Epoxy resin material, preparation method therefor and application thereof

Abstract

The present invention provides an epoxy resin material, a preparation method therefor and an application thereof. The present method for preparing an epoxy resin material comprises: heating a mixture of an epoxy resin main agent and a curing agent that are placed at room temperature to 40-85° C. for reaction and curing. The curing agent contains an adduct of an olefinic nitrile compound and an amine compound. The present method for preparing an epoxy resin material has the characteristics of low mixing viscosity, long operation time, and low amount of heat released during preparation.

Claims

1. A preparation method of an epoxy resin material, characterized in that, said preparation method comprises the following step(s): heating a mixture placed at room temperature to 40-85° C. for reaction and curing, wherein said mixture comprises an epoxy resin main agent and a curing agent; and wherein said curing agent comprises an adduct of an olefinic nitrile compound and an amine compound; wherein, said adduct of an olefinic nitrile compound and an amine compound is obtained by a method comprising the following steps: subjecting the amine compound and the olefinic nitrile compound to an addition reaction at 45-85° C.; wherein, said addition reaction is carried out under the action of an alkaline catalyst, and the amount of the alkaline catalyst used is 0.01%-0.3% by mass of the amine compound.

2. The preparation method of an epoxy resin material according to claim 1, characterized in that, after said mixture is heated, the reaction is carried out for 3-7 h.

3. The preparation method of an epoxy resin material according to claim 1, characterized in that, before said mixture is heated for reaction and curing, said mixture is placed at room temperature for 24 h or more.

4. The preparation method of an epoxy resin material according to claim 1, characterized in that, said adduct of an olefinic nitrile compound and an amine compound comprises one or more of the compounds having the following structural formula (I): ##STR00006## Wherein, the structural formula of R.sub.1 in formula (I) is selected from one of the following formulas: ##STR00007## wherein the value of n is an integer from 1 to 6; the structural formula of R.sub.2 is selected from one of the following formulas: ##STR00008## R.sub.3 is selected from H or selected from one of the following structural formulas: ##STR00009##

5. The preparation method of an epoxy resin material according to claim 1, characterized in that, said olefinic nitrile compound is one or more of acrylonitrile, 3-butenenitrile, 2-pentenenitrile, 3-pentenenitrile and 4-pentenenitrile; said amine compound is one or more of diethylenetriamine, triethylenetetramine, polyether amine, 1,3-cyclohexyldimethylamine, isophorone diamine, 4,4′-diaminodicyclohexylmethane, diaminomethylcyclohexylmethane and diphenylmethanediamine.

6. The preparation method of an epoxy resin material according to claim 1, characterized in that, said adduct is obtained by an addition reaction of the amine compound and the olefinic nitrile compound-, wherein the molar ratio of the amine compound to the olefinic nitrile compound is 1:(1-4).

7. The preparation method of an epoxy resin material according to claim 1, characterized in that, the addition reaction is carried out for a period of 5-10 h.

8. The preparation method of an epoxy resin material according to claim 1, characterized in that, said olefinic nitrile compound has a purity of 50 wt % or more.

9. The preparation method of an epoxy resin material according to claim 8, characterized in that, said olefinic nitrile compound is obtained through purifying by a method comprising the following steps: distilling the olefinic nitrile compound under a vacuum degree of −0.5˜−0.05 MPa, and at a temperature of 20˜60° C.

10. The preparation method of an epoxy resin material according to claim 1, characterized in that, the mass ratio of said epoxy resin main agent to said curing agent is (3-8):1.

11. The preparation method of an epoxy resin material according to claim 1, characterized in that, said epoxy resin main agent comprises the following components in mass percentage: 60-80 wt % of epoxy resin, 2-20 wt % of diluent, and 1-20 wt% of defoamer, based on the mass of the epoxy resin main agent.

12. The preparation method of an epoxy resin material according to claim 11, characterized in that, said epoxy resin is one or more of a bisphenol A type epoxy resin and a bisphenol F type epoxy resin.

13. The preparation method of an epoxy resin material according to claim 12, characterized in that, said epoxy resin has an epoxy value of 0.1-0.65, and is a liquid at room temperature.

14. The preparation method of an epoxy resin material according to claim 11, characterized in that, said diluent is selected from one or more of butyl glycidyl ether, benzyl glycidyl ether, butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, 1,2-cylohexanediol diglycidyl ether, poly(ethylene glycol) diglycidyl ether, trimethylolpropane triglycidyl ether, glycidyl ether having a molecular main chain comprising a C12-C14 alkyl, benzyl alcohol, phenylethanol, nonylphenol, propylene carbonate, trimethylolpropane triacrylate, diisopropanol methyl ether, toluene and xylene; said defoamer is selected from one or more of a polyacrylate and a modified organosilicon.

15. The preparation method of an epoxy resin material according to claim 1, characterized in that, said curing agent comprises 55 wt %-75 wt % of the adduct of an olefinic nitrile compound and an amine compound, based on the total mass of the curing agent.

16. The preparation method of an epoxy resin material according to claim 15, characterized in that, said curing agent also comprises 25-45 wt % of polyether amine, based on the total mass of the curing agent.

17. The preparation method of an epoxy resin material according to claim 1, characterized in that, said mixture is heated to 50-80° C. for reaction and curing; after said mixture is heated, the reaction is carried out for 4-7 h.

18. The preparation method of an epoxy resin material according to claim 17, characterized in that, before said mixture is heated for reaction and curing, said mixture is placed at room temperature for 24 h or more.

19. The preparation method of an epoxy resin material according to claim 1, characterized in that, after the amine compound is heated to 45-85° C., the olefinic nitrile compound is added in a dropwise manner.

Description

DETAILED DESCRIPTION

(1) In order to better understand the technical solution of the present invention, the content of the present invention will be further elaborated in combination with embodiments below, but the content of the present invention is not only limited to the following embodiments.

(2) The raw materials used in the following examples and sources thereof are shown in Table 1.

(3) TABLE-US-00001 TABLE 1 raw materials and sources thereof Chemical Name Manufacturer isophorone diamine (IPDA) Wanhua Chemical Group Co., ltd. diethylenetriamine (DETA) Japan Tosoh Corporation diphenylmethanediamine (MDA) Wanhua Chemical Group Co., ltd. polyether amine (D-230) Huntsman Chemical acrylonitrile Sinopharm Chemical Reagent Co., Ltd 3-butenenitrile Sinopharm Chemical Reagent Co., Ltd 3-pentenenitrile Sinopharm Chemical Reagent Co., Ltd 4-pentenenitrile Sinopharm Chemical Reagent Co., Ltd DER 331 Dow Chemical XY622 Anhui Xinyuan Chemical Co., Ltd

(4) The viscosity that may be involved in the following examples was measured under the following test conditions: Brookfield viscometer was used, at a temperature of 25° C., with a 18 # rotor.

COMPARATIVE EXAMPLE 1

(5) (1) Preparation of an Adduct of an Olefinic Nitrile Compound and an Amine Compound (Hereinafter Referred to as Adduct)

(6) {circle around (1)} The acrylonitrile was purified by using a rotary evaporator which was vacuumed with a water pump; the vacuum degree was −0.2 Mpa, and the temperature was 45° C.; the fraction having an acrylonitrile content of about 65 wt % was collected.

(7) {circle around (2)} 170 g of IPDA was added into a reactor, the reactor was purged with nitrogen and heated to 55° C.; under the action of 0.085 g triethylamine, 106 g of the fraction obtained from {circle around (1)} was added dropwise into the reactor; after the dropwise addition was completed, the reaction was carried out for 6 h and then the temperature was lowered to room temperature, and the adduct of the olefinic nitrile compound and the amine compound was obtained.

(8) (2) Preparation of Epoxy Resin Material

(9) Preparation of epoxy resin main agent: 70 g of DER 331 was added into a mixing equipment, and heated to 55° C. and then maintained at the same temperature; 15 g of XY622 and 15 g of BYKA530 (produced by BYK Chemical) were added and continuously stirred at 70° C. for 2.5 hours to be uniformly mixed and then the mixture obtained was left standing. Preparation of curing agent: 45 g of D-230 and 55 g of the adduct prepared in (1) were added into a reactor, and fully stirred for 1.5 hours to be uniformly mixed while the temperature of the reactor was maintained at 35° C.; the mixture obtained was then left standing for 1 hour; the obtained curing agent was placed in a product container, and then sealed and stored at room temperature;

(10) The obtained epoxy resin main agent and curing agent were uniformly mixed at a mass ratio of 4:1; after being defoamed, the obtained mixture was poured into a mold, and placed at room temperature for 24 h to obtain the epoxy resin material.

(11) For 100 g of the epoxy resin material prepared in Comparative Example 1, its pot life at 25° C. was 3 h, its maximum exothermic peak temperature was 50° C., and the time when the maximum exothermic peak appeared was at 430 min; the Tg of the cured product was 90° C.; and no significant changes were observed in the epoxy resin material which was immersed in 5% HCl for 60 days, and the tensile strength was 60 MPa.

EXAMPLE 1

(12) (1) Preparation of an Adduct of an Olefinic Nitrile Compound and an Amine Compound (Hereinafter Referred to as Adduct)

(13) {circle around (1)} The acrylonitrile was purified by using a rotary evaporator which was vacuumed with a water pump; the vacuum degree was −0.2 Mpa, and the temperature was 45° C.; the fraction having an acrylonitrile content of about 65 wt % was collected;

(14) {circle around (2)} 170 g of IPDA was added into a reactor, the reactor was purged with nitrogen and heated to 55° C.; under the action of 0.085 g triethylamine, 106 g of the fraction obtained from {circle around (1)} was added dropwise into the reactor; after the dropwise addition was completed, the reaction was carried out for 6 h and then the temperature was lowered to room temperature, and the adduct was obtained.

(15) (2) Preparation of Epoxy Resin Material

(16) Preparation of epoxy resin main agent: 70 g of DER 331 was added into a mixing equipment, and heated to 55° C. and then maintained at the same temperature; 15 g of XY622 and 15 g of BYKA530 were added and continuously stirred at 70° C. for 2.5 hours to be uniformly mixed and then the mixture obtained was left standing;

(17) Preparation of curing agent: 45 g of D-230 and 55 g of the adduct prepared in (1) were added into a reactor, and fully stirred for 1.5 hours to be uniformly mixed while the temperature of the reactor was maintained at 35° C.; the mixture obtained was then left standing for 1 hour; the obtained curing agent was placed in a product container, and then sealed and stored at room temperature;

(18) The obtained epoxy resin main agent and curing agent were uniformly mixed at a mass ratio of 4:1; after being defoamed, the obtained mixture was poured into a mold, and placed at room temperature for 24 hours; then it was heated to 40° C. and reacted for 3 h to obtain the epoxy resin material.

(19) For 100 g of the epoxy resin material prepared in Example 1, its pot life at 25° C. was 3 h, its maximum exothermic peak temperature was 50° C., and the time when the maximum exothermic peak appears was at 430 min; the Tg of the cured product was 102° C.; and no significant changes were observed in the epoxy resin material which was immersed in 5% HCl for 70 days, and the tensile strength was 71 MPa.

EXAMPLE 2

(20) (1) Preparation of an Adduct of an Olefinic Nitrile Compound and an Amine Compound (Hereinafter Referred to as Adduct)

(21) {circle around (1)} The acrylonitrile was purified by using a rotary evaporator which was vacuumed with a water pump; the vacuum degree was −0.2 Mpa, and the temperature was 45° C.; the fraction having an acrylonitrile content of about 65 wt % was collected.

(22) {circle around (2)} 170 g of IPDA was added into a reactor, the reactor was purged with nitrogen and heated to 55° C.; in the presence of 0.085 g triethylamine, 106 g of the fraction obtained from {circle around (1)} was added dropwise into the reactor; after the dropwise addition was completed, the reaction was carried out for 6 h and then the temperature was lowered to room temperature, and the adduct was obtained.

(23) (2) Preparation of Epoxy Resin Material

(24) Preparation of epoxy resin main agent: 70 g of DER 331 was added into a mixing equipment, and heated to 55° C. and then maintained at the same temperature; 15 g of XY622 and 15 g of BYKA530 were added and continuously stirred at 70° C. for 2.5 hours to be uniformly mixed and then the mixture obtained was left standing;

(25) Preparation of curing agent: 45 g of D-230 and 55 g of the adduct prepared in (1) were added into a reactor, and fully stirred for 1.5 hours to be uniformly mixed while the temperature of the reactor was maintained at 35° C.; the mixture obtained was then left standing for 1 hour; the obtained curing agent was placed in a product container, and then sealed and stored at room temperature.

(26) The obtained epoxy resin main agent and curing agent were uniformly mixed at a mass ratio of 4:1; after being defoamed, the obtained mixture was poured into a mold, and placed at room temperature for 24 h; then it was heated to 85° C. and reacted for 7 h to obtain the epoxy resin material.

(27) For 100 g of the epoxy resin material prepared in Example 2, its pot life at 25° C. was 3 h, its maximum exothermic peak temperature was 50° C., and the time when the maximum exothermic peak appears was at 430 min; the Tg of the cured product was 93° C.; and no significant changes were observed in the epoxy resin material which was immersed in 5% HCl for 62 days, and the tensile strength was 65 MPa.

EXAMPLE 3

(28) (1) Preparation of an Adduct of an Olefinic Nitrile Compound and an Amine Compound (Hereinafter Referred to as Adduct)

(29) {circle around (1)} The 3-butenenitrile was purified by using a rotary evaporator which was vacuumed with a water pump; the vacuum degree was −0.2 Mpa, and the temperature was 45° C.; the fraction having an 3-butenenitrile content of about 65 wt % was collected;

(30) {circle around (2)} 103 g of DETA (diethylenetriamine) was added into a reactor, the reactor was purged with nitrogen and heated to 55° C.; under the catalysis of 0.26 g KOH, 201 g of the fraction obtained from {circle around (1)} was added dropwise into the reactor; after the dropwise addition was completed, the reaction was carried out for 6 h and then the temperature was lowered to room temperature, and the adduct was obtained.

(31) (2) Preparation of Epoxy Resin Material

(32) The preparation of epoxy resin main agent: 70 g of DER 331 was added into a mixing equipment, and heated to 55° C. and then maintained at the same temperature; 15 g of XY622 and 15 g of BYKA530 were added and continuously stirred at 70° C. for 2.5 hours to be uniformly mixed and then the mixture obtained was left standing.

(33) Preparation of curing agent: 25 g of D-230 and 75 g of the adduct prepared in (1) were added into a reactor, and fully stirred for 1.5 hours to be uniformly mixed while the temperature of the reactor was maintained at 35° C.; the mixture obtained was then left standing for 1 hour; the obtained curing agent was placed in a product container, and then sealed and stored at room temperature.

(34) The obtained epoxy resin main agent and curing agent were uniformly mixed at a mass ratio of 7:1; after being defoamed, the obtained mixture was poured into a mold, and placed at room temperature for 24 hours; then it was heated to 50° C. and reacted for 4 h to obtain the epoxy resin material.

(35) For 100 g of the epoxy resin material prepared in Example 3, its pot life at 25° C. was 6 h, its maximum exothermic peak temperature was 35° C., and the time when the maximum exothermic peak appears was at 600 min; the Tg of the cured product was 120° C.; and no significant changes were observed in the epoxy resin material which was immersed in 5% HCl for 90 days, and the tensile strength was 80 MPa.

EXAMPLE 4

(36) (1) Preparation of an Adduct of an Olefinic Nitrile Compound and an Amine Compound (Hereinafter Referred to as Adduct)

(37) {circle around (1)} The 4-pentenenitrile was purified by using a rotary evaporator which was vacuumed with a water pump; the vacuum degree was −0.2 Mpa, and the temperature was 45° C.; the fraction having an 4-pentenenitrile content of about 65 wt % was collected.

(38) {circle around (2)} 230 g of D-230 (polyether amine) was added into a reactor, the reactor was purged with nitrogen and heated to 55° C.; under the catalysis of 0.23 g hexahydropyridine, 243 g of the fraction obtained from {circle around (1)} was added dropwise into the reactor; after the dropwise addition was completed, the reaction was carried out for 6 h and then the temperature was lowered to room temperature, and the adduct was obtained.

(39) (2) Preparation of Epoxy Resin Material

(40) Preparation of epoxy resin main agent: 70 g of DER 331 was added into a mixing equipment, and heated to 55° C. and then maintained at the same temperature; 15 g of XY622 and 15 g of BYKA530 were added and continuously stirred at 70° C. for 2.5 hours to be uniformly mixed and then the mixture obtained was left standing;

(41) Preparation of curing agent: 25 g of D-230 and 75 g of the adduct prepared in (1) were added into a reactor, and fully stirred for 1.5 hours to be uniformly mixed while the temperature of the reactor was maintained at 35° C.; the mixture obtained was then left standing for 1 hour; the obtained curing agent was placed in a product container, and then sealed and stored at room temperature.

(42) The obtained epoxy resin main agent and curing agent were uniformly mixed at a mass ratio of 5:1; after being defoamed, the obtained mixture was poured into a mold, and placed at room temperature for 24 h; then it was heated to 80° C. and reacted for 7 h to obtain the epoxy resin material.

(43) For 100 g of the epoxy resin material prepared in Example 4, its pot life at 25° C. was 4.7 h, its maximum exothermic peak temperature was 43° C., and the time when the maximum exothermic peak appears was at 520 min; the Tg of the cured product was 114° C.; and no significant changes were observed in the epoxy resin material which was immersed in 5% HCl for 85 days, and the tensile strength was 76 MPa.

(44) In the above Examples 1-4, the adducts of an olefinic nitrile compound and an amine compound used may also be not prepared by the methods of the examples described-above, and may be existing raw materials that can be directly used and meet the same requirements, or may be commercially available.

(45) During the preparation of the epoxy resin material in Comparative Example 1, it does not contain a step of reacting at a raised temperature, but only a step of placing at room temperature. Compared with examples which contain a subsequent reaction at a temperature raised to 40-85° C., the epoxy resin material prepared in Comparative Example 1 has a lower Tg value, a poor solvent resistance and tensile strength. In Examples 1 and 2, the temperatures for the reaction at a raised temperature were 40° C. and 85° C., respectively; compared with Examples 3-4 wherein the temperatures for the reaction at a raised temperature were 50-80° C., the solvent resistance, Tg value, and tensile strength of the products prepared in Examples 1 and 2 were inferior to those prepared in Examples 4-5. In addition, Examples 3-4 show a longer pot life, a higher exothermic temperature and also a greatly delayed time when the maximum exothermic peak appears.

(46) Those skilled in the art would appreciate that many modifications or adjustments of the present invention can be made in the teachings of the present disclosure. Such modifications or adjustments should also be within the scope of the claims of the present invention.