CN104072687A - Epoxy vinyl ester resin compound catalytic synthesis technology - Google Patents
Epoxy vinyl ester resin compound catalytic synthesis technology Download PDFInfo
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- CN104072687A CN104072687A CN201410294684.0A CN201410294684A CN104072687A CN 104072687 A CN104072687 A CN 104072687A CN 201410294684 A CN201410294684 A CN 201410294684A CN 104072687 A CN104072687 A CN 104072687A
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Abstract
The invention relates to an epoxy vinyl ester resin compound catalytic synthesis technology, aiming at solving the technical problems of excessively high reaction temperature and more side reactions during the epoxy vinyl ester resin synthesis process, and belonging to the technical field of high-molecular polymer. The epoxy vinyl ester resin compound catalytic synthesis technology is characterized in that when epoxy resin and unsaturated monocarboxylic acid are in ring-opening polymerization reaction, a quaternary ammonium salt and acetylacetone metal salt complex composition is adopted as a compound catalyst, wherein the weight ratio of the quaternary ammonium salt to acetylacetone metal salt complex is (1:3)-(3:1). The epoxy vinyl ester resin compound catalytic synthesis technology has the positive effects that the adopted compound catalyst achieves a synergistic effect, the reaction activation energy can be reduced, and the reaction temperature is reduced to 60-85DEG C from generally 100-130DEG C; various side reactions such as self ring-opening polymerization and cross-linking, esterification reaction between hydroxyl and carboxyl and etherification reaction between epoxy group and hydroxyl are fewer; the product epoxy vinyl ester resin is good in comprehensive performances of mechanical performance, corrosion resistance property, electrical property and the like.
Description
Technical field
The present invention relates to a kind of synthesis technique of epoxy vinyl ester resin, relate in particular to a kind of synthesis technique that adopts catalyst compounded epoxy vinyl ester resin, belong to high molecular polymer technical field.
Background technology
Epoxy vinyl ester resin is to take epoxy resin with to contain ethylene linkage unsaturated monocarboxylic acid (as methacrylic acid, vinylformic acid) be main raw material, under the effect of catalyzer, carry out ring-opening polymerization and obtain, and form a double bond containing class unsaturated polyester resin with the active cross-linking monomer dilution of low viscosity.
Chemical structure, epoxy vinyl ester resin molecule two ends are containing vinyl group, and backbone structure is epoxy resin.Therefore, epoxy vinyl ester resin is a kind of performance resins with epoxy resin and two kinds of resin property advantages of unsaturated polyester resin, have on the one hand that unsaturated polyester resin viscosity is low, convenient formation, can be by features such as peroxide initiator ambient cures; Mechanical property, electrical property and the resistance to chemical corrosion on the other hand with epoxy resin excellence.Epoxy vinyl ester resin has been widely used in the resistance to chemical attack fields such as oil, chemical industry, chlor-alkali, metallurgy, by the polymer matrix composites of its making, in composite material tube tank, electrolyzer, flue gas desulfurization, communications and transportation, build a bridge, the field such as electronic apparatus is widely used.
Under catalyzer existence and suitable reactions temperature condition, the epoxy group(ing) in epoxy resin is reacted with unsaturated monocarboxylic acid generation esterification by ring opening.In order guaranteeing to react, towards esterification by ring opening main reaction, to carry out, to reduce the interference of side reaction as far as possible, it is crucial selecting suitable catalyzer.Conventional catalyzer is quaternary ammonium salt at present, and temperature of reaction is at 100-130 ℃.When temperature of reaction is too high, can there is following several side reaction: epoxy group(ing) and epoxy group(ing) self ring-opening polymerization is crosslinked; Esterification between hydroxyl and carboxyl; The etherification reaction of epoxy group(ing) and hydroxyl etc.There are to reduce mechanical property, corrosion resistance nature and the electrical property etc. of epoxy vinyl ester resin in above-mentioned side reaction.
Summary of the invention
The object of this invention is to provide that a kind of temperature of reaction is low, side reaction is few, the composite catalysis synthesizing technology of the epoxy vinyl ester resin of the mechanical property of product, corrosion resistance nature and good electrical property.
Object of the present invention realizes like this, in epoxy vinyl ester resin synthetic, when epoxy resin and unsaturated monocarboxylic acid ring-opening polymerization, adopt quaternary ammonium salt and acetyl acetone salt complex compound catalyst compounded, the weight ratio of catalyst compounded middle quaternary ammonium salt and acetyl acetone salt complex compound is 1: 3-3: 1.
For achieving the above object, the technical scheme of employing is:
The composite catalysis synthesizing technology of epoxy vinyl ester resin, is characterized in that: comprise the steps:
(1) batching is standby with mass percent formula batching:
A. epoxy resin 40%-60%
B. unsaturated monocarboxylic acid 10%-26%
C. saturated dicarboxylic acid 0%-8%
D. catalyst compounded 0.10%-1.0%
E. stopper 0.01%-0.05%
F. crosslinkable monomers 30%-45%
(2) in esterification by ring opening reaction response device, drop into material A, B, C, D, E, pass in the situation of nitrogen and stir, be warming up to gradually 60-85 ℃, reaction system all even transparent rear maintenance temperature that becomes, are less than 10mgKOH/g until record acid number;
(3) after dilution cooling, in reaction product, add crosslinkable monomers F, fully stir and obtain epoxy vinyl ester resin.
The described catalyst compounded composition that refers to acetyl acetone salt complex compound and quaternary amine of step (1), wherein the weight ratio of acetyl acetone salt complex compound and quaternary ammonium salt is 1: 3-3: 1.
Described acetyl acetone salt complex compound is a kind of in chromium acetylacetonate, methyl ethyl diketone zirconium, acetylacetone cobalt, titanium acetylacetone, manganese acetylacetonate, ferric acetyl acetonade;
Described
quaternary aminerefer to a kind of in benzyldimethylamine, benzyl diethylamine, tetramethyl ammonium chloride, 4 bromide, etamon chloride, tetraethylammonium bromide, benzyl trimethyl ammonium chloride, benzyltrimethylammonium bromide, benzyltriethylammoinium chloride, benzyl triethyl ammonium bromide.
Wherein epoxy resin refers to bisphenol A type epoxy resin, bisphenol F epoxy resin, novolac epoxy, brominated epoxy resin or Racemic glycidol amine epoxy resin.
Described unsaturated monocarboxylic acid is a kind of of vinylformic acid, methacrylic acid.
Described saturated dicarboxylic acid refers to the monounsaturated dicarboxylic acid with fat hydrocarbon long-chain, a kind of in pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid.
Stopper is Resorcinol, Resorcinol, methyl hydroquinone, t-butyl catechol, 2,6-tert-butyl catechol, 2,5 di tert butyl hydroquinone, para benzoquinone or copper naphthenate solution a kind of.
Linking agent is one or more in vinylbenzene, Vinylstyrene, Vinyl toluene, chloro-styrene, alpha-methyl styrene, t-butyl styrene, dicyclopentadiene acrylate, Phthalic acid, diallyl ester, triallyl cyanurate, butyl acrylate, methyl methacrylate, dicyclopentadiene acrylate, Phthalic acid, diallyl ester.
Compared with prior art, positively effect of the present invention is: the present invention is when epoxy resin and unsaturated monocarboxylic acid ring-opening polymerization, what adopt catalyst compoundedly has a synergy, has reduced reaction activity, and temperature of reaction is reduced to 60-85 ℃ from common 100-130 ℃; In reaction process, epoxy group(ing) and epoxy group(ing) self ring-opening polymerization is crosslinked, esterification between hydroxyl and carboxyl, the various side reactions such as the etherification reaction of epoxy group(ing) and hydroxyl are few: the good combination properties such as the mechanical property of product epoxy vinyl ester resin, corrosion resistance nature and electrical property.
Embodiment
Below in conjunction with embodiment, describing in more detail the present invention, is in order to make those of ordinary skills better understand and to implement the present invention, to should be noted that the present invention is never confined to embodiment simultaneously.
Embodiment 1:
At 1000ml, drop into bisphenol f type epoxy resin (epoxy equivalent (weight) is 162 ~ 182g/mol) 340g, methacrylic acid 200g, benzyl trimethyl ammonium chloride 0.60g, chromium acetylacetonate 0.30g, methyl hydroquinone 0.10g in thermometer, agitator, nitrogen ingress pipe and condenser there-necked flask, pass in the situation of nitrogen and stir, be warming up to gradually 80 ℃, reaction system all even transparent rear maintenance temperature that becomes, are less than 10mgKOH/g until record acid number.In reaction product, add Tert. Butyl Hydroquinone 0.05g, vinylbenzene 190g, Vinylstyrene 110g, fully stir, be finally cooled to room temperature, filter and obtain light yellow viscous liquid.
Embodiment 2:
In reactor, dropping into epoxy equivalent (weight) is bisphenol A type epoxy resin 340g, methacrylic acid 65g, benzyldimethylamine 0.5g, methyl ethyl diketone zirconium 0.5g, the Resorcinol 0.15g of 480g/mol.Pass in the situation of nitrogen and be warming up to gradually 75 ℃, reaction system becomes after homogeneous transparent and keeps temperature, until record acid number, is less than 10mgKOH/g.Add vinylbenzene 260g, fully stir, add 0.1g 4-TBP, fully stir, be finally cooled to room temperature, filter and obtain light yellow viscous liquid.
Embodiment 3:
In reactor, drop into bisphenol A type epoxy resin (epoxy equivalent (weight) is 455 ~ 500g/mol) 170g, methacrylic acid 110g, tetramethyl ammonium chloride 0.8g, acetylacetone cobalt, the Tert. Butyl Hydroquinone 0.15g of bisphenol A type epoxy resin (epoxy equivalent (weight) the is 179 ~ 192g/mol) 170g of low epoxy equivalent (weight), high epoxy equivalent (weight).Pass in the situation of nitrogen and be warming up to gradually 80 ℃, keep temperature, until record acid number, be less than 10mgKOH/g.In reaction product, add vinylbenzene 260g, methyl methacrylate 20g, fully stirs, and is finally cooled to room temperature, filters and obtain light yellow viscous liquid.
Embodiment 4:
At 1000ml, drop into E51 bisphenol A epoxide resin 196g, methacrylic acid 70g, dicyclopentadiene maleate 50g, 4 bromide 1g, manganese acetylacetonate 0.5g, methyl hydroquinone 0.10g in thermometer, agitator, nitrogen ingress pipe and condenser reactor, open and stir, heat up gradually, be controlled at reaction at 70 ℃, every one hour, measuring acid number, is reaction end until acid number is down to 10mgKOH/g below.In reaction product, add 150g vinylbenzene, control after 70 ℃ of temperature of charge stir below and obtain air-dry type oxirene ester resin.
Embodiment 5:
In reactor, drop into 505g sebacic acid, 138g glycol ether, 2g dibutyl tin laurate, is warming up to gradually 220 ℃ of insulation reaction until acid number reaches 240mgKOH/g and obtains holding carboxyl long-chain monounsaturated dicarboxylic acid monoesters.
End carboxyl long-chain monounsaturated dicarboxylic acid monoesters 24g, tetraethylammonium bromide 1g, acetylacetone cobalt 0.5g that in another reactor, to drop into epoxy equivalent (weight) be 185～208g/mol bisphenol A epoxide resin 300g, methacrylic acid 127g, made by above-mentioned steps, Resorcinol 0.20g, open and stir, heat up gradually, be controlled at 80 ℃ of reactions, every one hour, measuring acid number, is reaction end until acid number is down to 10mgKOH/g below.Reaction product is added to 250g vinylbenzene, after stirring, obtain intramolecular toughening epoxy vinyl esters resin.
Embodiment 6:
At 1000ml, drop into E51 bisphenol A epoxide resin 196g, methacrylic acid 88g, benzyl trimethyl ammonium chloride 3.0g, chromium acetylacetonate 1.8g, methyl hydroquinone 0.10g in thermometer, agitator, nitrogen ingress pipe and condenser reactor, open and stir, heat up gradually, be controlled at 75 ℃ of reactions, every one hour, measuring acid number, is reaction end until acid number is down to 10mgKOH/g below.In reaction product, add 100g vinylbenzene and 100g dicyclopentadiene acrylate, after stirring, obtain modified epoxy vinyl ester resin composition.
Embodiment 7:
In there-necked flask at 1000ml with thermometer, agitator prolong, drop into high bromine content EX-48 bisphenol A epoxide resin 600g, methacrylic acid 105g, fumaric acid 11.6g, Resorcinol 0.35g, benzyltrimethylammonium bromide 1g, acetylacetone cobalt 0.5g, be warming up to 75 ℃, every one hour test acid number, until acid number is less than 10mgKOH/g, be reaction end, stopped reaction.Reaction product is cooling, add vinylbenzene 320g, stir and be cooled to outdoor temp, obtain high bromine content epoxy vinyl ester resin.
Embodiment 8:
At 1000ml, drop into novolac epoxy 200g in thermometer, agitator, nitrogen ingress pipe and condenser there-necked flask, progressively heat and stir; When rising to 70 ℃, temperature starts to drip methacrylic acid 117g, and add benzyltriethylammoinium chloride 1g, chromium acetylacetonate 0.5g, Tert. Butyl Hydroquinone 1g, 2,6-ditertbutylparacresol 1g, control temperature of reaction between 80 ℃, every one hour, measuring acid number, is reaction end until acid number is down to 10mgKOH/g below.Reaction product is cooling and add 128g hydroxyethyl methylacrylate, after stirring, obtain heat resist modification epoxy vinyl ester resin.
Embodiment 9:
At 500ml, drop into E51 bisphenol A epoxide resin 196g, methacrylic acid 60g, fumaric acid 37.5g, benzyl trimethyl ammonium chloride 1g, titanium acetylacetone 1g, 4-tert-butyl catechol 0.12g in thermometer, agitator, nitrogen ingress pipe and condenser reactor, open and stir, heat up gradually, be controlled at reaction at 80 ℃.In reaction system, slowly drip dicyclopentadiene 48g, control 80 ℃ of reactions of temperature 3 hours, until acid number drops to below 10mgKOH/g.In reaction product, add 180g vinylbenzene, stir and obtain lurid viscous liquid.
In each embodiment, the typical quality index of gained resin is as follows above:
The typical mechanical performance index of this casting resin is as follows:
Claims (3)
1. the composite catalysis synthesizing technology of epoxy vinyl ester resin, is characterized in that: comprise the steps:
(1) batching is standby with mass percent formula batching:
A. epoxy resin 40%-60%
B. unsaturated monocarboxylic acid 10%-26%
C. saturated dicarboxylic acid 0%-8%
D. catalyst compounded 0.10%-1.0%
E. stopper 0.01%-0.05%
F. crosslinkable monomers 30%-45%
(2) in esterification by ring opening reaction response device, drop into material A, B, C, D, E, pass in the situation of nitrogen and stir, be warming up to gradually 60-85 ℃, reaction system all even transparent rear maintenance temperature that becomes, are less than 10mgKOH/g until record acid number;
(3) after dilution cooling, in reaction product, add crosslinkable monomers F, fully stir and obtain epoxy vinyl ester resin;
The described catalyst compounded composition that refers to acetyl acetone salt complex compound and quaternary amine of step (1), wherein the weight ratio of acetyl acetone salt complex compound and quaternary ammonium salt is 1: 3-3: 1.
2. the composite catalysis synthesizing technology of a kind of epoxy vinyl ester resin according to claim 1, is characterized in that: described acetyl acetone salt complex compound is a kind of in chromium acetylacetonate, methyl ethyl diketone zirconium, acetylacetone cobalt, titanium acetylacetone, manganese acetylacetonate, ferric acetyl acetonade.
3. the composite catalysis synthesizing technology of a kind of epoxy vinyl ester resin according to claim 1, is characterized in that: described quaternary amine refers to a kind of in benzyldimethylamine, benzyl diethylamine, tetramethyl ammonium chloride, 4 bromide, etamon chloride, tetraethylammonium bromide, benzyl trimethyl ammonium chloride, benzyltrimethylammonium bromide, benzyltriethylammoinium chloride, benzyl triethyl ammonium bromide.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2017127506A1 (en) * | 2016-01-19 | 2017-07-27 | Ut-Battelle, Llc | Stimuli-responsive liquid crystalline networks |
| CN107312160A (en) * | 2017-06-28 | 2017-11-03 | 常州华日新材有限公司 | The composition and formed products of a kind of epoxy vinyl ester resin |
| CN110669224A (en) * | 2019-10-09 | 2020-01-10 | 上海昭和高分子有限公司 | Vinyl ester resin and preparation method and application thereof |
| WO2023134036A1 (en) * | 2022-01-12 | 2023-07-20 | 广东美亨新材料科技有限公司 | Environment-friendly vinyl ester resin |
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| US20090107632A1 (en) * | 2007-10-30 | 2009-04-30 | General Electric Company | Adhesive compositions for high temperature sensors and methods of making the same |
| CN103342798A (en) * | 2013-07-16 | 2013-10-09 | 华东理工大学 | Synthesis method for low-viscosity high-temperature-resistant modified epoxy resin |
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2014
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1445255A (en) * | 2003-04-17 | 2003-10-01 | 中山大学 | Method for catalysis synthesizing methylic metlbond epoxy acryl resin |
| US20090107632A1 (en) * | 2007-10-30 | 2009-04-30 | General Electric Company | Adhesive compositions for high temperature sensors and methods of making the same |
| CN103342798A (en) * | 2013-07-16 | 2013-10-09 | 华东理工大学 | Synthesis method for low-viscosity high-temperature-resistant modified epoxy resin |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017127506A1 (en) * | 2016-01-19 | 2017-07-27 | Ut-Battelle, Llc | Stimuli-responsive liquid crystalline networks |
| US10253261B2 (en) | 2016-01-19 | 2019-04-09 | Ut-Battelle, Llc | Stimuli-responsive liquid crystalline networks |
| CN107312160A (en) * | 2017-06-28 | 2017-11-03 | 常州华日新材有限公司 | The composition and formed products of a kind of epoxy vinyl ester resin |
| CN107312160B (en) * | 2017-06-28 | 2020-05-08 | 常州华日新材有限公司 | Composition of epoxy vinyl ester resin and formed product |
| CN110669224A (en) * | 2019-10-09 | 2020-01-10 | 上海昭和高分子有限公司 | Vinyl ester resin and preparation method and application thereof |
| CN110669224B (en) * | 2019-10-09 | 2021-08-03 | 上海昭和高分子有限公司 | Vinyl ester resin and preparation method and application thereof |
| WO2023134036A1 (en) * | 2022-01-12 | 2023-07-20 | 广东美亨新材料科技有限公司 | Environment-friendly vinyl ester resin |
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Application publication date: 20141001 |