CN103044635A - Production method for modified epoxy vinyl ester resin composition - Google Patents
Production method for modified epoxy vinyl ester resin composition Download PDFInfo
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- CN103044635A CN103044635A CN2012105805597A CN201210580559A CN103044635A CN 103044635 A CN103044635 A CN 103044635A CN 2012105805597 A CN2012105805597 A CN 2012105805597A CN 201210580559 A CN201210580559 A CN 201210580559A CN 103044635 A CN103044635 A CN 103044635A
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- vinyl ester
- ester resin
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Abstract
The invention belongs to the technical field of macromolecular polymer and relates to a modified epoxy vinyl ester resin composition. A production method is characterized by comprising the following steps: throwing 35 to 50 mass percent of epoxy resin, 10 to 30 mass percent of unsaturated monocarboxylic acid, 0.1 to 1.0 mass percent of catalyst and 0.01 to 0.1 mass percent of polymerization inhibitor into a reaction kettle; reacting at the temperature between 100 and 120 DEG C until the acid value is reduced to be below 10 mg KOH/g, which is the reaction endpoint; and cooling to be below 100 DEG C, adding 0 to 40 mass percent of styrene and 5 to 40 mass percent of dicyclopentadiene (methyl) acrylic ester, and stirring uniformly to obtain the modified epoxy vinyl ester resin. The production method has the advantages that the crosslinking monomer styrene is partially or completely replaced by the dicyclopentadiene (methyl) acrylic ester, so that the method is simple to operate, few in side reaction and environment-friendly, the reaction endpoint is easy to control, and the product has high air-drying property, high curing speed, high adhesive force, low shrinkage rate and high corrosion resistance. The production method is applicable to manufacturing various composite material products and dies.
Description
Technical field
The invention belongs to the high molecular polymer technical field, the production method that relates to a kind of modified epoxy vinyl ester resin composition, particularly a kind of air-drying property is good, shrinking percentage is low, the production method of the high-performance modified epoxy vinyl ester resin composition of low waving property.
Background technology
Epoxy vinyl ester resin has the premium properties of Resins, epoxy and unsaturated polyester resin concurrently, therefore is widely used at everyways such as chemical anticorrosion, flue gas desulfurization, communications and transportation, electronic apparatus, ships and light boats.But during epoxy vinyl ester resin generation copolymerization, in the easy phenomenon that is clamminess that produces of the upper layer of ingress of air.The upper layer that is clamminess, the corrodibility of acid-and base-resisting, salt or solvent is poor, the white phenomenon of chance steeping in water for reconstitution hair tonic, has affected the quality of composite products, even products waste, and this phenomenon is especially obvious in Application of coatings.Analyze from curing mechanism, upper layer was clamminess and is because the formation of superpolymer is reacted and blocked in the participation of airborne oxygen when epoxy vinyl ester resin solidified, and institute causes solidifies not exclusively.
In order to prevent the inhibition of oxygen in the air, typical thin films covers or adds the inhibition of the anti-block of paraffin solution (forming the paraffin unimolecular layer on the surface) at present.But paraffin is not dissolved in resin, can separate out on the surface during resin solidification, has affected the interlayer combination of matrix material, has reduced the mechanical property of matrix material; Can't cover with film for some complex-shaped and large-scale matrix materials.
Along with the deep application of epoxy vinyl ester resin in prepare composite, people have higher requirement to its performance, and wherein the air-drying property of resin, low contraction, low volatilization are important technical indicators.Chinese patent 200810036708.7 discloses a kind of synthetic method of air-dry type oxirene ester resin, but the shortcoming that this synthetic method exists is: the first step reaction generates the terminal point of epoxy vinyl ester resin and judges with the reaction times, the first step reaction exists reaction that the situation of partial reaction thing is not exclusively still arranged when finishing, the dicyclopentadiene that in second step reaction, drips easily and above-mentioned raw materials produce unwanted all kinds of side reaction, cause end product quality unstable, reduced product performance etc.
Summary of the invention
The composition that the purpose of this invention is to provide the modified epoxy vinyl ester resin that a kind of production cost is low, air-drying property is good, shrinking percentage is low.
For achieving the above object, the technical scheme of employing is: a kind of production method of modified epoxy vinyl ester resin composition is characterized in that comprising the steps: successively
(1) in band thermometer, agitator, nitrogen ingress pipe and condenser reactor, by mass percentage, drops into Resins, epoxy 35～50%, unsaturated monocarboxylic acid 10～30%, catalyzer 0.1～1.0% and stopper 0.01～0.1%;
(2) heat up gradually, guarantee temperature of charge 100～120 ℃ of lower reactions, every one hour mensuration acid number, be reaction end below the 10mgKOH/g until acid number is down to;
(3) reaction product is cooled to below 100 ℃, by mass percentage, adds vinylbenzene 0～40% and dicyclopentadiene (methyl) acrylate 5～40%, obtain the modified epoxy vinyl ester resin composition after stirring.
Described Resins, epoxy refers to that epoxy equivalent (weight) is the bisphenol A diglycidyl ether (such as E44 bisphenol A epoxide resin, E51 bisphenol A epoxide resin) of 176～263g/mol, the diglycidylether of epoxy equivalent (weight) 222～263g/mol tetrabromo-bisphenol, epoxy equivalent (weight) 175～195g/mol novolac epoxy (as F51 novolac epoxy, F48 novolac epoxy) in a kind of.
Described unsaturated monocarboxylic acid is a kind of in vinylformic acid, methacrylic acid, butenoic acid, phenyl propylene-(2) acid.
Described catalyzer is a kind of in benzyldimethylamine, benzyl diethylamine, tetramethyl ammonium chloride, 4 bromide, etamon chloride, tetraethylammonium bromide, benzyl trimethyl ammonium chloride, benzyltrimethylammonium bromide, benzyltriethylammoinium chloride, the benzyl triethyl ammonium bromide.
Described stopper is one or both in Resorcinol, methyl hydroquinone, tert-butyl catechol, Tert. Butyl Hydroquinone, the para benzoquinone.
The surface can stickness when usually epoxy vinyl ester resin solidified, this be when solidifying in the air oxygen participate in polyreaction and cause: what the initial stage generated crosses oxyradical ﹝ RO from be combined the generation polymkeric substance with molecular oxygen by basic ﹝ R ﹞
2, the Huo of R ﹞ is Bi ﹝ RO
2﹞'s is active large, stops Zai ﹝ RO at product surface
2This one-phase of ﹞ has just suppressed the growth of polymericular weight.Compare with the two keys in the unsaturated polyester resin, unsaturated double-bond in the dicyclopentadiene on the alicyclic ring is preferentially captured oxygen, be combined with airborne oxygen and generate superoxide, realization is similar to the crosslinked drying of oiliness, therefore the inhibition of oxygen to the two keys on the maleic acid and vinylbenzene crosslinking curing slowed down, the multipolymer that itself and vinyl monomer form just is not subjected to the inhibition of oxygen in the atmosphere, makes surperficial rapid drying, makes resin have the air-drying property energy.
Compared with prior art, the present invention has the following advantages:
1) compare with Chinese patent 200810036708.7, present method is by dicyclopentadiene propionic ester Partial Replacement reactive monomer vinylbenzene, and simple to operate, control of reaction end point is clear and definite, and side reaction is few, and the resin that obtains is constant consistent, constant product quality.
2) synthesis technique of the present invention is simple, and environmental protection produces without " three wastes ", and product has good air-drying property, low-shrinkage, low volatilization, energy ambient cure, the good performances such as curing speed is fast, sticking power is high, good corrosion resistance.Be applicable to make various composite products, composite material mould.
Embodiment
Below in conjunction with embodiment the present invention is described in more detail; disclose the best implementation method of the present invention; in order to make those of ordinary skill in the art can implement the present invention; but it should be noted that the present invention never is limited to the following embodiment of announcement; enlighten based on the present invention; any apparent conversion or be equal to alternatively also should be considered to fall into protection scope of the present invention.
In the specific embodiment, each component all is calculated in mass percent except indicating especially.Dicyclopentadiene (methyl) acrylate can outsourcing, or synthetic voluntarily.When synthesizing voluntarily, with acrylic or methacrylic acid and mole dicyclopentadiene (dicyclopentadiene is from the by product C 5 fraction of coal tar or petroleum cracking ethene processed) reaction, the control temperature is reacted 3hr between 110～130 ℃ be reaction end, generates dicyclopentadiene (methyl) acrylate.
Embodiment 1:
Drop into E51 bisphenol A epoxide resin 196g, methacrylic acid 88g, tetramethyl ammonium chloride 2g, methyl hydroquinone 0.10g at 1000ml in thermometer, agitator, nitrogen ingress pipe and condenser reactor, open and stir, heat up gradually, be controlled at 110 ℃ of lower reactions, measuring acid number every one hour, is reaction end until acid number is down to 10mgKOH/g following.Reaction product is cooled to add below 110 ℃ 100g vinylbenzene and 100g dicyclopentadiene acrylate, obtains the modified epoxy vinyl ester resin composition after the control temperature of charge stirs below 70 ℃.
Embodiment 2:
Drop into F51 novolac epoxy 377g, methacrylic acid 176g, benzyltriethylammoinium chloride 2g, Resorcinol 0.20g at 1000ml in thermometer, agitator, nitrogen ingress pipe and condenser reactor, open and stir, heat up gradually, be controlled at 110 ℃ of lower reactions, measuring acid number every one hour, is reaction end until acid number is down to 10mgKOH/g following.Reaction product is cooled to add below 110 ℃ 100g vinylbenzene, and 300g dicyclopentadiene methacrylic ester obtains the modified epoxy vinyl ester resin composition after the control temperature of charge stirs below 70 ℃.
Embodiment 3:
Drop into diglycidylether 500g, methacrylic acid 176g, benzyl trimethyl ammonium chloride 2g, the tert-butyl catechol 0.20g of tetrabromo-bisphenol in thermometer, agitator, nitrogen ingress pipe and condenser reactor at 1000ml, open and stir, heat up gradually, be controlled at 110 ℃ of lower reactions, measuring acid number every one hour, is reaction end until acid number is down to 10mgKOH/g following.Reaction product is cooled to add below 110 ℃ the 400g dicyclopentadiene acrylate, and the control temperature of charge stirs below 70 ℃, obtains the modified epoxy vinyl ester resin composition.
Embodiment 4:
Drop into E44 bisphenol A epoxide resin 454g, methacrylic acid 176g, benzyltrimethylammonium bromide 2g, Tert. Butyl Hydroquinone 0.20g at 1000ml in thermometer, agitator, nitrogen ingress pipe and condenser reactor, open and stir, heat up gradually, be controlled at 110 ℃ of lower reactions, measuring acid number every one hour, is reaction end until acid number is down to 10mgKOH/g following.Reaction product is cooled to add below 110 ℃ 300g vinylbenzene, 100g dicyclopentadiene methacrylic ester, the control temperature of charge obtains the modified epoxy vinyl ester resin composition below 70 ℃ after stirring.
Embodiment 5:
Drop into F48 novolac epoxy 416g, butenoic acid 176g, benzyl trimethyl ammonium chloride 2g, Tert. Butyl Hydroquinone 0.20g at 1000ml in thermometer, agitator, nitrogen ingress pipe and condenser reactor, open and stir, heat up gradually, be controlled at 110 ℃ of lower reactions, measuring acid number every one hour, is reaction end until acid number is down to 10mgKOH/g following.Reaction product is cooled to add below 110 ℃ 200g vinylbenzene, and the 200g dicyclopentadiene acrylate obtains the modified epoxy vinyl ester resin composition after the control temperature of charge stirs below 70 ℃.
Embodiment 6:
Drop into E51 bisphenol A epoxide resin 392g, vinylformic acid 148g, benzyltrimethylammonium bromide 4g, para benzoquinone 0.20g at 1000ml in thermometer, agitator, nitrogen ingress pipe and condenser reactor, open and stir, heat up gradually, be controlled at 110 ℃ of lower reactions, measuring acid number every one hour, is reaction end until acid number is down to 10mgKOH/g following.Reaction product is cooled to add below 110 ℃ 200g vinylbenzene, and 200g dicyclopentadiene methacrylic ester obtains the modified epoxy vinyl ester resin composition after the control temperature of charge stirs below 70 ℃.
Embodiment 7:
Drop into F51 novolac epoxy 380g, phenyl propylene-(2) sour 301g, benzyl triethyl ammonium bromide 3g, Tert. Butyl Hydroquinone 0.20g at 1000ml in thermometer, agitator, nitrogen ingress pipe and condenser reactor, open and stir, heat up gradually, be controlled at 110 ℃ of lower reactions, measuring acid number every one hour, is reaction end until acid number is down to 10mgKOH/g following.Reaction product is cooled to add below 110 ℃ 300g vinylbenzene, and the 100g dicyclopentadiene acrylate obtains the modified epoxy vinyl ester resin composition after the control temperature of charge stirs below 70 ℃.
Embodiment 8:
Drop into E44 bisphenol A epoxide resin 454g, vinylformic acid 148g, benzyltriethylammoinium chloride 4g, methyl hydroquinone 0.25g at 1000ml in thermometer, agitator, nitrogen ingress pipe and condenser reactor, open and stir, heat up gradually, be controlled at 110 ℃ of lower reactions, measuring acid number every one hour, is reaction end until acid number is down to 10mgKOH/g following.Reaction product is cooled to add below 110 ℃ 300g vinylbenzene, and 100g dicyclopentadiene methacrylic ester obtains the modified epoxy vinyl ester resin composition after the control temperature of charge stirs below 70 ℃.
Embodiment 9:
Drop into 638 novolac epoxy 360g, methacrylic acid 148g, 4 bromide 3g, tert-butyl catechol 0.20g at 1000ml in thermometer, agitator, nitrogen ingress pipe and condenser reactor, open and stir, heat up gradually, be controlled at 110 ℃ of lower reactions, measuring acid number every one hour, is reaction end until acid number is down to 10mgKOH/g following.Reaction product is cooled to add below 110 ℃ 100g vinylbenzene, and the 300g dicyclopentadiene acrylate obtains the modified epoxy vinyl ester resin composition after the control temperature of charge stirs below 70 ℃.
Claims (5)
1. the production method of a modified epoxy vinyl ester resin composition is characterized in that comprising the steps: successively
(1) in band thermometer, agitator, nitrogen ingress pipe and condenser reactor, by mass percentage, drops into Resins, epoxy 35～50%, unsaturated monocarboxylic acid 10～30%, catalyzer 0.1～1.0% and stopper 0.01～0.1%;
(2) heat up gradually, guarantee temperature of charge 100～120 ℃ of lower reactions, every one hour mensuration acid number, be reaction end below the 10mgKOH/g until acid number is down to;
(3) reaction product is cooled to below 100 ℃, by mass percentage, adds vinylbenzene 0～40% and dicyclopentadiene (methyl) acrylate 5～40%, obtain the modified epoxy vinyl ester resin composition after stirring.
2. the production method of described a kind of modified epoxy vinyl ester resin composition according to claim 1, it is characterized in that, described Resins, epoxy refers to that epoxy equivalent (weight) is the bisphenol A diglycidyl ether of 176～263g/mol, a kind of in epoxy equivalent (weight) 222～263g/mol tetrabromo-bisphenol diglycidylether, the epoxy equivalent (weight) 175～195g/mol novolac epoxy.
3. the production method of described a kind of modified epoxy vinyl ester resin composition according to claim 1 is characterized in that, described unsaturated monocarboxylic acid is a kind of in vinylformic acid, methacrylic acid, butenoic acid, phenyl propylene-(2) acid.
4. the production method of described a kind of modified epoxy vinyl ester resin composition according to claim 1, it is characterized in that described catalyzer is a kind of of benzyldimethylamine, benzyl diethylamine, tetramethyl ammonium chloride, 4 bromide, etamon chloride, tetraethylammonium bromide, benzyl trimethyl ammonium chloride, benzyltrimethylammonium bromide, benzyltriethylammoinium chloride, benzyl triethyl ammonium bromide.
5. the production method of described a kind of modified epoxy vinyl ester resin composition according to claim 1, it is characterized in that described stopper is one or both in Resorcinol, methyl hydroquinone, tert-butyl catechol, Tert. Butyl Hydroquinone, the para benzoquinone.
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| CN2012105805597A CN103044635A (en) | 2012-12-28 | 2012-12-28 | Production method for modified epoxy vinyl ester resin composition |
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| CN2012105805597A CN103044635A (en) | 2012-12-28 | 2012-12-28 | Production method for modified epoxy vinyl ester resin composition |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110776644A (en) * | 2019-11-29 | 2020-02-11 | 华东理工大学 | Toughened modified vinyl ester resin and synthetic method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4690988A (en) * | 1985-01-22 | 1987-09-01 | The Dow Chemical Company | Polymer-modified vinylized epoxy resins |
| CN101450983A (en) * | 2007-12-05 | 2009-06-10 | 华东理工大学华昌聚合物有限公司 | Synthetic process of high temperature resistant epoxy vinyl ester resin |
| CN102532427A (en) * | 2011-12-30 | 2012-07-04 | 华东理工大学华昌聚合物有限公司 | Synthesizing method for tough epoxy vinyl ester resin |
-
2012
- 2012-12-28 CN CN2012105805597A patent/CN103044635A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4690988A (en) * | 1985-01-22 | 1987-09-01 | The Dow Chemical Company | Polymer-modified vinylized epoxy resins |
| CN101450983A (en) * | 2007-12-05 | 2009-06-10 | 华东理工大学华昌聚合物有限公司 | Synthetic process of high temperature resistant epoxy vinyl ester resin |
| CN102532427A (en) * | 2011-12-30 | 2012-07-04 | 华东理工大学华昌聚合物有限公司 | Synthesizing method for tough epoxy vinyl ester resin |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110776644A (en) * | 2019-11-29 | 2020-02-11 | 华东理工大学 | Toughened modified vinyl ester resin and synthetic method thereof |
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Application publication date: 20130417 |