CN109467651A - Light-cured epoxy vinyl ester resin and its synthetic method - Google Patents
Light-cured epoxy vinyl ester resin and its synthetic method Download PDFInfo
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- CN109467651A CN109467651A CN201811321253.3A CN201811321253A CN109467651A CN 109467651 A CN109467651 A CN 109467651A CN 201811321253 A CN201811321253 A CN 201811321253A CN 109467651 A CN109467651 A CN 109467651A
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- light
- vinyl ester
- cured epoxy
- ester resin
- epoxy vinyl
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
- C08F283/105—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule on to unsaturated polymers containing more than one epoxy radical per molecule
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1494—Polycondensates modified by chemical after-treatment followed by a further chemical treatment thereof
Abstract
The invention discloses a kind of light-cured epoxy vinyl ester resin and its synthetic methods, the light-cured epoxy vinyl ester resin, it is to be prepared using the component of following mass percent: A epoxy resin 30%~50%, B amino acrylates 6%~15%, C catalyst 0.05%~2%, D polymerization inhibitor 0.01%~0.05%, the organic unsaturated acids 4%~15% of E, F acrylate monomer 30%~60%, reaction process of the present invention are steady, exothermic heat of reaction is easily controllable, and the extent of reaction is high.Resin viscosity is moderate, and reactivity is high, can use cation photocuring system, can be fully cured in normal temperature air environment, and the transparency is good, and photocuring depth is big, and adhesive force is strong, wear-resisting, hardness is high, and the transparency is good.
Description
Technical field
The present invention relates to a kind of epoxy vinyl ester resin and its synthetic methods.
Background technique
Light-cured resin is also known as photosensitive resin, is that after one kind is irradiated by light, object can occur rapidly in a relatively short period of time
Reason and chemical change, and then the oligomer of crosslinking curing.Light-cured resin is a kind of lower photonasty tree of relative molecular mass
Rouge has the reactive group that can carry out photocuring, such as unsaturated double-bond or epoxy group.Light-cured resin whole process is purple using UV
The solidification of outer lamp, curing time is only 5~20 minutes, is not necessarily to field mix, without additionally adding any curing agent, promotor and dilute
Release agent, directly paste, wind, being wrapped in the base wait protect or repair, eliminate in traditional handicraft live hand paste, impregnation,
The problems such as brushing and trouble.Epoxy vinyl ester resin be by epoxy resin and acrylic or methacrylic acid through esterification by ring opening and
It is made, is current widely used Photocurable oligomers.
Although epoxy vinyl ester has the advantages that a lot in curing field, there is also some problems.First, epoxy
The catalyst of resin open loop generally uses tertiary amine or quaternary ammonium salt, and triethylamine is although inexpensive, but catalytic activity is relatively low, and product is stablized
Property is slightly worse；Quaternary ammonium salt catalytic activity is slightly strong, but cost is slightly higher；Triphenylphosphine, antimony triphenyl, chromium acetylacetonate catalytic activity are high,
Product viscosity is low, but color is deeper.Second, epoxy vinyl ester uses free radical UV curing system, free radical light at present
It is serious to polymerize oxygen inhibition, easily causes surface cure bad；Usually along with biggish volume contraction when radical photopolymerization solidifies.
Third, in existing photocuring system, amino acrylates are all physical mixeds, there are layerings as a thinner composition
Situation, and amino acrylates are as diluent, it is difficult to and fully crosslinked, polymerization speed is slow, and product solidification effect is bad, performance
It is poor, to limit its practical application.Therefore a kind of energy overcoming existing epoxy vinyl ester photocuring product defects is provided
The UV photocuring product of enough crosslinkings of rapid curing at normal temperature becomes urgent problem to be solved in the prior art.
Summary of the invention
The object of the present invention is to provide a kind of light-cured epoxy vinyl ester resin and its synthetic methods, to overcome existing skill
Defect existing for art.
The light-cured epoxy vinyl ester resin is prepared using the component of following mass percent:
The sum of percentage of each component is 100%；
Preferably, the light-cured epoxy vinyl ester resin is prepared using the component of following mass percent:
The epoxy resin is selected from one of bisphenol A type epoxy resin, novolac epoxy resin and brominated epoxy resin
Or it is several；
The amino acrylates are selected from amino acrylates based on methyl-etherified melamine resin, and preferably 3
~4 degrees of functionality, 25 DEG C of viscosity are less than the amino acrylates of 1500mPa.s；
The catalyst is mercaptan amine or derivatives thereof；
The polymerization inhibitor is tert-butyl hydroquinone, tert-butyl catechol, 1,4-benzoquinone, hydroquinone, methyl to benzene two
One or more of phenol；
Organic unsaturated acids is methacrylic acid, acrylic acid, butenoic acid or fumaric acid etc.；
The acrylate monomer is selected from the low high boiling acrylate monomer of smell high-flash, including trimethylolpropane
One of triacrylate, tripropylene glycol diacrylate, neopentylglycol diacrylate, pentaerythritol triacrylate etc.
Or it is several.
The preparation method of the light-cured epoxy vinyl ester resin, including the following steps:
(1) by the epoxy resin (A), catalyst (C) and polymerization inhibitor (D), under inert atmosphere such as nitrogen protection, 50
~80 DEG C of addition amino acrylates (B), it is preferred to be dripped off within 0.5~1 hour using the method being added dropwise, until system epoxy is worked as
Amount increases to original 1.2~1.5 times；
(2) organic unsaturated acids (E) is added, 90~120 DEG C are reacted 2~3 hours, until acid value expands less than 10mgKOH/g
Chain:
(3) 80 DEG C are cooled to hereinafter, be added acrylate monomer (F), be cooled to room temperature it is preferred that 65~75 DEG C, is filtered, i.e.,
Obtain Pale yellow viscous liquid, as the light-cured epoxy vinyl ester resin.
In recent years, as the continuous development of photocuring technology and progress and the enhancing of people's energy conservation and environmental awareness, light are solid
Change resin to be rapidly developed, application field is constantly expanded, the light-cured epoxy vinyl ester resin that the present invention is developed, not only
Applied to a variety of substrates such as woodenware, paper, plastics, leather, metal, glass, ceramics, and can be applied in optical fiber, print
The materials such as printed circuit board, electronic component encapsulation.
Compared with the prior art, the present invention has the following advantages:
Present invention pre-reaction in the case where having catalyst and polymerization inhibitor by epoxy resin and amino acrylates, then in reactant
Organic unsaturated acids chain extension is put into system, then is diluted with acrylate monomer, and light-cured epoxy vinyl ester resin is synthesized.This hair
Bright is a kind of safe and environment-friendly, synthetic method of the easily controllable light-cured epoxy vinyl ester resin of reaction process, using efficient
Catalyst reaction, reaction process is easily controllable, and reaction carries out thoroughly, reducing residual.Improve oxygen inhibition, improves reaction and live
Property, realize quickly and completely polymerize, reduce and shrink have many advantages, such as that adhesive force is strong, wear-resisting, hardness is high in air atmosphere.
Catalyst mercaptan amine and its derivative used in the present invention can be with catalyzed epoxies open loops, with amino acrylates
It is reacted with organic unsaturated acids, keeps reaction process steady, exothermic heat of reaction is easily controllable, and the extent of reaction is high, and residual is few, and mercaptan
Amine and its derivative also can be used as the promotor or active constituent of photocuring, participate in photocuring production process, improve solidification
Speed.In addition resin system is of light color, and the transparency is good, and photocuring depth is big.
In existing photocuring system, amino acrylates are all physical mixeds as a component.The present invention is in asphalt mixtures modified by epoxy resin
Grafted amino group acrylate on rouge, stable structure is not stratified, and rapid curing may be implemented, fully crosslinked, improves product properties.
Grafted amino group acrylate on epoxy resin can use cation photocuring system, because its triggering mechanism is not
It is related to free radical, because without it is bad not will cause surface cure by oxygen inhibition.Amino acrylates also contribute to system
Flexibility, reduce shrink, color inhibition.
Without using the volatile cross-linking monomer dilution of phenylethylene, and use the low high boiling acrylate list of smell high-flash instead
Body, environmental protection, no styrene discharge are environmental-friendly.
Reaction process of the present invention is steady, and exothermic heat of reaction is easily controllable, and the extent of reaction is high.Resin viscosity is moderate, reactivity
Height can use cation photocuring system, can be fully cured in normal temperature air environment, transparent good, photocuring depth
Greatly, can rapid curing, improve production efficiency.
Specific embodiment
Embodiment 1
450g bisphenol A type epoxy resin E51, three ethyl mercaptan amine 4.0g of catalyst, tert-butyl o benzene are put into the reactor
Diphenol 0.15g is gradually heated to 80 DEG C in the case where being passed through nitrogen, keep temperature and stirring, and 3 degrees of functionality, 25 DEG C of viscosity are added dropwise
The amino acrylates 100g of 1200cps, drips off, adds methacrylic acid 60g, be sufficiently stirred, be gradually warming up to for 0.5 hour
90 DEG C are reacted 2.5 hours, and acid value is less than 10mgKOH/g；It is cooled to 75 DEG C or less addition trimethylolpropane trimethacrylates
360g is finally cooled to room temperature, filtering, as the light-cured epoxy vinyl ester resin, is Pale yellow viscous liquid.
Testing result is as follows:
Embodiment 2
400g brominated epoxy resin Ex-48, three ethyl mercaptan amine 2.5g of catalyst, hydroquinone are put into the reactor
0.20g is gradually heated to 60 DEG C in the case where being passed through nitrogen, keep temperature and stirring, and 3 degrees of functionality, 25 DEG C of viscosity 700cps are added dropwise
Amino acrylates 120g, drip off within 1 hour, add acrylic acid 50g, be sufficiently stirred, it is 2 small to be gradually warming up to 110 DEG C of reactions
When, acid value is less than 10mgKOH/g；70 DEG C or less addition neopentylglycol diacrylate 450g are cooled to, room temperature is finally cooled to,
It filters up to Pale yellow viscous liquid.
Testing result is as follows:
Embodiment 3
350g novolac epoxy resin F51, catalyst n, N- diisopropyl ethyl mercaptan amine 3.8g, tertiary fourth are put into the reactor
Base hydroquinone 0.10g is gradually heated to 70 DEG C in the case where being passed through nitrogen, keep temperature and stirring, and 4 degrees of functionality, 25 are added dropwise
The amino acrylates 90g of DEG C viscosity 300cps, drips off, adds fumaric acid 65g, be sufficiently stirred, gradually rise for 0.5 hour
Temperature to 100 DEG C react 3 hours, acid value be less than 10mgKOH/g；It is cooled to 65 DEG C or less addition trimethylolpropane trimethacrylates
400g is finally cooled to room temperature, filters up to Pale yellow viscous liquid.
Testing result is as follows:
Embodiment 4
420g novolac epoxy resin F48 is put into the reactor, and catalyst 2- dimethylamino ethyl mercaptan 2.5g, methyl is to benzene
Diphenol 0.12g is gradually heated to 70 DEG C in the case where being passed through nitrogen, keep temperature and stirring, and 3 degrees of functionality, 25 DEG C of viscosity are added dropwise
The amino acrylates 120g of 900cps, drips off, adds methacrylic acid 80g, be sufficiently stirred, be gradually warming up to for 0.5 hour
90 DEG C are reacted 3 hours, and acid value is less than 10mgKOH/g；70 DEG C or less addition pentaerythritol triacrylate 430g are cooled to, finally
It is cooled to room temperature, filters up to Pale yellow viscous liquid.
Testing result is as follows:
Embodiment 5
420g novolac epoxy resin E44 is put into the reactor, and catalyst 2- dimethylamino ethyl mercaptan 2.9g, methyl is to benzene
Diphenol 0.10g is gradually heated to 70 DEG C in the case where being passed through nitrogen, keep temperature and stirring, and 4 degrees of functionality, 25 DEG C of viscosity are added dropwise
The amino acrylates 130g of 800cps, drips off, adds methacrylic acid 55g, be sufficiently stirred, be gradually warming up to for 0.5 hour
100 DEG C are reacted 2 hours, and acid value is less than 10mgKOH/g；80 DEG C or less addition pentaerythritol triacrylate 400g are cooled to, most
After be cooled to room temperature, filter up to Pale yellow viscous liquid.
Testing result is as follows:
Embodiment 6
350g novolac epoxy resin F51, catalyst n, N- diisopropyl ethyl mercaptan amine 3.8g, tertiary fourth are put into the reactor
Base hydroquinone 0.10g is gradually heated to 70 DEG C in the case where being passed through nitrogen, keep temperature and stirring, and 4 degrees of functionality, 25 are added dropwise
The amino acrylates 90g of DEG C viscosity 300cps, drips off, adds methacrylic acid 70g, be sufficiently stirred, gradually rise for 0.5 hour
Temperature to 90 DEG C react 1.5 hours, acid value be less than 10mgKOH/g；It is cooled to 60 DEG C or less addition trimethylolpropane tris acrylic acid
Ester 360g, is finally cooled to room temperature, filters up to Pale yellow viscous liquid.
Testing result is as follows:
。
Claims (10)
1. light-cured epoxy vinyl ester resin, which is characterized in that prepared using the component of following mass percent:
2. light-cured epoxy vinyl ester resin, which is characterized in that prepared using the component of following mass percent:
3. light-cured epoxy vinyl ester resin according to claim 1 or 2, which is characterized in that the epoxy resin
Selected from one or more of bisphenol A type epoxy resin, novolac epoxy resin and brominated epoxy resin.
4. light-cured epoxy vinyl ester resin according to claim 1 or 2, which is characterized in that the amino propylene
Acid esters is selected from the amino acrylates based on methyl-etherified melamine resin.
5. light-cured epoxy vinyl ester resin according to claim 4, which is characterized in that the amino acrylates
It is less than the amino acrylates of 1500mPa.s for 3~4 degrees of functionality, 25 DEG C of viscosity.
6. light-cured epoxy vinyl ester resin according to claim 1 or 2, which is characterized in that the catalyst is sulphur
Hydramine or derivatives thereof.
7. light-cured epoxy vinyl ester resin according to claim 1 or 2, which is characterized in that the polymerization inhibitor is uncle
One or more of butylhydroquinone, tert-butyl catechol, 1,4-benzoquinone, hydroquinone or methyl hydroquinone.
8. light-cured epoxy vinyl ester resin according to claim 1 or 2, which is characterized in that organic unsaturation
Acid is one or more of methacrylic acid, acrylic acid, butenoic acid or fumaric acid, and the acrylate monomer is selected from three hydroxyls
Propane tri, tripropylene glycol diacrylate, neopentylglycol diacrylate or pentaerythritol triacrylate
One or more of.
9. the preparation method of described in any item light-cured epoxy vinyl ester resins, feature exist according to claim 1~8
In, including the following steps:
(1) by the epoxy resin (A), catalyst (C) and polymerization inhibitor (D), under inert atmosphere protection, amino propylene is added
Acid esters (B)；
(2) organic unsaturated acids (E), reaction is added, until acid value is less than 10mgKOH/g chain extension:
(3) cool down, be added acrylate monomer (F), be cooled to room temperature, filter to get Pale yellow viscous liquid, as described
Light-cured epoxy vinyl ester resin.
10. according to the method described in claim 9, it is characterized in that, by the epoxy resin (A), being catalyzed in step (1)
Agent (C) and polymerization inhibitor (D), under inert atmosphere protection, using the method for dropwise addition, 50~80 DEG C of addition amino acrylates (B),
It drips off within 0.5~1 hour；
It in step (2), is added organic unsaturated acids (E), 90~120 DEG C are reacted 2~3 hours；
In step (3), 65~75 DEG C are cooled to, is added acrylate monomer (F).
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| CN201811321253.3A CN109467651B (en) | 2018-11-07 | 2018-11-07 | Light-cured epoxy vinyl ester resin and synthetic method thereof |
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| CN201811321253.3A CN109467651B (en) | 2018-11-07 | 2018-11-07 | Light-cured epoxy vinyl ester resin and synthetic method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110669224A (en) * | 2019-10-09 | 2020-01-10 | 上海昭和高分子有限公司 | Vinyl ester resin and preparation method and application thereof |
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| CN102558456A (en) * | 2011-12-30 | 2012-07-11 | 华东理工大学华昌聚合物有限公司 | Method for synthesizing epoxy vinyl ester resin |
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| KR20180039844A (en) * | 2016-10-11 | 2018-04-19 | 주식회사 파인텍 | Resin composition for uv-curable, optical member formed by using the same, backlight unit and display device comprising the same |
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2018
- 2018-11-07 CN CN201811321253.3A patent/CN109467651B/en active Active
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|---|---|---|---|---|
| CN1965267A (en) * | 2004-05-26 | 2007-05-16 | 昭和电工株式会社 | Photosensitive resin composition, and cured product and use thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110669224A (en) * | 2019-10-09 | 2020-01-10 | 上海昭和高分子有限公司 | Vinyl ester resin and preparation method and application thereof |
| CN110669224B (en) * | 2019-10-09 | 2021-08-03 | 上海昭和高分子有限公司 | Vinyl ester resin and preparation method and application thereof |
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| CN109467651B (en) | 2021-01-15 |
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