CN107739441A - A kind of synthetic method of novel organosilicon modified epoxy - Google Patents
A kind of synthetic method of novel organosilicon modified epoxy Download PDFInfo
- Publication number
- CN107739441A CN107739441A CN201710938706.6A CN201710938706A CN107739441A CN 107739441 A CN107739441 A CN 107739441A CN 201710938706 A CN201710938706 A CN 201710938706A CN 107739441 A CN107739441 A CN 107739441A
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- CN
- China
- Prior art keywords
- synthetic method
- resin
- added dropwise
- bisphenol
- silicone oil
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Classifications
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- 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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
-
- 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
Abstract
The present invention relates to a kind of synthetic method of novel organosilicon modified epoxy, including：(1) bisphenol A epoxide resin and three (five fluorine) phenylborinanes are dissolved in toluene in four-hole boiling flask, at room temperature, stir 10~30min, resin solution is made；(2) hydrogeneous methyl phenyl silicone oil will be held to be slowly added dropwise in system, after being added dropwise, is warming up to 50~80 DEG C, negative pressure is less than 0.5Mpa, reacts 4~6h；(3) solvent finally is removed under the conditions of 100~120 DEG C, vacuum condition of the vacuum less than 0.085Mpa, finally gives the epoxy resin of the modification of organic siliconresin containing phenyl.The present invention avoids the high-boiling and low-boiling components content caused by system jaundice, alkoxy hydrolysis caused by Si―H addition reaction, ensure that epoxide number is constant, and post-processing approach is simple by methods of the Si H based on C OH base dehydrogenative condensations.
Description
Technical field
The present invention relates to a kind of synthetic method of novel organosilicon modified epoxy, belong to epoxy resin modification field.
Technical background
Bisphenol A epoxide resin is because of its good corrosion resistance, electrical insulating property is good, cementability is high, solidified after-product mechanical property is excellent
It is different and be widely used in the fields such as electronics, machinery, but density is big after the crosslinking of its cured product, toughness and humidity resistance are poor.Have
Machine silicon materials have excellent low-surface-energy, heat endurance, low temperature flexibility etc..Therefore, the introducing of organosilicon reduces bisphenol-A
The internal stress of epoxy resin, improve the performances such as its pliability, resistance to oxidation, wet-heat resisting.
At present, the method for modifying epoxy resin by organosilicon is divided into physical modification and chemical modification.Epoxy resin and organosilicon
The solubility parameter difference of resin is larger.Mixed by churned mechanically method, due to poor compatibility, cause the uniformity of product
It is poor, it is the state being separated is presented more.And by the method for chemical modification, can not only solve toughness, the heat endurance of resin
Deng the compatibility of the two can also be improved.Use polymethyl siloxane at present for modified epoxy more, but it is wherein substantial amounts of
Methyl causes its poor compatibility with epoxy resin.The introducing of appropriate phenyl, has very to the describing property of organosilicon and epoxy resin
Big facilitation.
The content of the invention
The present invention prepares modifying epoxy resin by organosilicon, benzene using the hydrogeneous polyphenyl methyl siloxane in the end containing phenyl
The presence of base further improves the compatibility of organosilicon and epoxy resin.And then improve the toughness of epoxy resin, thermostabilization
Property etc..
Reaction equation of the present invention is：
Wherein, m is 80~100 natural number, and n is 3~5 natural number.
The present invention, as catalyst, realizes Si -- H bond and C-OH dehydrogenation polymerizations using three (five fluorine) phenylborinanes.
The technical scheme that the present invention takes is：
(1) bisphenol A epoxide resin and three (five fluorine) phenylborinanes are dissolved in toluene in four-hole boiling flask, at room temperature,
10~30min is stirred, resin solution is made；
(2) hydrogeneous methyl phenyl silicone oil will be held to be slowly added dropwise in system, after being added dropwise, is warming up to 50~80 DEG C, born
Pressure is less than 0.5Mpa, reacts 4~6h；
(3) solvent finally is removed under the conditions of 100~120 DEG C, vacuum condition of the vacuum less than 0.085Mpa, it is final to obtain
The epoxy resin being modified to organic siliconresin containing phenyl；
In the step (1), (2), stirring uses mechanical agitation, and rotating speed is 100~150 turns/min.
In the step (1), resin toluene solution mass fraction preferably 30~50wt%.
In the step (1), mixing time preferably 10~30min at room temperature.
In the step (2), the preferred n of the hydrogeneous methyl phenyl silicone oil in end (Ph):n(CH3)=1, relative molecular mass
For 1000~2000 silicone oil.
In the step (2), preferably 50~80 DEG C of the warming temperature, negative pressure is preferably smaller than 0.5Mpa, and the reaction time is excellent
Select 4~6h.
In the step (3), the vacuum is preferably smaller than 0.085Mpa vacuum condition.
The present invention realizes modifying epoxy resin by organosilicon by a kind of new method.C-OH base dehydrogenative condensations are based on by Si-H
Method, avoid the system jaundice caused by the Si―H addition reaction, high-boiling and low-boiling components content caused by alkoxy hydrolysis, ensure that epoxy
It is worth constant, and post-processing approach is simple.Product is not in the feelings for occurring again polymerizeing or cracking during storage in neutrality
Condition.The generation without toxic gas, waste liquid, waste residue, environmentally friendly in production process.
Embodiment
Embodiment 1：
Bisphenol-A epoxy tree is added in the 500mL four-hole boiling flasks equipped with reflux condensing tube, thermometer and constant pressure funnel
Fat (wherein n=4) 160g, toluene 200g, three (five fluorine) phenylborinane 0.8g, 10~30min is stirred at room temperature, will hold hydrogeneous first
Base phenyl silicone oil (wherein m=90) 40g is slowly added dropwise in system, and after being added dropwise, 30min is stirred at room temperature, then raises temperature to
60 DEG C, in the case where negative pressure is less than 0.5Mpa, 5h is reacted, is finally less than 0.085Mpa in vacuum, toluene is removed under the conditions of 120 DEG C,
Obtain mass ratio m (epoxy)：M (organosilicon)=80:20 modifying epoxy resin by organosilicon (EH-1).
Embodiment 2：
Bisphenol-A epoxy tree is added in the 500mL four-hole boiling flasks equipped with reflux condensing tube, thermometer and constant pressure funnel
Fat (wherein n=4) 140g, toluene 200g, three (five fluorine) phenylborinane 0.8g, 10~30min is stirred at room temperature.Hydrogeneous first will be held
Base phenyl silicone oil (wherein m=90) 60g is slowly added dropwise in system, and after being added dropwise, 30min is stirred at room temperature, then raises temperature to
60 DEG C, in the case where negative pressure is less than 0.5Mpa, 5h is reacted, is finally less than 0.085Mpa in vacuum, is removed under the conditions of 100~120 DEG C
Toluene, obtain mass ratio m (epoxy)：M (organosilicon)=70:30 modifying epoxy resin by organosilicon (EH-2).
Embodiment 3：
Bisphenol-A epoxy tree is added in the 500mL four-hole boiling flasks equipped with reflux condensing tube, thermometer and constant pressure funnel
Fat (wherein n=4) 120g, toluene 200g, three (five fluorine) phenylborinane 0.8g, 10~30min is stirred at room temperature.Hydrogeneous first will be held
Base phenyl silicone oil (wherein m=90) 80g is slowly added dropwise in system, and after being added dropwise, 30min is stirred at room temperature, then raises temperature to
60 DEG C, in the case where negative pressure is less than 0.5Mpa, 5h is reacted, is finally less than 0.085Mpa in vacuum, toluene is removed under the conditions of 120 DEG C,
Obtain mass ratio m (epoxy)：M (organosilicon)=60:40 modifying epoxy resin by organosilicon (EH-3).
Resulting three kinds of modifying epoxy resin by organosilicon EH-1, EH-2, EH-3 are solidified by being necessarily formulated, Gu
Product increasing with organosilicon introducing content after change, its heat resistance gradually steps up.
Presently preferred embodiments of the present invention is the foregoing is only, is not intended to limit the invention scope, it is every in the present invention
Spirit and principle within, any modification, equivalent substitution and improvements done etc. should be included in protection scope of the present invention
Within.
Claims (5)
- A kind of 1. synthetic method of novel organosilicon modified epoxy, it is characterised in that including：(1) bisphenol A epoxide resin and three (five fluorine) phenylborinanes are dissolved in toluene in four-hole boiling flask, at room temperature, stirring 10~30min, resin solution is made；(2) hydrogeneous methyl phenyl silicone oil will be held to be slowly added dropwise in system, after being added dropwise, is warming up to 50~80 DEG C, negative pressure is small In 0.5Mpa, 4~6h is reacted；(3) solvent finally is removed under the conditions of 100~120 DEG C, vacuum condition of the vacuum less than 0.085Mpa, finally gives and contain The epoxy resin that phenyl organic siliconresin is modified；The epoxy resin that the organic siliconresin is modified, its structural formula are：Wherein, m is 80~100 natural number, and n is 3~5 natural number.
- 2. synthetic method according to claim 1, it is characterised in that the structural formula of the bisphenol A epoxide resin is：
- 3. synthetic method according to claim 1, it is characterised in that the hydrogeneous methyl phenyl silicone oil in end is n (Ph):n (CH3)=1, relative molecular mass are 1000~2000 silicone oil, and its structural formula is：
- 4. synthetic method according to claim 1, it is characterised in that in the step (1), resin toluene solution quality point Number is 30~50wt%；In step (1), (2), rotating speed is 100~150 turns/min, the use of catalyst three (five fluorine) phenylborinane Measure as 10~15ppm.
- 5. synthetic method according to claim 1, it is characterised in that bisphenol A epoxide resin is with holding hydrogeneous aminomethyl phenyl silicon The reaction mass ratio of oil is 80:20~60:40.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710938706.6A CN107739441A (en) | 2017-09-30 | 2017-09-30 | A kind of synthetic method of novel organosilicon modified epoxy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710938706.6A CN107739441A (en) | 2017-09-30 | 2017-09-30 | A kind of synthetic method of novel organosilicon modified epoxy |
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| Publication Number | Publication Date |
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| CN107739441A true CN107739441A (en) | 2018-02-27 |
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| CN201710938706.6A Pending CN107739441A (en) | 2017-09-30 | 2017-09-30 | A kind of synthetic method of novel organosilicon modified epoxy |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114262601A (en) * | 2021-12-28 | 2022-04-01 | 烟台德邦科技股份有限公司 | Corrosion-resistant high-adhesion organosilicon sealant |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6355740B1 (en) * | 1999-08-02 | 2002-03-12 | Kukdo Chemical Co., Ltd. | Silicone-modified epoxy resin and its preparing method and silicone-modified epoxy resin composition |
| CN102532556A (en) * | 2011-11-17 | 2012-07-04 | 杭州师范大学 | Chemical method for preparing organic silicon modified epoxy resin |
| CN104788646A (en) * | 2015-04-16 | 2015-07-22 | 广州惠利电子材料有限公司 | Silicone-modified epoxy resin and synthesis method as well as method for alleviating luminous attenuation with silicone-modified epoxy resin |
| CN105176092A (en) * | 2015-10-27 | 2015-12-23 | 巨轮智能装备股份有限公司 | Preparation method for epoxy resin compound organic silicon thermal-insulation material |
-
2017
- 2017-09-30 CN CN201710938706.6A patent/CN107739441A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6355740B1 (en) * | 1999-08-02 | 2002-03-12 | Kukdo Chemical Co., Ltd. | Silicone-modified epoxy resin and its preparing method and silicone-modified epoxy resin composition |
| CN102532556A (en) * | 2011-11-17 | 2012-07-04 | 杭州师范大学 | Chemical method for preparing organic silicon modified epoxy resin |
| CN104788646A (en) * | 2015-04-16 | 2015-07-22 | 广州惠利电子材料有限公司 | Silicone-modified epoxy resin and synthesis method as well as method for alleviating luminous attenuation with silicone-modified epoxy resin |
| CN105176092A (en) * | 2015-10-27 | 2015-12-23 | 巨轮智能装备股份有限公司 | Preparation method for epoxy resin compound organic silicon thermal-insulation material |
Non-Patent Citations (1)
| Title |
|---|
| SCOTT E. LAENGERT等: ""Sequential Functionalization of a Natural Crosslinker Leads to Designer Silicone Networks"", 《CHEMISTRY-AN ASIAN JOURNAL》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114262601A (en) * | 2021-12-28 | 2022-04-01 | 烟台德邦科技股份有限公司 | Corrosion-resistant high-adhesion organosilicon sealant |
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Effective date of registration: 20190203 Address after: 264006 Renewable Resource Processing Demonstration Zone No. 3-21 Kaifeng Road, Yantai Development Zone, Shandong Province Applicant after: Yantai Darbond Technology Co., Ltd. Address before: 264006 Kaifeng Road 3-3 Resource Regeneration and Processing Demonstration Zone, Yantai Development Zone, Shandong Province Applicant before: Yantai Debang Advanced Silicon Materials Co.,Ltd. |
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