CN100509889C - Technique for synthesizing air-dry type oxirene ester resin - Google Patents
Technique for synthesizing air-dry type oxirene ester resin Download PDFInfo
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- CN100509889C CN100509889C CNB2006101178007A CN200610117800A CN100509889C CN 100509889 C CN100509889 C CN 100509889C CN B2006101178007 A CNB2006101178007 A CN B2006101178007A CN 200610117800 A CN200610117800 A CN 200610117800A CN 100509889 C CN100509889 C CN 100509889C
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Abstract
This invention relates to a process for synthesizing air-drying epoxy vinyl ester resin. The process comprises: reacting bisphenol A type epoxy resins with low and high epoxy equivalent, and organic unsaturated monocarboxylic acid at 120-160 deg.C in the presence of catalyst and polymerization inhibitor, and then diluting with crosslinkable monomer. The resin has good air-drying performance, with surface drying time less than or equal to 0.5 h, and inner drying time less than or equal to 4 h. Besides, the resin has appropriate viscosity, good wettability with glass fibers and glass mats, good physical and mechanical performance, and good chemical corrosion resistance, and is suitable for various molding processes of fiber reinforced plastics such as manual pasting, coiling, drawing and spraying. The method has such advantages as simple process, low energy consumption, and stable product quality.
Description
Technical field
The invention belongs to the high molecular polymer technical field, be specifically related to a kind of prescription and synthesis technique of air-dry type oxirene ester resin.
Background technology
Molecule two ends of epoxy vinyl ester resin contain the vinyl ester group, and middle skeleton is a Resins, epoxy, and they are to carry out the esterification by ring opening reaction by unsaturated organic monocarboxylic acid and Resins, epoxy to obtain.Epoxy vinyl ester resin is owing to have the excellent corrosion resistance and the mechanical property of Resins, epoxy concurrently, have unsaturated polyester resin machine-shaping processing performance easily again, become the main body material of corrosion-resistant glass fiber reinforced plastics product, application surface is very wide, spreads all over the protection against corrosion field of national economy all departments such as chemical industry, metallurgy, building.
At present, common epoxy vinyl ester resin is to carry out the esterification by ring opening reaction with the Resins, epoxy that hangs down epoxy equivalent (weight) and unsaturated organic monocarboxylic acid to obtain.Because the curing that epoxy vinyl ester resin is filmed realizes by means of vinylbenzene and the copolyreaction of resin unsaturated double-bond radical, copolymerization has had strong inhibitory effects (anaerobism phenomenon) and airborne oxygen is to radical, the air-drying property of common epoxy vinyl ester resin is not ideal enough, general coating surface drying time≤4 hours, do solid work time≤24 hour, therefore do not take the necessary measures when the epoxy vinyl ester resin surface that contacts with air of filming, the top layer can be clamminess forever, not done, and the result forms runny top layer and solidified lower floor.
In order to overcome the poly-problem of air resistance, solution commonly used is:
A. add a kind of material (as paraffin), to form the mechanical masking to air, it can be dissolved in coating, and can be diffused into the surface after construction.But the adding of paraffin not only can reduce performances such as sticking power, sharpness, gloss, but also needs polishing, polishing, very inconvenience, and effect is undesirable.
B. with polylol allyl ether, cellulose acetate butyrate resin is carried out modification, half esterification process and blocking method modification are not suitable for using when synthesis of vinyl ester resin, initial method modification drops into reactor simultaneously with allyl ethers and other dibasic alcohol, diprotic acid, carry out esterification to required acid number in 185 ℃, but in esterification process, must add a large amount of stoppers, in case product gelling in reactor makes production of resins complicated.
C. also have a kind of method exactly curing to be placed in rare gas element such as the nitrogen and carry out, but cost an arm and a leg, be not suitable for large-scale industrialization production.
Summary of the invention
The purpose of this invention is to provide a kind of air-dry type oxirene ester resin, this resin air-drying property is good, surface drying time≤0.5 hour, do solid work time≤4 hour, coating hardness is good, paint film fullness ratio height, flow leveling are good, physical and mechanical property is good, and the resistance to chemical corrosion excellence is suitable for various glass reinforced plastic moulding processs such as hand paste, winding, pultrusion, injection.
For achieving the above object, the technical scheme that adopts is: a kind of air-dry type oxirene ester resin has reaction in the presence of catalyzer and the stopper by low epoxy equivalent (weight) and the normal bisphenol A type epoxy resin of high epoxy, organic monobasic unsaturated carboxylic acid at 120～160 ℃, and is synthetic by the crosslinkable monomers dilution again.Concrete steps are:
(1) batching is standby with mass percent prescription batching:
The bisphenol A type epoxy resin 20%～30% of the low epoxy equivalent (weight) of A
The normal bisphenol A type epoxy resin 20%～30% of the high epoxy of B
The organic monobasic unsaturated carboxylic acid 9%～18% of C
D catalyzer 0.05%～0.25%
E stopper 0.01%～0.05%
F anti-aging agent 0.01%～0.05%
G crosslinkable monomers 34%～45%
Wherein low epoxy equivalent (weight) bisphenol A type epoxy resin is meant that epoxy equivalent (weight) is 176～263g/mol bisphenol A type epoxy resin, and high epoxy equivalent (weight) bisphenol A type epoxy resin is meant that epoxy equivalent (weight) is 455～1000g/mol bisphenol A type epoxy resin; Organic monobasic unsaturated carboxylic acid is meant methacrylic acid or vinylformic acid; Catalyzer is benzyldimethylamine, benzyl trimethyl ammonium chloride or benzyltriethylammoinium chloride; Stopper is Tert. Butyl Hydroquinone, tert-butyl catechol, para benzoquinone, Resorcinol, methyl hydroquinone; Crosslinkable monomers is one or more in vinylbenzene, Vinylstyrene, Vinyl toluene, methacrylic ester, acrylate, the Phthalic acid, diallyl ester; Anti-aging agent is N-cyclohexyl-N '-diphenyl-para-phenylene diamine, N-sec.-propyl-N '-diphenyl-para-phenylene diamine, N-(1, the 3-dimethyl) butyl-N '-diphenyl-para-phenylene diamine, N, N '-two (betanaphthyl) Ursol D, N-phenyl-1-naphthylamine, N-phenyl-2-naphthylamines, N, N '-diphenyl-para-phenylene diamine.
(2) drop into A, B, C, D and E described in the step (1) in the esterification by ring opening reaction response device, feed under the nitrogen situation and stir, be warming up to 120～160 ℃ gradually, and keep temperature, up to the acid number that records less than 30mgKOH/g;
(3) dilution is cooled to and adds G described in the step (1) below 110 ℃, fully stirs; Temperature is reduced to and is added F described in the step (1) below 60 ℃ again, fully stirs;
(4) filtration is cooled to room temperature, filters and promptly gets light yellow viscous liquid.
The air-dry type oxirene ester resin that the present invention makes compared with prior art has the following advantages:
(1) this resin air-drying property is good, surface drying time≤0.5 hour, do solid work time≤4 hour, just energy rapid drying under the normal temperature condition in air, have that paint film adhesion is strong, fullness ratio is high, look shallow transparent, hardness is high, wear resistance good, the characteristics that flow leveling is good, and have many premium propertiess such as heat-resisting, moisture resistance, chemical proofing be good.The ill effect of having avoided materials such as interpolation paraffin to bring.
(2) in building-up process, simplified production technique, reduced production energy consumption, workable.For example; Initial method is introduced the allyl ethers structure in polyester molecule, allyl ethers and other dibasic alcohol, diprotic acid are dropped into reactor simultaneously, carry out esterification to required acid number in 185 ℃, must add a large amount of stoppers in the esterification process, in case product gelling in reactor.Temperature of reaction required for the present invention only is 120～160 ℃, far below 185 ℃, and only needs a small amount of stopper can guarantee that reaction carries out smoothly, and gel does not take place product.
Embodiment
Followingly the present invention is described in more detail by embodiment.
Embodiment 1:
(epoxy equivalent (weight) is 179～192g/mol) 170g, (epoxy equivalent (weight) is 455～500g/mol) 170g, methacrylic acid 110g, benzyldimethylamine 0.8g, Tert. Butyl Hydroquinone 0.15g to the normal bisphenol A type epoxy resin of high epoxy to drop into low epoxy equivalent (weight) bisphenol A type epoxy resin in reactor.Feed under the nitrogen situation and be warming up to 120 ℃ gradually, keep temperature, up to recording acid number less than 30mgKOH/g; Be cooled to the vinylbenzene of adding below 110 ℃ 260g, methyl methacrylate 20g fully stirs, and reduces to when temperature to add 0.1gN-cyclohexyl-N '-diphenyl-para-phenylene diamine below 60 ℃, and fully stirring is cooled to room temperature at last, filters promptly to get light yellow viscous liquid.
Embodiment 2:
(epoxy equivalent (weight) is 185～196g/mol) 150g, (epoxy equivalent (weight) is that 455～556g/mol) 200g, vinylformic acid 85g, benzyl trimethyl ammonium chloride 0.38g, tert-butyl catechol 0.08g drop in the device shown in the example 1 to the normal bisphenol A type epoxy resin of high epoxy with the bisphenol A type epoxy resin of low epoxy equivalent (weight), be warming up to 130 ℃ gradually under the situation of feeding nitrogen, keep temperature, up to recording acid number less than 30mgKOH/g.Be cooled to the vinylbenzene of adding below 110 ℃ 300g, fully stir, reduce to the 0.30gN-of adding below 60 ℃ sec.-propyl-N '-diphenyl-para-phenylene diamine when temperature, fully stirring is cooled to room temperature at last, filters promptly to get light yellow viscous liquid.
Embodiment 3:
(epoxy equivalent (weight) is 185～208g/mol) 175g, (epoxy equivalent (weight) is that 714～833g/mol) 230g, vinylformic acid 85g, benzyltriethylammoinium chloride 1.6g, para benzoquinone 0.20g drop in the device shown in the example 1 to the normal bisphenol A type epoxy resin of high epoxy with the bisphenol A type epoxy resin of low epoxy equivalent (weight), feed under the nitrogen situation and be warming up to 140 ℃ gradually, keep temperature, up to recording acid number less than 30mgKOH/g.Be cooled to the vinylbenzene of adding below 110 ℃ 320g, Vinylstyrene 50g, fully stir, when temperature is reduced to the 0.25g of adding below 60 ℃ N-(1, the 3-dimethyl) butyl-N '-diphenyl-para-phenylene diamine, fully stir, be cooled to room temperature at last, filter and promptly get light yellow muddy viscous liquid.
Embodiment 4:
(epoxy equivalent (weight) is 222～238g/mol) 210g, (epoxy equivalent (weight) is 750～1000g/mol) 190g, methacrylic acid 95g, benzyldimethylamine 0.7g, Resorcinol 0.26g, drops in the device shown in the example 1 the normal bisphenol A type epoxy resin of high epoxy with the bisphenol A type epoxy resin of low epoxy equivalent (weight), be warming up to 140 ℃ gradually under the situation of feeding nitrogen, keep temperature, up to recording acid number less than 30mgKOH/g.Be cooled to below 110 ℃ and add vinylbenzene 240g, methyl acrylate 50g, fully stir, reduce to below 60 ℃ when temperature and add 0.15gN, N '-two (betanaphthyl) Ursol D, fully stir, be cooled to room temperature at last, filter and promptly get light yellow muddy viscous liquid.
Embodiment 5:
(epoxy equivalent (weight) is 213～244g/mol) 160g, (epoxy equivalent (weight) is that 455～500g/mol) 210g, vinylformic acid 80g, benzyltriethylammoinium chloride 0.65g, para benzoquinone 0.30g drop in the device shown in the example 1 to the normal bisphenol A type epoxy resin of high epoxy with the bisphenol A type epoxy resin of low epoxy equivalent (weight), be warming up to 160 ℃ gradually under the situation of feeding nitrogen, keep temperature, up to recording acid number less than 30mgKOH/g.Be cooled to the vinylbenzene of adding below 110 ℃ 230g, Vinyl toluene 90g, fully stir, reduce to the 0.08g of adding below 60 ℃ N-phenyl-1-naphthylamine when temperature, fully stirring is cooled to room temperature at last, filters promptly to get light yellow viscous liquid.
Embodiment 6:
(epoxy equivalent (weight) is 222～263g/mol) 170g, (epoxy equivalent (weight) is that 455～556g/mol) 180g, methacrylic acid 90g, benzyltriethylammoinium chloride 1.4g, Tert. Butyl Hydroquinone 0.10g drop in embodiment 1 shown device to the normal bisphenol A type epoxy resin of high epoxy with the bisphenol A type epoxy resin of low epoxy equivalent (weight), feed under the nitrogen situation and be warming up to 120 ℃ gradually, keep temperature, up to recording acid number less than 30mgKOH/g.Be cooled to the vinylbenzene of adding below 110 ℃ 190g, methyl methacrylate 100g, fully stir, reduce to the 0.2g of adding below 60 ℃ N-phenyl-2-naphthylamines when temperature, fully stirring is cooled to room temperature at last, filters promptly to get light yellow muddy viscous liquid.
Embodiment 7:
(epoxy equivalent (weight) is 176～181g/mol) 215g, (epoxy equivalent (weight) is that 750～1000g/mol) 160g, vinylformic acid 100g, benzyl trimethyl ammonium chloride 1.1g, methyl hydroquinone 0.35g drop in the device shown in the embodiment 1 to the normal bisphenol A type epoxy resin of high epoxy with the bisphenol A type epoxy resin of low epoxy equivalent (weight), be warming up to 130 ℃ gradually under the situation of feeding nitrogen, keep temperature, until recording acid number less than 30mgKOH/g.Be cooled to below 110 ℃ and add vinylbenzene 250g, fully stir, reduce to below 60 ℃ when temperature and add 0.18gN, N '-diphenyl-para-phenylene diamine fully stirs, and is cooled to room temperature at last, filters and promptly gets light yellow muddy viscous liquid.
Embodiment 8:
(epoxy equivalent (weight) is 185～208g/mol) 170g, (epoxy equivalent (weight) is that 714～833g/mol) 230g, methacrylic acid 95g, benzyldimethylamine 1.8g, Tert. Butyl Hydroquinone 0.20g drop in the device shown in the example 1 to the normal bisphenol A type epoxy resin of high epoxy with the bisphenol A type epoxy resin of low epoxy equivalent (weight), feed under the nitrogen situation and be warming up to 140 ℃ gradually, keep temperature, until recording acid number less than 30mgKOH/g.Be cooled to and add vinylbenzene 300g below 110 ℃, Phthalic acid, diallyl ester 30g, fully stirring, reduce to the 0.35g of adding below 60 ℃ N when temperature, N '-two (betanaphthyl) Ursol D fully stirs, be cooled to room temperature at last, filter and promptly get light yellow muddy viscous liquid.
More than among each embodiment the typical quality index of gained resin as follows:
The typical mechanical performance index of this casting resin is as follows:
| Project | Data | Testing method |
| Tensile strength MPa | 60～80 | GB/T2568-1995 |
| Tensile modulus GPa | 3.0～3.5 | GB/T2568-1995 |
| Elongation at break % | 3～5 | GB/T2568-1995 |
| Flexural strength MPa | 100～120 | GB/T2570-1995 |
| Modulus in flexure GPa | 3.2～3.8 | GB/T2570-1995 |
| Heat-drawn wire ℃ (1.8MPa) | 100～110 | GB/T1634-1989 |
Air-dry type oxirene ester resin provided by the invention, air-drying property is good, and coating hardness is good, paint film fullness ratio height, flow leveling are good, and physical and mechanical property is good, the resistance to chemical corrosion excellence is suitable for various glass reinforced plastic moulding processs such as hand paste, winding, pultrusion, injection.
Claims (5)
1 one kinds of air-dry type oxirene ester resin synthesis techniques comprise the following steps:
(1) batching is standby with mass percent prescription batching:
The bisphenol A type epoxy resin 20%～30% of A 176～263g/mol epoxy equivalent (weight)
The bisphenol A type epoxy resin 20%～30% of B 455～1000g/mol epoxy equivalent (weight)
The organic monobasic unsaturated carboxylic acid 9%～18% of C
D catalyzer 0.05%～0.25%
E stopper 0.01%～0.05%
F anti-aging agent 0.01%～0.05%
G crosslinkable monomers 34%～45%
Described crosslinkable monomers is one or more in vinylbenzene, Vinylstyrene, Vinyl toluene, methacrylic ester, acrylate, the Phthalic acid, diallyl ester;
(2) drop into the described A of step (1), B, C, D and E in the esterification by ring opening reaction response device, feed under the nitrogen situation and stir, be warming up to 120～160 ℃ gradually, and keep temperature, up to recording acid number less than 30mgKOH/g;
(3) dilution is cooled to and adds the described G of step (1) below 110 ℃, fully stirs; Temperature is reduced to and is added the described F of step (1) below 60 ℃ again, fully stirs;
(4) filtration is cooled to room temperature, filters and promptly gets light yellow viscous liquid.
2 by the described air-dry type oxirene ester resin synthesis technique of claim 1, it is characterized in that described organic monobasic unsaturated carboxylic acid is meant methacrylic acid or vinylformic acid.
3 by the described air-dry type oxirene ester resin synthesis technique of claim 1, it is characterized in that described catalyzer is a kind of in benzyldimethylamine, benzyl trimethyl ammonium chloride or the benzyltriethylammoinium chloride.
4 by the described air-dry type oxirene ester resin synthesis technique of claim 1, it is characterized in that described stopper is a kind of in Tert. Butyl Hydroquinone, tert-butyl catechol, para benzoquinone, Resorcinol, the methyl hydroquinone.
5 by the described air-dry type oxirene ester resin synthesis technique of claim 1, it is characterized in that anti-aging agent is N-cyclohexyl-N '-diphenyl-para-phenylene diamine, N-sec.-propyl-N '-diphenyl-para-phenylene diamine, N-(1, the 3-dimethyl) butyl-N '-diphenyl-para-phenylene diamine, N, N '-two (betanaphthyl) Ursol D, N-phenyl-1-naphthylamine, N-phenyl-2-naphthylamines, N, a kind of among N '-diphenyl-para-phenylene diamine.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103228437A (en) * | 2010-09-29 | 2013-07-31 | 株式会社斗山 | Laminate comprising epoxy resin having superior formability, and method for producing same |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101787179B (en) * | 2010-03-19 | 2011-08-31 | 新时代(济南)民爆科技产业有限公司 | Air-drying epoxy vinylit resin and processing technic thereof |
| CN102559120B (en) * | 2011-12-30 | 2013-11-06 | 浙江天和树脂有限公司 | Temperature-resistant, corrosion-resistant and high-adhesion adhesive and preparation method thereof |
| CN102875741A (en) * | 2012-10-18 | 2013-01-16 | 海洋化工研究院有限公司 | Anticorrosive paint used for aluminum evaporator of refrigerator |
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2006
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103228437A (en) * | 2010-09-29 | 2013-07-31 | 株式会社斗山 | Laminate comprising epoxy resin having superior formability, and method for producing same |
| CN103228437B (en) * | 2010-09-29 | 2015-09-16 | 株式会社斗山 | Containing duplexer and the manufacture method thereof of the epoxy resin of good forming ability |
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