WO2009132504A1

WO2009132504A1 - A method for preparing air-drying epoxy vinyl ester resin

Info

Publication number: WO2009132504A1
Application number: PCT/CN2009/000103
Authority: WO
Inventors: 钱建华; 刘坐镇
Original assignee: 华东理工大学华昌聚合物有限公司
Priority date: 2008-04-28
Filing date: 2009-01-23
Publication date: 2009-11-05
Also published as: CN101397364B; CN101397364A

Abstract

A method for preparing air-drying epoxy vinyl ester resin, which comprises reacting bisphenol A type epoxy resin with acrylic acid or methacrylic acid, and fumaric acid for 2-6 hours, then adding dropwise dicyclopentadiene and reacting for 1-3 hours at 110-130℃ till an acid number below 20mgKOH/g is reached, finally cooling the reaction product to a temperature blow 110℃ and adding styrene for diluting.

Description

Preparation method of air-drying epoxy vinyl ester resin

Technical field

The invention belongs to the technical field of high molecular polymers, and particularly relates to a preparation method of an air-drying epoxy vinyl ester resin. Background technique

Epoxy vinyl ester resin has excellent corrosion resistance and mechanical properties of epoxy resin, and has convenient processability for processing of unsaturated polyester resin. It has become the main matrix material of corrosion-resistant glass fiber reinforced plastic products. Wide, throughout the chemical, metallurgical, construction and other anti-corrosion areas.

The epoxy vinyl ester resin has a vinyl group at both ends, and the intermediate skeleton is an epoxy resin, and belongs to a class of unsaturated polyester resins. The curing of the epoxy vinyl ester resin occurs by a crosslinking reaction by a radical activation resin generated by an initiator and a double bond in a crosslinking agent. Generally, epoxy vinyl ester resins are only suitable for the production of FRP products with unsatisfactory surface finish, and are not suitable as coatings because copolymers composed of epoxy vinyl esters, vinyl monomers, organic peroxides and accelerators are used. When the layer is thin, it is affected by atmospheric oxygen and causes the surface of the product to be sticky and incompletely cured.

With the deep application of epoxy vinyl ester resin in the fields of anti-corrosion, composite materials, etc., people put forward higher requirements for its performance, especially when used as FRP gel coat and anti-corrosion paint. High, this requires modification of the existing epoxy vinyl ester resin. At present, fumaric acid or isocyanate is generally used to modify the bisphenol A epoxy vinyl ester resin to improve the mechanical properties and process properties of the vinyl ester resin. ZL20041007573 discloses a method for synthesizing a corrosion-resistant epoxy vinyl ester resin having a particularly high molecular weight by using acrylic acid and bisphenol A epoxy resin as main raw materials and using fumaric acid and toluene diisocyanate as chain extenders, the surface of the resin cured product Good air drying, 0.15mm thick coating, dry time 4h, surface hardness up to 3H. However, this synthesis method also has the disadvantages of a long production cycle, and the viscosity of the resin at the end of the reaction is too fast to be easily controlled. Chinese Patent No. 200610117800.7 discloses a synthesis process of an epoxy vinyl ester resin, which uses a low epoxy equivalent and a high epoxy equivalent of a bisphenol A epoxy resin, an organic monounsaturated carboxylic acid synthesis gas dry epoxy vinyl ester. The method of resin. The resin is air-drying, and the surface is dry for 0.5 hours, which is 4 hours. However, this synthesis method also has a disadvantage of high raw material cost and high reaction temperature. Summary of the invention

The object of the present invention is to provide a method for preparing an air-drying epoxy vinyl ester resin which has low production cost, excellent air drying property and low shrinkage rate, and the epoxy vinyl ester resin produced by the method is suitable for metal, wood and concrete. And the coating of the surface of the structure and the like, and the production of FRP gel coat.

The object of the present invention, as achieved by the air dry epoxy vinyl ester resin, is in mass percent, including:

Bisphenol A type epoxy resin 20~50%

Acrylic or methacrylic acid 5~20%

Fumaric acid 2~12%

Dicyclopentadiene 0~10%

Catalyst 0.1~1.0%

Inhibitor 0.01~0.1%

Styrene 30~50%

The preparation method comprises the following steps: reacting bisphenol A type epoxy resin, acrylic acid or methacrylic acid, fumaric acid, and modifying the formed epoxy vinyl ester resin with dicyclopentadiene, and then diluting with a diluent. The product was obtained. The specific steps include:

(1) According to the above mass percentage, the bisphenol A epoxy resin, acrylic acid or methacrylic acid, fumaric acid, catalyst, and polymerization inhibitor are put into the reaction kettle, the stirring is started, and the temperature is gradually increased, and the temperature is controlled at 90 to 130 ° C. The reaction is carried out for 2 to 6 hours.

(2) Dicyclopentadiene is added dropwise to the above reaction system, and the temperature is controlled at 110 to 130 Torr for 1 to 3 hours until the acid value falls below 20 fflgK0H/g.

(3) The reaction product is cooled to below 110 ° C, styrene is added, and the mixture is uniformly mixed to obtain an air-drying epoxy vinyl ester resin.

The bisphenol A type epoxy resin includes E-51, E-44 bisphenol A type epoxy resin, etc.; the catalyst is benzyldimethylamine, benzyldiethylamine or benzyltriethylammonium chloride One; the polymerization inhibitor is one of hydroquinone, methyl hydroquinone, 4-tert-butyl catechol, 2, 5-di-tert-butyl hydroquinone, p-benzoquinone.

Dicyclopentadiene using technical grade dicyclopentadiene, weight percentage of about 80 to 95%, may be from ethylene cracker byproduct of coal tar or petroleum C ₅ fractions.

Usually, when the epoxy vinyl ester resin is cured, the surface will be sticky, which is the oxygen in the air during curing. The reaction causes: the radical R generated in the initial stage combines with molecular oxygen to form a polymer peroxy radical R0 ₂ *, and the activity of R* is larger than that of R0 ₂ , and stays at the surface of the product at R0 ₂ , at this stage, The increase in molecular weight of the polymer is inhibited. Compared with the double bond in the unsaturated polyester resin, the unsaturated double bond on the alicyclic ring in the dicyclopentadiene preferentially captures oxygen, and combines with oxygen in the air to form a peroxide, thereby achieving dry oil-like cross-linking drying. Therefore, the inhibition of the crosslinking of the double bond on the maleic acid with the styrene by oxygen is slowed down, the surface is quickly dried, and the resin has air-drying properties.

Compared with the prior art, the present invention has the following advantages:

A gas-drying biscyclopentadienyl group is introduced into the molecule of the epoxy vinyl ester resin, and the copolymer of the addition product and styrene is free from the inhibition of oxygen in the atmosphere, and has good air drying property. . For a 0.1 mm thick coating, the surface dry time is 0.5 h, the dry time is 4 h, and the surface hardness can reach 3H.

2 The use of dicyclopentadiene modified raw materials is low in cost, and it is not necessary to use a higher cost toluene diisocyanate or a high epoxy equivalent epoxy resin to increase the molecular weight of the polymer and improve the air drying property of the resin.

3 The synthesis process is simple, environmental protection has no "three wastes", and the product has good stability.

4 The product provided by the invention has excellent performances such as curing at room temperature, fast curing speed, high adhesion of paint film, low shrinkage rate and good corrosion resistance. detailed description

The invention is described in more detail below with reference to examples, but the invention is by no means limited to the examples.

Example 1

In a 500ml reactor equipped with a thermometer, a stirrer, a nitrogen inlet tube and a condenser, 196g of E51 bisphenol A epoxy resin, 70g of methacrylic acid, 23.5g of fumaric acid, lg of benzyldimethylamine, hydroquinone 0.10 g, the stirring was started, the temperature was gradually raised, and the reaction was controlled at 110 Torr for 4 hours. In the reaction system, 28 g of dicyclopentadiene was slowly added dropwise, and the temperature was controlled at 11 (TC reaction for 3 hours until the acid value fell below 20 ragK0H/g. The reaction product was cooled to below 110 ° C to add 180 g of styrene, and the mixture was uniformly cooled. The output was filtered to 60 ,, and a pale yellow viscous liquid was obtained by filtration. Example 2:

In a 1000ml reactor equipped with a thermometer, a stirrer, a nitrogen inlet tube and a condenser, 392g of E51 bisphenol A epoxy resin, 160g of methacrylic acid, 24g of fumaric acid, 3g of benzyldiethylamine, methyl-p-benzene The diphenol was 0.24 g, the stirring was started, and the temperature was gradually raised, and the reaction was controlled at 90 ° for 6 hours. 30 g of dicyclopentadiene was slowly added dropwise to the reaction system, and the temperature was controlled at 130 ° C for 1 hour until the acid value fell below 20 mg K0H / g. The reaction product was cooled to below 110 Torr and 395 g of styrene was added. After mixing, the mixture was cooled to a temperature of 60 Torr, and filtered to obtain a pale yellow viscous liquid. Example 3 _:

In a 500 ml reactor equipped with a thermometer, a stirrer, a nitrogen inlet tube and a condenser, 196 _{g of} E51 bisphenol A epoxy resin, 60 _g of methacrylic acid, 37.5 g of fumaric acid, 2 g of benzyltriethylammonium chloride, and the like. 0.12 g of 4-tert-butyl catechol, stirring was started, and the temperature was gradually raised, and the reaction was controlled at 130 Torr for 2 hours. 48 g of dicyclopentadiene was slowly added dropwise to the reaction system, and the temperature was controlled at 110 ° C for 3 hours until the acid value fell below 20 mg K0H / g. The reaction product was cooled to below 110 ° C to add 180 g of styrene, and after mixing uniformly, the temperature was lowered to 60 Torr, and filtered to obtain a pale yellow viscous liquid. Example 4:

In a 500ml reactor equipped with a thermometer, a stirrer, a nitrogen inlet tube and a condenser, 227g of E44 bisphenol A epoxy resin, 75g of methacrylic acid, 17g of fumaric acid, 2g of benzyldimethylamine, and hydroquinone 0.12 were charged. g, the stirring was started, the temperature was gradually raised, and the reaction was controlled at 100 ° C for 5 hours. 20 g of dicyclopentadiene was slowly added dropwise to the reaction system, and the temperature was controlled at 110 Torr for 3 hours until the acid value fell below 20 mg K0H/g. The reaction product was cooled to below 110 ° C to add 210 g of styrene, mixed uniformly, and then cooled to 6 CTC discharge, and filtered to obtain a pale yellow viscous liquid. Example 5

In a 1000ml reactor equipped with a thermometer, a stirrer, a nitrogen inlet tube and a condenser, 454g of E44 bisphenol A epoxy resin, 120g of methacrylic acid, 75g of fumaric acid, benzyldiethylamine, 2, 5-di-tert 0.24 g of butyl hydroquinone, stirring was started, and the temperature was gradually raised, and the reaction was controlled at 110 ° C for 4 hours. 95 g of dicyclopentadiene was slowly added dropwise to the reaction system, and the temperature was controlled at 13 CTC for 1 hour until the acid value fell below 20 mg 0 H/g. The reaction product was cooled to below 110 ° C to add 450 g of styrene, and the mixture was uniformly mixed, and then cooled to 60 ° C to discharge, and filtered to obtain a pale yellow viscous liquid. In a 1000 ml reactor equipped with a thermometer, a stirrer, a nitrogen inlet tube and a condenser, 392 g of E51 bisphenol A epoxy resin, 116 g of acrylic acid, 48 g of fumaric acid, 4 g of benzyltriethylammonium chloride, and p-benzoquinone were charged. 0.20 g, the stirring was started, the temperature was gradually raised, and the reaction was controlled at 130 ° C for 2 hours. 60 g of dicyclopentadiene was slowly added dropwise to the reaction system, and the temperature was controlled at 110 ° C for 3 hours until the acid value fell below 20 mgKOH/g. The reaction product was cooled to 11 (330 g of styrene was added below TC, mixed uniformly, and then cooled to 60 ° C to discharge, and filtered to obtain a pale yellow viscous liquid. Example 7:

In a 1000 ml reactor equipped with a thermometer, a stirrer, a nitrogen inlet tube and a condenser, 392 g of E51 bisphenol A epoxy resin, 125 g of acrylic acid, 35 g of fumaric acid, 4 g of benzyldimethylamine, 2, 5-di-tert-butyl 0.20 g of hydroquinone was added, stirring was started, and the temperature was gradually raised, and the reaction was controlled at 120 ° C for 3 hours. In the reaction system, 44 g of dicyclopentadiene was slowly added dropwise, and the temperature was controlled at 120 ° C for 2 hours until the acid value fell below 20 mg K0H / g. The reaction product was cooled to below 110 ° C to add 320 g of styrene, and the mixture was homogenized and then cooled to 60 ° C to discharge, and filtered to obtain a pale yellow viscous liquid. Example 8

In a 500ml reactor equipped with a thermometer, a stirrer, a nitrogen inlet tube and a condenser, 227g of E44 bisphenol A epoxy resin, 50g of acrylic acid, 37.5g of fumaric acid, benzyldiethylamine 3⁄4, methyl hydroquinone 0.10 g, the stirring was started, the temperature was gradually raised, and the reaction was controlled at 110 ° C for 4 hours. 47 g of dicyclopentadiene was slowly added dropwise to the reaction system, and the temperature was controlled at 130 ° C for 1 hour until the acid value fell below 20 mg K0H / g. The reaction product was cooled to below 110 ° C to add 220 g of styrene, and the mixture was uniformly mixed, and then cooled to 60 ° C to discharge, and filtered to obtain a pale yellow viscous liquid. Example 9

In a 1000 ml reactor equipped with a thermometer, a stirrer, a nitrogen inlet tube and a condenser, 454 g of E51 bisphenol A epoxy resin, 134 g of acrylic acid, 24 g of fumaric acid, 4 g of benzyltriethylammonium chloride, 4 t-butylene 0.20 g of benzenediol, stirring was started, and the temperature was gradually raised, and the reaction was controlled at 110 ° C for 4 hours. 28 g of dicyclopentadiene was slowly added dropwise to the reaction system, and the temperature was controlled at 120 ° C for 2 hours until the acid value fell. 20mgK0H/g or less. The reaction product was cooled to below 110 ° C to add 390 g of styrene, and the mixture was uniformly mixed, and then cooled to 60 ° C to discharge, and filtered to obtain a pale yellow viscous liquid.

Typical quality indicators for the resins obtained in the above various examples are as follows:

Typical mechanical properties of the resin casting are as follows:

Claims

Claims: 1 A method for preparing an air-drying epoxy vinyl ester resin, comprising the steps of:

(1) Ingredients in the mass percentage formula:

Fumaric acid 2~12%

Dicyclopentadiene 0~10%

Catalyst 0.1~ 1.0%

Inhibitor 0.01-0.1%

Styrene 30~50 ⁰ / ₀

(2) Putting bisphenol A epoxy resin, acrylic acid or methacrylic acid, fumaric acid, catalyst, and polymerization inhibitor into the reaction kettle, stirring is started, and the temperature is gradually increased, and the reaction is controlled at 90 to 130 Torr for 2 to 6 hours;

(3) dicyclopentadiene is added dropwise in the above reaction system, and the reaction temperature is controlled at 110 to 130 ° C for 1 to 3 hours until the acid value falls below 20 ragK0H/g;

(4) The reaction product was cooled to below 110 ° C, styrene was added, and the mixture was uniformly mixed to obtain an air-drying epoxy vinyl ester resin.

2 . The method for preparing an air-drying epoxy vinyl ester resin according to claim 1 , wherein the bisphenol A epoxy resin is E-51 or E-44 bisphenol A epoxy resin .

A method for preparing an air-drying epoxy vinyl ester resin according to claim 1, wherein the catalyst is benzyldimethylamine, benzyldiethylamine or benzyltriethylammonium chloride. One of them.

A method for preparing an air-drying epoxy vinyl ester resin according to claim 1, wherein the polymerization inhibitor is hydroquinone, methyl hydroquinone, 4-tert-butyl ortho- 2 One of phenol, 2,5-di-tert-butyl hydroquinone, p-benzoquinone.

The method for preparing an air-drying epoxy vinyl ester resin according to claim 1, wherein the dicyclopentadiene is industrial grade dicyclopentadiene, and the weight percentage thereof is 80 to 95. %, a by-product C ₅ fraction from coal tar or petroleum cracking to ethylene.