CN100528960C - Epoxy resin composition - Google Patents
Epoxy resin composition Download PDFInfo
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- CN100528960C CN100528960C CNB2006101175969A CN200610117596A CN100528960C CN 100528960 C CN100528960 C CN 100528960C CN B2006101175969 A CNB2006101175969 A CN B2006101175969A CN 200610117596 A CN200610117596 A CN 200610117596A CN 100528960 C CN100528960 C CN 100528960C
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Abstract
本发明属固化剂技术领域，具体为一种新型环氧树脂组合物。该组合物由环氧树脂化合物和固化抑制剂混合组成。其中，固化剂为多杂酸和配合剂的混合物，抑制固化剂为杂环氮化合物、硫化合物、鏻化合物等。环氧树脂为双酚A型、环烃型、线性酚醛型等。与目前的固化剂相比，本发明具有快速固化的能力、优异的机械性能和热性能。根据配比不同，可在很宽的范围内控制混合物固化速度，这使得从瞬间凝胶到室温长使用期的宽范围内的应用成为可能。The invention belongs to the technical field of curing agents, in particular to a novel epoxy resin composition. The composition consists of an epoxy resin compound mixed with a cure inhibitor. Wherein, the curing agent is a mixture of polyheteroacid and compounding agent, and the curing inhibitor is a heterocyclic nitrogen compound, a sulfur compound, a phosphonium compound, and the like. Epoxy resins are bisphenol A type, cyclohydrocarbon type, novolac type and the like. Compared with the current curing agent, the present invention has the ability of rapid curing, excellent mechanical properties and thermal properties. According to the different proportions, the curing speed of the mixture can be controlled in a wide range, which makes it possible to apply in a wide range from instant gel to long pot life at room temperature.
Description
Technical field
The invention belongs to the solidifying agent technical field, be specifically related to a kind of neo-epoxy resin composition.
Background technology
Resins, epoxy is the thermosetting resin that average each molecule contains two or more epoxy group(ing).The tradition epoxy hardener mainly comprises acid anhydrides, polyamine or negatively charged ion solidifying agent, and its shortcoming is that curing speed is slow, shrinking percentage is big.
Over nearly 20 years, on the basis of free fundamental mode photopolymerization research, developed the photopolymerization of cationic epoxy resin type, had efficient, energy-saving and environmental protection, cured article strong adhesion, advantage such as shrinking percentage is low.In Resins, epoxy, add photosensitizers, arranged very long working life at normal temperatures, and, can play curing reaction rapidly through ultraviolet irradiation.Photosensitizers has diazonium salt, salt compounded of iodine, sulfonium salt etc., can cause the cationic epoxy resin polymerization under uviolizing.
As the Resins, epoxy of cation photocuring, available aliphatics type and alicyclic type, but universal resin is too slow owing to curing speed, and cured article fragility there is no much practical values greatly.The Resins, epoxy of cation photocuring and solidifying agent require the purity height, cause price high.
Existing positively charged ion heat cured system exists hardener dose big equally, costs an arm and a leg and defective such as synthetic complexity.
Heteropolyacid is to contain the oxygen polyacid by the class that heteroatoms (as P, Si, Fe, Co etc.) and polyatom (as Mo, W, V, Nb, Ta etc.) are formed by the oxygen atom ligand bridging by certain structure.As the novel catalytic material of a class, heteropolyacid and salt compounds thereof are subjected to investigators' extensive attention in the catalyticing research field with acidity, " accurate liquid phase " behavior, the multi-functional advantages such as (acid, oxidation, photoelectrocatalysiss) of its uniqueness.
Heteropolyacid belongs to solid super-strong acid, and for example after the dehydration of 12 phospho-wolframic acids, acidity reaches-13.16, is higher than Nafion resin and present industrial HF commonly used, H
2SO
4And AlCl
3Etc. liquid acid.The acidity of heteropolyacid can be by following method modulation in addition: (1) changes component, and the acid size order of different heteropolyacids is: HPW＞HsiW＞HPMo＞HSiMo.(2) change structure, the acid size order of different structure heteropolyacid is: Keggin＞Dowson＞other structure.(3) change activation temperature, regulate crystal water content.
Chuvaev, V.F etc. have announced that in russian patent SU1397458 the aqueous solution with the heteropolyacid metal-salt is that solidifying agent can solidify bisphenol A type epoxy resin, but are solvent with water to the dispersion of solidifying agent and the performance after solidifying all has negative impact
At Japanese Patent JP60028426, JP60072918, among the JP62048975 etc., the iodine of heteropolyacid, sulphur father-in-law salt are used as cation light initiator, and can solidify bisphenol A epoxide resin.
Summary of the invention
The objective of the invention is to shortcoming, provide that a kind of curing speed is fast, mechanical property and the good composition epoxy resin of thermal characteristics at existing solidifying agent.
The composition epoxy resin that the present invention proposes, its moiety is as follows:
(a) epoxy resin compound;
(b) solidifying agent is the mixture of heteropolyacid and Synergist S-421 95, and the weight ratio of solidifying agent and Resins, epoxy is 0.1-20: 100;
(c) curing inhibitors is heterocyclic nitrogen compounds, amine, phosphine or ammonium compound, phosphonium compounds, sulphur compound, diketone, polyethers, the mixture of one or more of crown ether; The mol ratio of inhibitor and solidifying agent is 0.1: 1-100: 1, preferred 1: 1-100-1.The gel time of adjusting ratio may command resin.
Among the present invention, described Resins, epoxy is one or more mixture of bisphenol A-type, cyclic hydrocarbon type, linear phenol aldehyde type, epoxidized vegetable oil, epoxy polymer, or its water-based system.
Among the present invention, described epoxidized vegetable oil is one or more a mixture of epoxidised soybean oil, epoxidation Oleum Gossypii semen, epoxidation rapeseed oil, epoxidized linseed.
Among the present invention, described epoxy polymer is epoxy natural rubber and epoxidation of olefins multipolymer.
Among the present invention, described heteropolyacid is that central atom is P, Si, Fe or Co, and ligating atom is heteropolyacid or its mixture of at least a element among Mo, W, V, Nb or the Ta.
Among the present invention, described Synergist S-421 95 is an oxo solvent, or one or more mixture of organic carboxyl acid, organic acid anhydride.
Among the present invention, described oxo solvent is one or more a mixture of methyl alcohol, ethanol, phenol, cresols, furfuryl alcohol, acetone, butanone, tetrahydrofuran (THF), dioxane.
Among the present invention, described organic carboxyl acid is that carbon chain lengths is one or more a mixture of 1 to 20 straight or branched lipid acid, aromatic carboxylic acid; Organic acid anhydride is simple function group or polyfunctional group acid anhydrides, comprises the straight or branched fatty acid anhydride, contains one or more mixture of unsaturated link(age) fatty acid anhydride, aromatic anhydride.
In the curing inhibitors of the present invention, heteroatomic organic compound such as nitrogenous, phosphorus, sulphur, comprise common organic solvent, as acetonitrile, N, N '-dimethyl formamide, N, N '-N,N-DIMETHYLACETAMIDE etc., compounds such as fat and aromatic amine, organophosphorus, thioether, because this compounds can form ionic linkage with heteropolyacid, can reduce curing speed significantly.Compounds such as diketone, polyethers, crown ether, can at high temperature solidify rapidly when prolonging the low temperature usage period owing to can form the reversible title complex with heteropolyacid.
In the used Resins, epoxy of the present invention, can be one or more mixture of the dihydroxyphenyl propane used always, cyclic hydrocarbon type, linear phenol aldehyde type.But contain heteroatomicly 4,4 '-diaminodiphenyl-methane, four glycidyl epoxy resins (TGDDM) etc. because the bonding of heteroatoms and heteropolyacid, and the reduction curing speed, or can not solidify fully.Epoxidized vegetable oil also can solidify well in addition, comprises epoxidised soybean oil, epoxidation Oleum Gossypii semen, epoxidation rapeseed oil, epoxidized linseed etc.
In addition, epoxy polymer can be epoxy natural rubber and epoxidation of olefins multipolymer, also can solidify as epoxidized polybutadiene-cinnamic two blocks or multi-block polymer etc.
In the used cooperation system of the present invention, mix with heteropolyacid by organic carboxyl acid or polyethers etc., in the solidified epoxy systems, the heteropolyacid consumption can solidify in the temperature range of room temperature to 170 ℃ and obtains high-performance epoxy resin between 0.05%--1% (weight).Adding curing inhibitors can extend working time.
The curing system of oxo solvent and heteropolyacid can foam simultaneously at solidified, obtains the epoxy foam material.
Use epoxidized vegetable oil can obtain Biodegradable Materials.
Adopt epoxy polymer can obtain the cross-linking type elastomerics.
In the above-mentioned system, also can use inorganic additives, inorganic additives commonly used has silica flour, talcum powder, clay, stone flour, Paris white, filamentary material (as glass fibre, composite fibre materials) etc., and low molecular weight rubber and thermoplastic resin also can be used for enhancing modified.
In the present invention, adopted the composite cation curing system of solid super-strong acid-heteropolyacid to solidify versatility Resins, epoxy and various special Resins, epoxy, can obtain completely crued epoxy cross-linking system moment or tens of minutes by adjusting hardener dose and temperature.
In the present invention, adjust the acidity of heteropolyacid, thereby change the speed of cationic curing process by component, organic carboxyl acid and the acid anhydrides of selecting heteropolyacid, add simultaneously can with the organic clement compound of heteropolyacid neutralization or complexing to adjust the usage period.Cured product can further improve performance by after fixing.
Compare with present solidifying agent, the present invention has the mechanical property and the thermal characteristics of quick-setting ability, excellence.According to the proportioning difference, can be in very wide scope inner control mixture solidified speed, this make from moment gel become possibility to the application in the long-lived wide region of room temperature.
Embodiment
Further illustrate content of the present invention below in conjunction with embodiment.
Embodiment 1
90 parts of polyoxyethylene glycol (molecular weight 400), 10 parts of 12 phospho-wolframic acids, mixed dissolution becomes clear solution.
(1) get 1 part of mixing solutions, oxirane value is 100 parts of 0.51 bisphenol A epoxide resins (E-51).The title complex room temperature surpasses 2 hours duration of service, is 30 seconds 140 ℃ set times, obtains sturdy material.Add 0.1 part of triphenyl in the title complex and see, mixture room temperature duration of service was above 4 hours.
(2) get 4 parts of mixing solutionss, 100 parts of E-51 Resins, epoxy, title complex room temperature duration of service is 10 minutes, is 10 seconds 100 ℃ set times, 150 ℃ of after fixing obtain sturdy material.
Embodiment 2
90 parts of methyl tetrahydro phthalic anhydrides, 10 parts of 12 phospho-wolframic acids, mixed dissolution becomes clear solution.
(1) get 1 part of mixing solutions, 100 parts of E-51 Resins, epoxy, the title complex room temperature surpasses half an hour duration of service, is 30 seconds 120 ℃ set times, obtains sturdy material.Add 0.1 part of diphenyl sulfide in the title complex, mixture room temperature duration of service was above 4 hours.
(2) get 4 parts of mixing solutionss, 100 parts of E-51 Resins, epoxy, the stirring at room gel, 150 ℃ of after fixing obtain sturdy material.
Embodiment 3
90 parts in acetone, 10 parts of 12 phospho-wolframic acids, mixed dissolution becomes clear solution.Get 10 parts of mixing solutionss, 100 parts of E-51 Resins, epoxy, suds-stabilizing agent is an amount of, and high-speed stirring is even, and at 50 ℃ thermal insulation foaming, 150 ℃ of after fixing obtain tough and tensile foam materials.
Embodiment 4
90 parts of Succinic anhydrieds, 10 parts of 12 silicotungstic acids, mixed dissolution becomes clear solution.Get 2 parts of mixing solutionss, 100 parts of epoxidised soybean oil, the title complex room temperature surpasses 1 hour duration of service, is 30 seconds 140 ℃ set times, obtains sturdy material.Add 0.1 part of diphenyl sulfide in the title complex, mixture room temperature duration of service was above 5 hours.
Claims (7)
1, a kind of composition epoxy resin is characterized in that moiety is as follows:
(a) epoxy resin compound;
(b) solidifying agent is the mixture of heteropolyacid and Synergist S-421 95, and the weight ratio of solidifying agent and Resins, epoxy is 0.1-20: 100; Wherein, in the solidified epoxy systems, the weight percent of heteropolyacid is 0.05%-1%; Described Synergist S-421 95 is an oxo solvent, or one or more mixture of organic carboxyl acid, organic acid anhydride;
(c) curing inhibitors is heterocyclic nitrogen compounds, amine, phosphine or ammonium compound, phosphonium compounds, sulphur compound, diketone, polyethers, the mixture of one or more of crown ether; The mol ratio of inhibitor and solidifying agent is 0.1: 1-100: 1.
2, composition epoxy resin according to claim 1 is characterized in that described Resins, epoxy is one or more mixture of bisphenol A-type, cyclic hydrocarbon type, linear phenol aldehyde type, epoxidized vegetable oil, epoxy polymer, or its water-based system.
3, composition epoxy resin according to claim 2 is characterized in that described epoxidized vegetable oil is one or more a mixture of epoxidised soybean oil, epoxidation Oleum Gossypii semen, epoxidation rapeseed oil, epoxidized linseed.
4, composition epoxy resin according to claim 2 is characterized in that described epoxy polymer is epoxy natural rubber and epoxidation of olefins multipolymer.
5, composition epoxy resin according to claim 1 is characterized in that described heteropolyacid is that central atom is P, Si, Fe or Co, and ligating atom is heteropolyacid or its mixture of at least a element among Mo, W, V, Nb or the Ta.
6, composition epoxy resin according to claim 1 is characterized in that described oxo solvent is one or more a mixture of methyl alcohol, ethanol, phenol, cresols, furfuryl alcohol, acetone, butanone, tetrahydrofuran (THF), dioxane.
7, composition epoxy resin according to claim 1 is characterized in that described organic carboxyl acid is that carbon chain lengths is one or more a mixture of 1 to 20 straight or branched lipid acid, aromatic carboxylic acid; Organic acid anhydride is simple function group or polyfunctional group acid anhydrides, comprises the straight or branched fatty acid anhydride, contains one or more mixture of unsaturated link(age) fatty acid anhydride, aromatic anhydride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006101175969A CN100528960C (en) | 2006-10-26 | 2006-10-26 | Epoxy resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006101175969A CN100528960C (en) | 2006-10-26 | 2006-10-26 | Epoxy resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1948392A CN1948392A (en) | 2007-04-18 |
| CN100528960C true CN100528960C (en) | 2009-08-19 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006101175969A Expired - Fee Related CN100528960C (en) | 2006-10-26 | 2006-10-26 | Epoxy resin composition |
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| CN (1) | CN100528960C (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101781443B (en) * | 2009-01-20 | 2012-03-28 | 财团法人工业技术研究院 | Thermosetting Solder Resist Film Composition |
| CN103319984B (en) * | 2013-06-27 | 2015-10-28 | 淮南市领异化工机械科技有限公司 | A kind of high temperature resistant stage curing epoxy-based lacquers and using method thereof |
| EP3555230B1 (en) * | 2016-12-14 | 2021-09-22 | Bromine Compounds Ltd. | Antimony free flame-retarded epoxy compositions |
-
2006
- 2006-10-26 CN CNB2006101175969A patent/CN100528960C/en not_active Expired - Fee Related
Non-Patent Citations (1)
| Title |
|---|
| 环氧树脂生产与应用. 王德中，198-199，化学工业出版社. 2001 * |
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| Publication number | Publication date |
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| CN1948392A (en) | 2007-04-18 |
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Granted publication date: 20090819 Termination date: 20121026 |