CN104262219A - Thiol-ene photocuring resin and preparation method thereof - Google Patents
Thiol-ene photocuring resin and preparation method thereof Download PDFInfo
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- CN104262219A CN104262219A CN201410437965.7A CN201410437965A CN104262219A CN 104262219 A CN104262219 A CN 104262219A CN 201410437965 A CN201410437965 A CN 201410437965A CN 104262219 A CN104262219 A CN 104262219A
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Abstract
The invention discloses a thiol-ene photocuring resin and a preparation method thereof. The preparation method comprises the following steps: by taking allyl glycidyl ether and carbon disulfide as raw materials, reacting and synthesizing into thiocarbonate alkyl ether under the catalysis of catalyst lithium bromate; respectively performing ring-opening reaction on thiocarbonate alkyl ether and n-butylamine, 1,6-hexanediamine and benzylamine, to produce thiol-ene photocuring monomer. On the presence of photoinitiator, chain transfer reaction on double bonds and sulfydryl in the photopolymerized monomer can enable the volume of a polymer to be shrunk and reduced in polymerization; oxygen inhibition does not exist; gel is delayed; according to different ethylene monomers, the crosslinking degree and the reaction speed can be controlled; less or zero photoinitiator is used, and the like.
Description
Technical field
The invention belongs to field of light-sensitive high molecular materials, be specifically related to mercaptan-alkene light-cured resin being applied to curing field and preparation method thereof.
Background technology
Light-cured resin, also known as photosensitive resin, is, after one is subject to irradiate light, rapidly physical and chemical changes can occur at short notice, and then the oligopolymer of crosslinking curing.Light-cured resin is the photosensitive resin that a kind of relative molecular weight is lower, has the reactive group that can carry out photocuring, as unsaturated double-bond or epoxy group(ing) etc.In the North America radiation curing international conference held in May, 2004, this technology is summarized as has " 5E " feature: efficient, and wide adaptability is economical, energy-conservation and environmental friendliness.
Can there is volumetric shrinkage in acrylic resin and monomer whose, cause sticking power, the degradation such as hardness in photopolymerisable process, and traditional acrylic resin oxygen inhibition is serious in the course of the polymerization process, cause film not done.
In sulfydryl alkene photopolymerization reaction, chainpropagation and chain tra nsfer are in race condition, make this polymkeric substance have larger polymerization shrinkage, but the chain transfer reaction between sulfydryl with double bond reduce the contraction being polymerized volume.And among sulfydryl alkene body of light system, the inhibition of oxygen is also not obvious, and this just eliminates oxygen inhibition effect.
Summary of the invention
The invention provides the preparation method of mercaptan-alkene light-cured resin.The present invention from Molecular Structure Design, thiol synthesis-alkene light-cured resin.In the presence of photo initiator, when being polymerized, polymkeric substance has volumetric shrinkage little to this light-cured resin, and without oxygen inhibition, delayed gel, is easy to control, on a small quantity or the advantage such as the use of zero light trigger.
Mercaptan-alkene light-cured resin structural formula of the present invention is as follows:
The preparation method of this mercaptan-alkene light-cured resin is as follows:
The first step is reacted: by the glycidyl allyl ether containing 1 molar fraction, be dissolved in 0.5-1.5L solvent solution-forming, the catalyzer of 0.005-0.05 molar fraction is added in solution, the dithiocarbonic anhydride of 1.2 ~ 1.4 molar fractions, stir 24 hours at 25 DEG C, underpressure distillation is except desolventizing, be dissolved in methylene dichloride, with 10mL-20mL deionized water wash 3 times, anhydrous sodium sulfate drying spends the night, and filters, and rotary evaporation removes methylene dichloride, vacuum-drying obtains intermediate product, and the structure of intermediate product is as shown in following molecular formula:
Wherein, solvent is selected from THF, DMF, methyl alcohol.
In addition, catalyzer is selected from lithium chloride, lithiumbromide, lithium iodide.
Second step reacts: in the intermediate product obtained in 1 part of the first step, add the n-Butyl Amine 99 of 1 molar fraction, 1,6-hexanediamine or benzylamine, at 25 DEG C of reaction 6-8 hour, reacts complete, obtains required product, containing the photo-curing monomer of mercaptan-thiazolinyl.
Embodiment
Embodiment 1
The first step is reacted: by the glycidyl allyl ether containing 1 molar fraction, be dissolved in the THF of 0.5L, wiring solution-forming, the lithium chloride of 0.005 molar fraction is added in solution, the dithiocarbonic anhydride of 1.2 molar fractions, stirs 24 hours at 25 DEG C, underpressure distillation removing THF, be dissolved in methylene dichloride, with 10mL deionized water wash 3 times, anhydrous sodium sulfate drying spends the night, and filters, rotary evaporation removes methylene dichloride, and vacuum-drying obtains intermediate product;
Second step reacts: in the intermediate product obtained in the first step of 1 part, add the n-Butyl Amine 99 of 1 molar fraction, 25 DEG C of reactions 6 hours, reacts complete, obtains the photo-curing monomer containing mercaptan-thiazolinyl.
Embodiment 2
The first step is reacted: by the glycidyl allyl ether containing 1 molar fraction, be dissolved in the DMF of 1.5L, wiring solution-forming, the lithiumbromide of 0.05 molar fraction is added in solution, the dithiocarbonic anhydride of 1.2 molar fractions, stirs 24 hours at 25 DEG C, and underpressure distillation is except desolventizing, be dissolved in methylene dichloride, with 10mL deionized water wash 3 times, anhydrous sodium sulfate drying spends the night, and filters, rotary evaporation removes methylene dichloride, and vacuum-drying obtains intermediate product;
Second step reacts: in the intermediate product obtained in 1 part of the first step, add the n-Butyl Amine 99 of 1 molar fraction, 25 DEG C of reactions 7 hours, reacts complete, obtains the photo-curing monomer containing mercaptan-thiazolinyl.
Embodiment 3
The first step is reacted: by the glycidyl allyl ether containing 1 molar fraction, be dissolved in the THF of 1L, wiring solution-forming, the lithium chloride of 0.005 molar fraction is added in solution, the dithiocarbonic anhydride of 1.4 molar fractions, stirs 24 hours at 25 DEG C, and underpressure distillation is except desolventizing, be dissolved in methylene dichloride, with 20mL deionized water wash 3 times, anhydrous sodium sulfate drying spends the night, and filters, rotary evaporation removes methylene dichloride, and vacuum-drying obtains intermediate product;
Second step reacts: in the intermediate product obtained in the first step of 1 part, add 1,6-hexanediamine of 0.5 molar fraction, 25 DEG C of reactions 6 hours, reacts complete, obtains the photo-curing monomer containing mercaptan-thiazolinyl.
Embodiment 4
The first step is reacted: by the glycidyl allyl ether containing 1 molar fraction, be dissolved in the methyl alcohol of 1.5L, wiring solution-forming, the lithium iodide of 0.05 molar fraction is added in solution, the dithiocarbonic anhydride of 1.4 molar fractions, stirs 24 hours at 25 DEG C, and underpressure distillation is except desolventizing, be dissolved in methylene dichloride, with 20mL deionized water wash 3 times, anhydrous sodium sulfate drying spends the night, and filters, rotary evaporation removes methylene dichloride, and vacuum-drying obtains intermediate product;
Second step reacts: in the intermediate product obtained in the first step of 1 part, add 1,6-hexanediamine of 0.5 molar fraction, 25 DEG C of reactions 8 hours, reacts complete, obtains the photo-curing monomer containing mercaptan-thiazolinyl.
Embodiment 5
The first step is reacted: by the glycidyl allyl ether containing 1 molar fraction, be dissolved in the THF of 1L, wiring solution-forming, the lithiumbromide of 0.05 molar fraction is added in solution, the dithiocarbonic anhydride of 1.3 molar fractions, stirs 24 hours at 25 DEG C, and underpressure distillation is except desolventizing, be dissolved in methylene dichloride, with 15mL deionized water wash 3 times, anhydrous sodium sulfate drying spends the night, and filters, rotary evaporation removes methylene dichloride, and vacuum-drying obtains intermediate product;
Second step reacts: in the intermediate product obtained in 1 part of the first step, add the benzylamine of 1 molar fraction, 25 DEG C of reactions 7 hours, reacts complete, obtains the photo-curing monomer containing mercaptan-thiazolinyl.
Embodiment 6
The first step is reacted: by the glycidyl allyl ether containing 1 molar fraction, be dissolved in the DMF of 1.5L, wiring solution-forming, the lithium iodide of 0.005 molar fraction is added in solution, the dithiocarbonic anhydride of 1.4 molar fractions, stirs 24 hours at 25 DEG C, and underpressure distillation is except desolventizing, be dissolved in methylene dichloride, with 20mL deionized water wash 3 times, anhydrous sodium sulfate drying spends the night, and filters, rotary evaporation removes methylene dichloride, and vacuum-drying obtains intermediate product;
Second step reacts: in the intermediate product obtained in the first step of 1 part, add the benzylamine of 1 molar fraction, at 25 DEG C of reaction 6-8 hour, reacts complete, obtains the photo-curing monomer containing mercaptan-thiazolinyl.
Claims (4)
1. mercaptan-alkene light-cured resin, its structural formula is as follows:
2. the preparation method of mercaptan-alkene light-cured resin according to claim 1, is characterized in that: comprise the steps:
The first step is reacted: by the glycidyl allyl ether containing 1 molar fraction, be dissolved in 0.5-1.5L solvent solution-forming, in solution, add the catalyzer of 0.005-0.05 molar fraction, the dithiocarbonic anhydride of 1.2 ~ 1.4 molar fractions, stir 24 hours at 25 DEG C, underpressure distillation except desolventizing, is dissolved in methylene dichloride, with 10mL-20mL deionized water wash 3 times, anhydrous sodium sulfate drying spends the night, filter, rotary evaporation removes methylene dichloride, and vacuum-drying obtains intermediate product;
Second step reacts: in the intermediate product obtained in 1 part of the first step, add the n-Butyl Amine 99 of 1 molar fraction, 1,6-hexanediamine or benzylamine, at 25 DEG C of reaction 6-8 hour, reacts complete, obtains required product, containing the photo-curing monomer of mercaptan-thiazolinyl.
3. the preparation method of mercaptan-alkene base photo-curing monomer as claimed in claim 2, is characterized in that: the solvent described in the first step is selected from THF, DMF, methyl alcohol, acetone or acetonitrile.
4. the preparation method of mercaptan-alkene base photo-curing monomer as claimed in claim 2, is characterized in that: the catalyzer described in the first step is selected from lithium chloride, lithiumbromide, lithium iodide.
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| CN201410437965.7A CN104262219B (en) | 2014-08-29 | 2014-08-29 | Mercaptan-alkene light-cured resin and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110607123A (en) * | 2019-10-04 | 2019-12-24 | 汤杰 | Room-temperature self-repairing coating and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08302010A (en) * | 1995-05-08 | 1996-11-19 | Nippon Oil & Fats Co Ltd | Polythiourethane |
| JPH11246632A (en) * | 1998-03-05 | 1999-09-14 | Kyowa Yuka Kk | Vinylic copolymer, its composition, and coating material and hardened product by using same |
| US20060293280A1 (en) * | 2003-08-15 | 2006-12-28 | Kazuya Uenishi | 1,3-Oxathiolane-2-thione compounds |
| CN103254105A (en) * | 2013-04-01 | 2013-08-21 | 常州大学 | Vinyl ether resin and preparation method thereof |
-
2014
- 2014-08-29 CN CN201410437965.7A patent/CN104262219B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08302010A (en) * | 1995-05-08 | 1996-11-19 | Nippon Oil & Fats Co Ltd | Polythiourethane |
| JPH11246632A (en) * | 1998-03-05 | 1999-09-14 | Kyowa Yuka Kk | Vinylic copolymer, its composition, and coating material and hardened product by using same |
| US20060293280A1 (en) * | 2003-08-15 | 2006-12-28 | Kazuya Uenishi | 1,3-Oxathiolane-2-thione compounds |
| CN103254105A (en) * | 2013-04-01 | 2013-08-21 | 常州大学 | Vinyl ether resin and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110607123A (en) * | 2019-10-04 | 2019-12-24 | 汤杰 | Room-temperature self-repairing coating and preparation method thereof |
| CN110607123B (en) * | 2019-10-04 | 2021-08-10 | 韶关长悦高分子材料有限公司 | Room-temperature self-repairing coating and preparation method thereof |
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