoxy oligomer and a copolymer of diallyl phthalate with ma 0 five linoic anhydride in the following ratio of components, wt.%: Diallyl phthalate 64,7-68,8 Diallyl phthalate oligomer 2,1-13,7 Diallyl phthalate copolymer with maleic anhydride8,1-15,5 The product of the interaction of epoxy-oligomer with stearic acid and maleic acid monoallyl ester 2,6-4,4 Peroxide initiator 2.5-3.5 Epoxy oligomer 2.6-6.9 Table 1 Continuation of table 1 20 table 2 Continuation of table 2 Tablez