CN103936962A - Epoxy curing agent synthesized through mercapto-vinyl addition - Google Patents
Epoxy curing agent synthesized through mercapto-vinyl addition Download PDFInfo
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- CN103936962A CN103936962A CN201410146241.7A CN201410146241A CN103936962A CN 103936962 A CN103936962 A CN 103936962A CN 201410146241 A CN201410146241 A CN 201410146241A CN 103936962 A CN103936962 A CN 103936962A
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Abstract
The invention discloses an epoxy curing agent synthesized through mercapto-vinyl addition. The epoxy curing agent is synthesized through carrying out addition reaction on a C=C double-bond containing acrylate or vinyl ether compound with difunctionality or polyfunctionality and a mercapto compound under the condition of light or heat initiation. A preparation method of the epoxy curing agent comprises the steps of adding a C=C double-bond containing difunctional or polyfunctional compound, the mercapto compound, a proper volume of solvent (such as 1,4-dioxane) and a free radical initiator or photoinitiator into a three-mouthed flask, reacting for certain time under the condition of heating or lighting, and removing the solvent, thereby obtaining the product. The epoxy curing agent overcomes the disadvantages of the existing modified amine and polymercaptan epoxy curing agents that the odor is strong, the toxicity is high, the heat release quantity is large during curing and the like; and the epoxy curing agent has the advantages of light color and luster, high index of refraction, low toxicity and the like and accordingly is particularly suitable for serving as a curing agent of epoxy encapsulation materials of electronic products, such as LED (Light Emitting Diode).
Description
Technical field:
The present invention relates to a kind of Novel Curing Agents for Epoxy Resins, the especially application of epoxy resin coating, tackiness agent, joint sealant aspect, particular content is the preparation method of modified epoxy solidifying agent.
Technical background:
Epoxy resin is a class important compound in synthetic resins field, because it has that shrinking percentage is little, cohesiveness good, intensity is high, chemical stability is good, mechanical property and the feature such as dielectric properties are good, and be widely used in the fields such as matrix material, electronics, chemical industry, civil engineering work.The high performance coating, ink, tackiness agent and the matrix material that adopt epoxy resin to make.
Because epoxy resin is low molecular heat thermoplastic polymer, make epoxy resin bring into play its good performance, epoxy resin and solidifying agent must be carried out to crosslinking reaction, form the macromole of linear or crosslinking structure.The solidifying agent of epoxy resin is various in style, and conventional have amine or modified amine, anhydrides or a latent curing agent.Organic amine or modified organic amine class solidifying agent toxicity are large, high to human body pungency, easy salify, and levelling property is bad, executes man-hour requirement maturation stage; Anhydrides, latent curing agent curing reaction temperature are high, and catalyst-free is difficult for curing molding when auxiliary.
Summary of the invention:
The object of the invention is synthetic a kind of epoxy hardener for purposes such as epoxy coating, ink, tackiness agent and matrix materials and preparation method thereof.It has overcome the shortcoming of above-mentioned modified organic amine, acid anhydrides and latent curing agent, has smell little, and toxicity is low, and reaction conditions is gentle, and refractive index advantages of higher, can directly be used without maturing process.
The object of the present invention is achieved like this: modified epoxy solidifying agent is by containing two two functionality of key of C=C or the acrylate of polyfunctionality or vinyl ether and compound containing sulfydryl, under hot or light-initiated condition, through the addition reaction of sulfydryl vinyl, makes.Realize when of the present invention, the mole number that is more than or equal to the two keys of C=C according to the mole number of sulfydryl feeds intake.In the building-up process of modified firming agent, can carry out nitrogen protection.
A synthetic method for modified epoxy solidifying agent, is characterized in that realizing in the steps below:
The first step: add in there-necked flask and contain two two functionality of key of C=C or acrylate or the vinyl compound of polyfunctionality, add (or not adding) a small amount of organic solvent;
Second step: proportionally add compounds containing thiol groups and heat or light trigger;
The 3rd step: under agitation condition, heating makes the decomposition of thermal initiator or uses UV-irradiation said mixture, initiation reaction.When mercapto groups disappears, reaction finishes.With the above-mentioned reaction of light-initiated initiation, the time is about 2 hours; With thermal initiator, cause above-mentioned reaction, the reaction times is depending on the transformation period of thermal initiator.
In addition, in above-mentioned reaction process, can pass into the rare gas elementes such as nitrogen.
The 4th step: if used organic solvent in the process of synthesis modification epoxy hardener, can be by vacuumizing or precipitate-dry method removes organic solvent.
Accompanying drawing explanation
The adduct of Fig. 1 oxyethyl group Viscoat 295 and thiohydracrylic acid
1h nmr spectrum, has shown the proton signal (2.55-2.88ppm) of obvious dipropyl sulfide, meanwhile, and the two completely dissolves of key peak of C=C at 5.81-6.22ppm place;
The adduct of Fig. 2 oxyethyl group Viscoat 295 and thiohydracrylic acid and the reactivity worth of epoxy;
The adduct of Fig. 3 propoxy-Viscoat 295 and thiohydracrylic acid
1h nmr spectrum, has shown the signal (7.39-8.45ppm) of hydrogen proton on the proton signal (2.55-2.88ppm) of obvious dipropyl sulfide and carboxyl;
The adduct of Fig. 4 trimethylolpropane allyl ether and 3-thiohydracrylic acid and the reactivity worth of epoxy resin;
The adduct of Fig. 5 tetramethylol methane tetraacrylate and 3-thiohydracrylic acid and the reactivity worth of epoxy resin;
The adduct of Fig. 6 trimethylolpropane allyl ether and 3-sulfydryl propylamine and the reactivity worth of epoxy resin.
Specific embodiment:
Below in conjunction with embodiment, the present invention is described in further detail.
Embodiment 1
In there-necked flask with whipping appts and thermometer, add the oxyethyl group Viscoat 295 of 50.5 parts, the 3-thiohydracrylic acid of 38.5 parts, 1 part of Diisopropyl azodicarboxylate.Start stirring, under nitrogen bubble condition, be warming up to 70 ℃, react cooling discharge 8 hours.Products therefrom is liquid colourless, transparent, thickness.Because this product is with three pendant carboxylic groups, can be as the solidifying agent of epoxy resin.With nuclear magnetic resonance analyser tested product nucleus magnetic hydrogen spectrum (
1hNMR) as Fig. 1, shown the proton signal (2.55-2.88ppm) of obvious dipropyl sulfide, meanwhile, the two completely dissolves of key peak of C=C at 5.81-6.22ppm place, have illustrated that C=C unsaturated double-bond is converted into carboxyl completely.In addition, after 1.275g product is mixed with 1.000g bisphenol A type epoxy resin (E-51), measure the reactivity worth of mixture with DSC, response curve is shown in Fig. 2.
The addition reaction of oxyethyl group Viscoat 295 and 3-thiohydracrylic acid
Embodiment 2
In there-necked flask with whipping appts and thermometer, add the propoxy-Viscoat 295 of 55.4 parts, the 3-thiohydracrylic acid of 38.5 parts, 2.5 parts of dimethoxybenzoins.Start stirring, under nitrogen bubble condition, with ultra violet lamp reaction 2 hours, cooling discharge.Products therefrom is liquid colourless, transparent, thickness.Because this product is with three pendant carboxylic groups, can be as the solidifying agent of epoxy resin.With nuclear magnetic resonance analyser tested product nucleus magnetic hydrogen spectrum (
1hNMR), as Fig. 3, shown the signal (7.39-8.45ppm) of hydrogen proton on the proton signal (2.55-2.88ppm) of obvious dipropyl sulfide and carboxyl.Illustrated that C=C unsaturated double-bond is converted into carboxyl completely.
Embodiment 3
In there-necked flask with whipping appts and thermometer, add the trimethylolpropane allyl ether of 40 parts, the 3-thiohydracrylic acid of 59 parts, 1 part of Diisopropyl azodicarboxylate (AIBN).Start stirring, under nitrogen bubble condition, be warming up to 70 ℃, react cooling discharge 8 hours.Products therefrom is liquid colourless or faint yellow, transparent, thickness.In order to confirm that products therefrom can be used as epoxy hardener and uses, it is mixed with bisphenol A type epoxy resin (E-44) etc. mole.The reactivity worth of measuring mixture by differential scanning calorimeter (DSC), response curve is shown in Fig. 4.
Sulfydryl-vinyl addition reaction of trimethylolpropane allyl ether and 3-thiohydracrylic acid
Embodiment 4
In there-necked flask with whipping appts and thermometer, add the tetramethylol methane tetraacrylate of 53.6 parts, the 3-thiohydracrylic acid of 45.5 parts, 2.0 parts of light trigger 2-hydroxy-2-methyl Propiophenones.Start stirring, under nitrogen bubble condition, the ultra violet lamp of use wavelength 365nm 3 hours, obtains modified firming agent.Products therefrom is colourless to liquid faint yellow, transparent, thickness.In order to confirm that products therefrom can be used as epoxy hardener and uses, it is mixed with bisphenol A type epoxy resin (E-51) etc. mole.The reactivity worth of measuring mixture with DSC, response curve is shown in Fig. 5.
Sulfydryl-vinyl addition reaction signal of tetramethylol methane tetraacrylate and 3-thiohydracrylic acid
Embodiment 5
In there-necked flask with whipping appts and thermometer, add the trimethylolpropane allyl ether (molecular weight 214g/mol) of 43.7 parts, 3-sulfydryl-1-propylamine of 55.3 parts, 1 part of Diisopropyl azodicarboxylate.Start stirring, under nitrogen bubble condition, be warming up to 70 ℃, react cooling discharge 8 hours.Products therefrom is colourless or faint yellow, transparent, thick liquid.Because product molecular structure contains two primary amine groups, can be as the solidifying agent of epoxy resin.In order to confirm this conclusion, products therefrom is mixed with bisphenol A type epoxy resin (E-51) etc. mole.The reactivity worth of measuring mixture with DSC, response curve is shown in Fig. 6.
Sulfydryl-vinyl addition reaction of trimethylolpropane allyl ether and 3-sulfydryl propylamine
The above, be only the specific embodiment of the present invention, but protection scope of the present invention is not limited to this, and any variation of expecting without creative work or replacement, within all should being encompassed in protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection domain that claims were limited.
Claims (9)
1. a modified epoxy solidifying agent, it is characterized in that by difunctionality or polyfunctional compound containing the two keys of C=C, sulfhydryl compound, heat or light trigger, carry out that the addition reaction of sulfydryl vinyl is synthetic to be obtained, wherein, the sulfydryl in sulfhydryl compound feeds intake according to the mole number that is more than or equal to C=C, and the quality of initiator is sulfydryl and C=C double bond compound total mass 0.01～0.04 times.
2. modified epoxy solidifying agent according to claim 1, is characterized in that the compound containing the two keys of C=C is acrylate or the vinyl ethers compound of difunctionality or polyfunctionality.
3. modified epoxy solidifying agent according to claim 1, is characterized in that sulfhydryl compound is the compound that contains a sulfydryl or two sulfydryls.
4. modified epoxy solidifying agent according to claim 1, is characterized in that being selected from one or more the combination in trimethylolpropane allyl ether, oxyethyl group Viscoat 295, propoxy-Viscoat 295, tetramethylol methane tetraacrylate or trimethylolpropane allyl ether containing the difunctionality of the two keys of C=C or polyfunctional compound.
5. modified epoxy solidifying agent according to claim 1, is characterized in that sulfhydryl compound is selected from 3-thiohydracrylic acid and/or 3-sulfydryl propylamine.
6. modified epoxy solidifying agent according to claim 1, it is characterized in that described thermal initiator is selected from Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), azo dicyano valeric acid, azo-bis-iso-dimethyl, 2,2'-azo two (4-methoxy-2,4-methyl pentane nitrile), Potassium Persulphate or ammonium persulphate.
7. modified epoxy solidifying agent according to claim 1; it is characterized in that described light trigger is selected from dimethoxybenzoin, 1-hydroxy-cyclohexyl phenyl ketone, phenylbenzene (2; 4,6-trimethylbenzoyl) phosphine oxide, 2-hydroxy-2-methyl Propiophenone, EHA or methyl benzoylformate.
8. modified epoxy solidifying agent according to claim 1, it is characterized in that described solvent is selected from water, benzene,toluene,xylene, chloroform, methylene dichloride, tetrahydrofuran (THF), diox, ethyl acetate, butylacetate, N, dinethylformamide, N,N-dimethylacetamide, methylethylketone, pimelinketone or N-Methyl pyrrolidone.
9. an epoxy hardener, the modified epoxy solidifying agent and the equimolar bisphenol A type epoxy resin that it is characterized in that containing described in claim 1-8 any one are mixed to get, and bisphenol A type epoxy resin model is preferably E-44 or E-51; Described epoxy hardener is directly used without maturing process.
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| CN201410146241.7A CN103936962B (en) | 2014-04-11 | 2014-04-11 | The epoxy hardener of sulfydryl vinyl addition synthesis |
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| CN201410146241.7A CN103936962B (en) | 2014-04-11 | 2014-04-11 | The epoxy hardener of sulfydryl vinyl addition synthesis |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2017019735A (en) * | 2015-07-08 | 2017-01-26 | 株式会社日本触媒 | Manufacturing method of primary or secondary amine compound having (poly)alkylene glycol chain and composition containing primary or secondary amine compound having (poly)alkylene glycol chain |
| CN106883377A (en) * | 2017-03-23 | 2017-06-23 | 苏州顶裕节能设备有限公司 | It is a kind of to utilize the curing agent and its method for producing the preparation of TMPTA waste water |
| CN109370508A (en) * | 2018-10-08 | 2019-02-22 | 东莞市联灏新材料技术开发有限公司 | A kind of radiation-curable black shading Adhesive composition |
| CN112795012A (en) * | 2020-12-30 | 2021-05-14 | 江苏富琪森新材料有限公司 | Emulsion type waterborne epoxy curing agent and preparation method and application thereof |
| CN113512361A (en) * | 2021-02-22 | 2021-10-19 | 烟台大学 | High-adhesion-strength shellac and preparation method thereof |
| CN115403541A (en) * | 2021-05-27 | 2022-11-29 | 北京化工大学 | Carboxyl-containing self-curing epoxy resin and preparation method thereof |
| CN117567076A (en) * | 2023-11-20 | 2024-02-20 | 中国人民解放军陆军工程大学 | Quick repair epoxy resin repair material and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1188109A (en) * | 1996-11-25 | 1998-07-22 | 株式会社日本触媒 | Process for production of sulfide group-containing mercaptocarboxylic acid and ester thereof |
| CN103221458A (en) * | 2010-10-01 | 2013-07-24 | 莫赛纳实验室公司 | Method for the manufacture of articles of thiol-ene polymers |
-
2014
- 2014-04-11 CN CN201410146241.7A patent/CN103936962B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1188109A (en) * | 1996-11-25 | 1998-07-22 | 株式会社日本触媒 | Process for production of sulfide group-containing mercaptocarboxylic acid and ester thereof |
| CN103221458A (en) * | 2010-10-01 | 2013-07-24 | 莫赛纳实验室公司 | Method for the manufacture of articles of thiol-ene polymers |
Non-Patent Citations (1)
| Title |
|---|
| 胡张燕等: "多支化聚硫醇与环氧树脂的固化研究", 《塑料》 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2017019735A (en) * | 2015-07-08 | 2017-01-26 | 株式会社日本触媒 | Manufacturing method of primary or secondary amine compound having (poly)alkylene glycol chain and composition containing primary or secondary amine compound having (poly)alkylene glycol chain |
| CN106883377A (en) * | 2017-03-23 | 2017-06-23 | 苏州顶裕节能设备有限公司 | It is a kind of to utilize the curing agent and its method for producing the preparation of TMPTA waste water |
| CN109370508A (en) * | 2018-10-08 | 2019-02-22 | 东莞市联灏新材料技术开发有限公司 | A kind of radiation-curable black shading Adhesive composition |
| CN109370508B (en) * | 2018-10-08 | 2021-05-18 | 东莞市联灏新材料技术开发有限公司 | Radiation-curable black shading adhesive composition |
| CN112795012A (en) * | 2020-12-30 | 2021-05-14 | 江苏富琪森新材料有限公司 | Emulsion type waterborne epoxy curing agent and preparation method and application thereof |
| CN113512361A (en) * | 2021-02-22 | 2021-10-19 | 烟台大学 | High-adhesion-strength shellac and preparation method thereof |
| CN115403541A (en) * | 2021-05-27 | 2022-11-29 | 北京化工大学 | Carboxyl-containing self-curing epoxy resin and preparation method thereof |
| CN115403541B (en) * | 2021-05-27 | 2023-12-15 | 北京化工大学 | Carboxyl-containing self-curing epoxy resin and preparation method thereof |
| CN117567076A (en) * | 2023-11-20 | 2024-02-20 | 中国人民解放军陆军工程大学 | Quick repair epoxy resin repair material and preparation method thereof |
| CN117567076B (en) * | 2023-11-20 | 2024-05-31 | 中国人民解放军陆军工程大学 | Quick repair epoxy resin repair material and preparation method thereof |
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| CN103936962B (en) | 2016-10-05 |
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