CN103450447B - A kind of synthetic method of modified bisphenol A epoxy acrylate - Google Patents
A kind of synthetic method of modified bisphenol A epoxy acrylate Download PDFInfo
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- CN103450447B CN103450447B CN201310375343.1A CN201310375343A CN103450447B CN 103450447 B CN103450447 B CN 103450447B CN 201310375343 A CN201310375343 A CN 201310375343A CN 103450447 B CN103450447 B CN 103450447B
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- Prior art keywords
- bisphenol
- epoxy acrylate
- epoxide resin
- modified bisphenol
- synthetic method
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- -1 modified bisphenol A epoxy acrylate Chemical class 0.000 title claims abstract description 24
- 238000010189 synthetic method Methods 0.000 title claims abstract description 11
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims abstract description 42
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000003822 epoxy resin Substances 0.000 claims abstract description 20
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 20
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 10
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical group COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 6
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical group [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 5
- 239000000463 material Substances 0.000 abstract description 6
- 238000000034 method Methods 0.000 abstract description 6
- 238000004383 yellowing Methods 0.000 abstract description 5
- 239000006223 plastic coating Substances 0.000 abstract description 2
- 229940106691 bisphenol a Drugs 0.000 description 14
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- 239000004593 Epoxy Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000009413 insulation Methods 0.000 description 5
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 5
- 238000003756 stirring Methods 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000007664 blowing Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 239000002826 coolant Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000001723 curing Methods 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 235000012424 soybean oil Nutrition 0.000 description 2
- 239000003549 soybean oil Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 102000009091 Amyloidogenic Proteins Human genes 0.000 description 1
- 108010048112 Amyloidogenic Proteins Proteins 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000003942 amyloidogenic effect Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Abstract
The present invention discloses a kind of synthetic method of modified bisphenol A epoxy acrylate.The method comprises bisphenol A epoxide resin, ethylene glycol, catalyzer and stopper Hybrid Heating, react at 80 ~ 90 DEG C after 1 ~ 2 hour and add vinylformic acid, 3 ~ 5 hours are incubated at 100 ~ 120 DEG C, namely modified bisphenol A epoxy acrylate is obtained, wherein, the consumption of described ethylene glycol is 0.1 ~ 0.4 times of bisphenol A epoxide resin weight, and described acrylic acid consumption is 10% ~ 30% of bisphenol A epoxide resin weight.Adopt the present invention to synthesize snappiness, the yellowing resistance that the modified bisphenol A epoxy acrylate obtained significantly improves product, reduce the viscosity of this material, expand the Application Areas of product, as can be applicable to light-curable ink, plastic coating etc.
Description
Technical field
The invention belongs to resins synthesis field, be specifically related to a kind of synthetic method of modified bisphenol A epoxy acrylate.
Background technology
In numerous epoxy acrylate, bisphenol-a epoxy acrylate is the fastest one of laser curing velocity, cured film hardness is large, high gloss, chemical resistance is excellent, thermotolerance and good electrical property, in addition its convenient sources, low price, be widely used in light and heat curing coating system in addition, but the aromatic ring in bisphenol-a epoxy acrylate molecular structure makes molecule have rigid structure, flexible not enough, fragility is high, viscosity is high, affect working viscosity and the rheological of coating, light aging resisting and resistance to spend amyloidogenic, therefore, scientific research personnel has done some effort and trial for above problem is also corresponding.Common methods is as introduced fatty acid modified epoxy acrylate to improve snappiness; Or with epoxy soybean oil synthesizing epoxy soybean oil acrylate to reduce viscosity, increase flexible; And first use dibasic acid anhydride (as Tetra hydro Phthalic anhydride) and Hydroxyethyl acrylate reactant to react with epoxy resin again to prepare the ordinary methods such as modified epoxy acrylic ester but all cannot overcome the above problems very well.
Summary of the invention
The object of the present invention is to provide a kind of synthetic method of modified bisphenol A epoxy acrylate, the modified bisphenol A epoxy acrylate that method obtains thus has low viscosity and higher anti-yellowing change and snappiness.
It is as follows that the present invention realizes technical scheme that above-mentioned purpose adopts:
A kind of synthetic method of modified bisphenol A epoxy acrylate, the method comprises bisphenol A epoxide resin, ethylene glycol, catalyzer and stopper Hybrid Heating, react at 80 ~ 90 DEG C after 1 ~ 2 hour and add vinylformic acid, 3 ~ 5 hours are incubated at 100 ~ 120 DEG C, namely modified bisphenol A epoxy acrylate is obtained, wherein, the consumption of described ethylene glycol is 0.1 ~ 0.4 times of bisphenol A epoxide resin weight, and described acrylic acid consumption is 10% ~ 30% of bisphenol A epoxide resin weight.
Further, the consumption of described ethylene glycol is 0.1 ~ 0.2 times of bisphenol A epoxide resin weight.
Further, described catalyzer is Tetrabutyl amonium bromide or triethylamine.
Further, the consumption of described catalyzer is 0.1% ~ 0.5% of bisphenol A epoxide resin weight.
Further, described stopper is MEHQ.
Further, the consumption of described stopper is 0.1% ~ 0.5% of bisphenol A epoxide resin weight.
Modified bisphenol A epoxy acrylate provided by the present invention significantly improves snappiness, the yellowing resistance of product compared with existing bisphenol A epoxy acrylate, reduce the viscosity of this material, expand the Application Areas of this material, as can be applicable to light-curable ink, plastic coating etc.The present invention's modified bisphenol A epoxy acrylate yellowing resistance that also discovery Tetrabutyl amonium bromide does catalyzer gained will be much better than and adopt triethylamine to make catalyzer.
Embodiment
The present invention is by below in conjunction with specific examples, for a more detailed description to the present invention, but can not be interpreted as limiting the scope of the invention.
Prepared by embodiment one bisphenol A epoxy acrylate
First by bisphenol A epoxide resin 1000g(epoxy equivalent (weight) 185 ~ 195g/eq, purchased from the wooden Chemical Co., Ltd. in Jiangsu three), vinylformic acid 240g, catalyst of triethylamine 2.7g, stopper MEHQ 3g all add in reactor.After raw material is all thrown, open and stir, regulate mixing speed at 80 ~ 100 revs/min, start slowly to heat up, within about 1 hour, be warming up to 115 DEG C.Then 115 ~ 120 DEG C of insulations 5 hours, insulation terminates rear detection acid number, treats that acid number is less than 5mgKOH/g, can open the cooling of water coolant raft, be down to 80 DEG C of blowings.During acid number of the present invention refers to and the mg value of potassium hydroxide needed for 1g sample.
The preparation of embodiment two modified bisphenol A epoxy acrylate
By bisphenol A epoxide resin 1000g(epoxy equivalent (weight) 185 ~ 195g/eq) and ethylene glycol 100g join in reaction vessel, and add catalyzer Tetrabutyl amonium bromide 2.1kg, stopper MEHQ 1.2kg, start to stir and be warming up to temperature of reaction 80 DEG C, react after 1 hour, add 240g vinylformic acid again, then 115 DEG C of insulations 5 hours, when acid number is less than 5, open the cooling of water coolant raft, be down to 80 DEG C of blowings.
The preparation of embodiment three modified bisphenol A epoxy acrylate
By bisphenol A epoxide resin 1000g(epoxy equivalent (weight) 185 ~ 195g/eq) and ethylene glycol 400g join in reaction vessel, and add catalyst of triethylamine 2.4kg, stopper MEHQ 1.2kg, start to stir and be warming up to temperature of reaction 90 DEG C, react after 1 hour, add 230g vinylformic acid again, then 100 DEG C of insulations 5 hours, when acid number is less than 5.
Prepared by embodiment four modified bisphenol A epoxy acrylate
By bisphenol A epoxide resin 1000g(epoxy equivalent (weight) 185 ~ 195g/eq) and ethylene glycol 200g join in reaction vessel, and add catalyzer Tetrabutyl amonium bromide 2.4kg, stopper MEHQ 1.1kg, start to stir and be warming up to temperature of reaction 80 DEG C, react 2 hours, add 114g vinylformic acid again, then 120 DEG C of insulations 3 hours, when acid number is less than 5.
Performance parameter test
1, viscosity test, snappiness test
Snappiness is detected according to standard GB/T/T1731-1993;
Viscosity: use rotational viscosimeter to test, 60 DEG C.
。
2, anti-yellowing change test
Testing method
Light trigger (model: 1173, chemical name: 2-hydroxy-methyl phenyl-propane-1-ketone
Proportioning: light trigger (1173): modified bisphenol A epoxy acrylate=3:97(mass ratio)
Base material: white polycarbonate sheet material
Technique: the mixture of light trigger and modified bisphenol A epoxy acrylate is stirred by above proportioning, with 10 μm of line rod blade coatings on white polycarbonate sheet material, thickness=10 μm, be placed in 60 DEG C of thermostatic drying chamber levelling 5min, take out with ultraviolet light curing, colorimetric case ready visual contrast xanthochromia situation.
Illuminate condition: lamp distance: 10cm; Linear speed: 10m/s
Test result
。
Claims (4)
1. the synthetic method of a modified bisphenol A epoxy acrylate, it is characterized in that: described synthetic method comprises bisphenol A epoxide resin, ethylene glycol, catalyzer and stopper Hybrid Heating, react at 80 ~ 90 DEG C after 1 ~ 2 hour and add vinylformic acid, 3 ~ 5 hours are incubated at 100 ~ 120 DEG C, namely modified bisphenol A epoxy acrylate is obtained, wherein, the consumption of described ethylene glycol is 0.1 ~ 0.4 times of bisphenol A epoxide resin weight, and described acrylic acid consumption is 10% ~ 30% of bisphenol A epoxide resin weight;
The consumption of described ethylene glycol is 0.1 ~ 0.2 times of bisphenol A epoxide resin weight;
Described catalyzer is Tetrabutyl amonium bromide.
2. the synthetic method of modified bisphenol A epoxy acrylate according to claim 1, is characterized in that: the consumption of described catalyzer is 0.1% ~ 0.5% of bisphenol A epoxide resin gross weight.
3. the synthetic method of modified bisphenol A epoxy acrylate according to claim 1, is characterized in that: described stopper is MEHQ.
4. the synthetic method of modified bisphenol A epoxy acrylate according to claim 1, is characterized in that: the consumption of described stopper is 0.1% ~ 0.5% of bisphenol A epoxide resin weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310375343.1A CN103450447B (en) | 2013-08-26 | 2013-08-26 | A kind of synthetic method of modified bisphenol A epoxy acrylate |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201310375343.1A CN103450447B (en) | 2013-08-26 | 2013-08-26 | A kind of synthetic method of modified bisphenol A epoxy acrylate |
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| Publication Number | Publication Date |
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| CN103450447A CN103450447A (en) | 2013-12-18 |
| CN103450447B true CN103450447B (en) | 2016-02-03 |
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| CN201310375343.1A Expired - Fee Related CN103450447B (en) | 2013-08-26 | 2013-08-26 | A kind of synthetic method of modified bisphenol A epoxy acrylate |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105885013B (en) * | 2016-04-26 | 2018-05-08 | 深圳市姿彩科技有限公司 | A kind of preparation method for the low viscosity epoxy acrylic resin that can be used for spraying |
| CN111574912A (en) * | 2020-06-24 | 2020-08-25 | 湖北锡太化工股份有限公司 | Epoxy acrylate |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101928508A (en) * | 2010-08-24 | 2010-12-29 | 华南理工大学 | Polyethylene glycol-modified epoxy acrylate coating and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101928508A (en) * | 2010-08-24 | 2010-12-29 | 华南理工大学 | Polyethylene glycol-modified epoxy acrylate coating and preparation method thereof |
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| CN103450447A (en) | 2013-12-18 |
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Effective date of registration: 20151231 Address after: 214000 Xinhua Road, Wuxi province national high tech Industrial Development Zone, No. innovation Creative Industrial Park, building, room 109, B, China, Jiangsu Applicant after: JIANGSU GAOBO ZHIRONG TECHNOLOGY Co.,Ltd. Address before: 214000 Jiangsu Province, Wuxi city Xishan District Beizhen Zhang Shan chemical District Jingquan tin Applicant before: Wuxi Jinsheng Auxiliaries Factory |
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| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
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Inventor after: Li Yiquan Inventor before: Zhu Renzu |
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| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20170324 Address after: Xinhui District Mu Zhou Mei Chong 529000 Guangdong city of Jiangmen Province in nanyo Patentee after: Jiangmen Hengzhiguang Environmental Protection New Material Co.,Ltd. Address before: 214000 Xinhua Road, Wuxi province national high tech Industrial Development Zone, No. innovation Creative Industrial Park, building, room 109, B, China, Jiangsu Patentee before: JIANGSU GAOBO ZHIRONG TECHNOLOGY Co.,Ltd. |
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| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160203 |