CN100396714C - Synthesis of organosilicon resin - Google Patents
Synthesis of organosilicon resin Download PDFInfo
- Publication number
- CN100396714C CN100396714C CNB2006100203618A CN200610020361A CN100396714C CN 100396714 C CN100396714 C CN 100396714C CN B2006100203618 A CNB2006100203618 A CN B2006100203618A CN 200610020361 A CN200610020361 A CN 200610020361A CN 100396714 C CN100396714 C CN 100396714C
- Authority
- CN
- China
- Prior art keywords
- raw material
- starting raw
- synthetic method
- silicone resin
- mixture
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Silicon Polymers (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
The present invention relates to a synthesis method of organosilicon resin. At least one alkyl tri-alkoxy silane with a structure general formula of RSi(OR1)3 is used as an initial raw material, wherein R represents a one-valent alkyl group, a one-valent aryl gorup, a one-valent unsaturated group, etc., and R1 represents an alkyl group with the carbon number of 1 to 4. Compounding ratio is determined by the raw material according to an R/Si value of 0.7 to 1.5, and meanwhile, water, low-pole or non-pole solvents and 0.1N of hydrochloric acid are added. The mixture can reflow for 1 to 6 hours at a temperature of 60 to 100 DEG C by mixing, and the mixture is secondly and continuously mixed for 0.5 hours without heating. The temperature of the mixture is subsequently raised to 65 to 130 DEG C, the reaction can be stopped after 40 to 120 minutes of maturing, and then the mixture is cooled so as to obtain a colorless transparent uniform organosilicon resin solution. The synthesis method can not generate HCl, corrode devices or pollute environment, and the synthesis method satisfies the special application requirements of coating or impregnating silicon resin solutions with a low water content or a zero water content.
Description
Technical field
The present invention relates to the preparation method of silicone resin, particularly, the present invention relates to a kind of synthetic method that can be dissolved in the silicon resin solution of toluene and so on low-pole or non-polar solvent.
Background technology
In some special application scenario, as when requiring to control the goods low-dielectric loss, need carry out special moistureproof coating processing to article interface.When using silicone resin solution as coating or matrix material steeping fluid, requirement can not be brought moisture content into, and therefore, the silicon resin solution of polar solvent is not allowed to such as ethanol.And in the present existing silicone resin synthetic method, be raw material synthetic silicon resin solution with organoalkoxysilane such as Union carbide A-162, phenyl triethoxysilane etc., all be solvent with ethanol.Because the organoalkoxysilane hydrolysis just directly produces ethanol, and the silicone resin that generates is dissolved in the corresponding solution of formation in the ethanol fully.The synthetic silicone resin can not be dissolved in toluene and so on low-pole or the non-polar solvent less than 1.5 o'clock in the R/Si value like this.Layering will occur when adding toluene, silicone resin can't enter in the toluene layer.
In known synthetic method, though can make chlorosilane such as METHYL TRICHLORO SILANE, phenyl-trichloro-silicane etc., the toluene solution of hydrolysis synthetic silicone resin in toluene, but this method can produce a large amount of hydrogenchloride, bring thus to the deep-etching effect of equipment with to the pollution problem of environment, make this method in small-scale production is used, be subjected to certain restriction.
Summary of the invention
The present invention is intended to overcome above-mentioned defective, and providing a kind of is raw material with the organoalkoxysilane, and direct hydrolysis is synthesized the method for the silicone resin solution that is dissolved in weak (non-) polar solvents such as toluene under the acid catalysis effect.
The objective of the invention is that following technical scheme realizes by implementing:
A kind of synthetic method of silicone resin is characterized in that: this synthetic method comprises that selecting to have at least a kind of is by general structure RSi (OR
1)
3The alkyl trialkoxy silane of expression is as starting raw material, in the described starting raw material or to include general structure be R
2Si (OR
1)
2Dialkyl dialkoxy silicane and/or general structure be Si (OR
1)
4Positive silicon ester, wherein, R represents univalent alkyl, monovalence aryl or monovalence unsaturated group etc., R
1Representing carbonatoms is 1～4 alkyl;
Above-mentioned starting raw material is 0.7～1.5 definite proportioning by silicone resin R/Si value, be incorporated as the water of 1～4 times of starting raw material mole number summation simultaneously, low-pole or non-polar solvent for 0.5～5 times of starting raw material gross weight, and the aforementioned 0.1N hydrochloric acid that adds material gross weight 3～20ppm, under agitation refluxed 1～6 hour in 60～100 ℃, be incorporated as the hexamethyldisilazane of 0～40 times of hydrochloric acid equivalents then, stop heating and continue stirring 0.5 hour, be warming up to 65～130 ℃ once more, slaking is stopped reaction after 40～120 minutes, cool off, promptly get the silicone resin solution of water white transparency homogeneous.
Described alkyl trialkoxy silane comprises Union carbide A-162, phenyl triethoxysilane or vinyltriethoxysilane etc.
Described dialkyl dialkoxy silicane comprises dimethyldiethoxysilane, dimethyldimethoxysil,ne, phenylbenzene diethoxy silane or aminomethyl phenyl diethoxy silane etc.
Described positive silicon ester comprises positive tetraethyl orthosilicate, positive quanmethyl silicate or positive silicic acid orthocarbonate etc.
Described low-pole or non-polar solvent comprise benzene,toluene,xylene, chlorobenzene, sherwood oil, lower paraffin hydrocarbons, naphthenic hydrocarbon or halohydrocarbon etc.
Described positive silicon ester comprises positive tetraethyl orthosilicate, positive quanmethyl silicate or positive silicic acid orthocarbonate etc.
Reflux technique of the present invention is that hydrolyzable alkoxy TMOS and/or general structure are Si (OR
1)
4Positive silicon ester, and balanced reaction generates the polymerization degree of silicone resin molecule; And the purpose of curing process is to steam ethanol, and improves the molecular weight of silicone resin simultaneously.
The invention has the advantages that:
1, the present invention is to be Si (OR with organoalkoxysilane and/or general structure
1)
4Positive silicon ester be raw material, direct hydrolysis is synthesized the silicone resin solution that is dissolved in weak (non-) polar solvents such as toluene under the acid catalysis effect, not only solved the solubility problem of synthetic silicone resin in weak (non-) polar solvent, also overcome silicon resin solution is brought moisture content into because of polar solvent problem simultaneously, some special occasions have been satisfied, as the application requiring of needs with low moisture or not moisture silicon resin solution coating or dipping.
2, the present invention adopts the organoalkoxysilane hydrolysis to prepare silicone resin, does not produce hydrogenchloride, can not cause equipment corrosion and problem of environmental pollution.
3, weak (non-) the polarity silicon resin solution of institute of the present invention synthetic with other a little less than (non-) polarity organic resin do not have the intermiscibility problem when carrying out cold assembly.
4, the convenient control easily of synthetic method of the present invention, the silicone resin that makes is the solution of clear homogeneous, its good stability does not stratifiedly precipitate yet, and is easy to preserve.
Embodiment
Below listed embodiment and comparative example only be the more detailed specific description of the present invention, data shown in it are not represented the restriction to characteristic range of the present invention.
Embodiment 1
With 1555g Union carbide A-162 and 780g tetraethoxy is starting raw material, add 520g water, 7g0.1N hydrochloric acid and 800g toluene, be warming up to 77 ℃ under stirring, keep refluxing 3.5 hours, under uniform temp, steam ethanol 845g then, slaking is stopped reaction after 1 hour, promptly gets the water white transparency silicon resin solution after adding toluene 45g.Resin R/Si value is 0.7.
Embodiment 2
With 534g Union carbide A-162 and 49g dimethyldiethoxysilane is starting raw material, add 222g water, 1.94g0.1N hydrochloric acid and 900g toluene, be warming up to 74～79 ℃ under stirring, keep to reflux 6 hours, and added the about 1g of hexamethyldisilazane then, stop heating and lasting stir about and be warming up to 74～89 ℃ after half an hour again and steam ethanol and part solvent, slaking is stopped reaction after 40 minutes, cooling gets water white transparency silicon resin solution 570g, and resin R/Si value is 1.1.
Embodiment 3
With 1753g Union carbide A-162 and 364g dimethyldiethoxysilane is starting raw material, add 620g water, 4.87g0.1N hydrochloric acid and 1058g toluene, be warming up to 74～79 ℃ under stirring, keep refluxing 4.5 hours, add the about 2.6g of hexamethyldisilazane then, stopping heating and lasting stir about is warming up to 75～116 ℃ again and steams ethanol and solvent partly after half an hour, slaking is stopped reaction after 2 hours, cooling, get water white transparency silicon resin solution 1940g after adding 1000g toluene, resin R/Si value is 1.2.
Embodiment 4
With the 712g Union carbide A-162 is starting raw material, add 234g water, 2.2g0.1N hydrochloric acid and 900g toluene, be warming up to 74～78 ℃ under stirring, keep to reflux 6 hours, and added the about 1.28g of hexamethyldisilazane then, stop heating and lasting stir about and be warming up to 75～89 ℃ after half an hour again and steam ethanol and part solvent, slaking is stopped reaction after 1.5 hours, cooling gets water white transparency silicon resin solution 565g, and resin R/Si value is 1.0.
Embodiment 5
With 640g Union carbide A-162 and 96g phenyl triethoxysilane is starting raw material, add 234g water, 2.2g0.1N hydrochloric acid and 900g toluene, be warming up to 74～80 ℃ under stirring, keep to reflux 6 hours, and added the about 1.2g of hexamethyldisilazane then, stop heating and lasting stir about and be warming up to 75～100 ℃ after half an hour again and steam ethanol and part solvent, slaking is stopped reaction after 2 hours, cooling gets water white transparency silicon resin solution 790g, and resin R/Si value is 1.0.
Embodiment 6
With 408g methyltrimethoxy silane and 40g dimethyldimethoxysil,ne is starting raw material, add 174g water, 1.8g0.1N hydrochloric acid and 700g sherwood oil (90～120 ℃ of boiling ranges), be warming up to 60～70 ℃ under stirring, keep refluxing 6 hours, add the about 0.5g of hexamethyldisilazane then, stopping heating and lasting stir about is warming up to 64～79 ℃ again and steams ethanol and solvent partly after half an hour, slaking is stopped reaction after 2 hours, cooling, get water white transparency silicon resin solution 590g, resin R/Si value is 1.1.
Reference examples 1
According to the synthetic method of embodiment 3, do not add toluene when feeding intake first, after reaction was finished, muddiness, stratified phenomenon appearred when adding toluene, can not obtain the resin solution of transparent homogeneous.
Claims (4)
1. the synthetic method of a silicone resin is characterized in that: this synthetic method comprises that selecting to have at least a kind of is by general structure RSi (OR
1)
3The alkyl trialkoxy silane of expression is as starting raw material, and including general structure in the described starting raw material is R
2Si (OR
1)
2Dialkyl dialkoxy silicane and/or general structure be Si (OR
1)
4Positive silicon ester, wherein, R represents univalent alkyl, monovalence aryl or monovalence unsaturated group, R
1Representing carbonatoms is 1～4 alkyl;
Above-mentioned starting raw material is 0.7～1.5 definite proportioning by silicone resin R/Si value, be incorporated as the water of 1～4 times of starting raw material mole number summation simultaneously, benzene for 0.5～5 times of starting raw material gross weight, toluene, dimethylbenzene, chlorobenzene, sherwood oil, lower paraffin hydrocarbons, naphthenic hydrocarbon or halohydrocarbon, and the aforementioned 0.1N hydrochloric acid that adds material gross weight 3～20ppm, under agitation refluxed 1～6 hour in 60～100 ℃, be incorporated as the hexamethyldisilazane of 0～40 times of hydrochloric acid equivalents then, stop heating and continue stirring 0.5 hour, be warming up to 65～130 ℃ once more, slaking is stopped reaction after 40～120 minutes, cool off, promptly get the silicone resin solution of water white transparency homogeneous.
2. synthetic method as claimed in claim 1 is characterized in that: described alkyl trialkoxy silane is selected from Union carbide A-162, phenyl triethoxysilane or vinyltriethoxysilane.
3. synthetic method as claimed in claim 1 is characterized in that: described dialkyl dialkoxy silicane is selected from dimethyldiethoxysilane, dimethyldimethoxysil,ne, phenylbenzene diethoxy silane or aminomethyl phenyl diethoxy silane.
4. synthetic method as claimed in claim 1 is characterized in that: described positive silicon ester is selected from positive tetraethyl orthosilicate, positive quanmethyl silicate or positive silicic acid orthocarbonate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100203618A CN100396714C (en) | 2006-02-27 | 2006-02-27 | Synthesis of organosilicon resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100203618A CN100396714C (en) | 2006-02-27 | 2006-02-27 | Synthesis of organosilicon resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1810858A CN1810858A (en) | 2006-08-02 |
| CN100396714C true CN100396714C (en) | 2008-06-25 |
Family
ID=36843990
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006100203618A Active CN100396714C (en) | 2006-02-27 | 2006-02-27 | Synthesis of organosilicon resin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100396714C (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101704953B (en) * | 2009-11-23 | 2011-10-26 | 株洲时代电气绝缘有限责任公司 | Synthesis method of organic silicon resin containing OH groups |
| CN103059306B (en) * | 2011-10-18 | 2015-02-18 | 北京化工大学 | High-refractive index transparent silicone resin and preparation method thereof |
| CN103804691B (en) * | 2012-11-05 | 2016-08-03 | 上海树脂厂有限公司 | The preparation method of toughness reinforcing high-temperature-resistant silicon resin |
| CN105585713A (en) * | 2016-03-23 | 2016-05-18 | 衢州市璀璨化工有限公司 | Method for preparing alcohol-solubility methyl silicone resin |
| CN106047158B (en) * | 2016-07-13 | 2018-06-26 | 山东省地质科学研究院 | A kind of dinosaur fossil efflorescence prevention material and preparation method thereof |
| CN107936254A (en) * | 2017-11-24 | 2018-04-20 | 李伟文 | LED chip bonds the synthetic method with organosilicon Special Resin |
| WO2020019277A1 (en) * | 2018-07-27 | 2020-01-30 | 湖州五爻硅基材料研究院有限公司 | Method for preparing spherical powder filler, spherical powder filler prepared thereby and application thereof |
| CN114188092B (en) * | 2021-12-02 | 2022-06-28 | 浙江荣泰电工器材股份有限公司 | Processing technology of special-shaped mica insulation product |
| CN116589682B (en) * | 2023-07-13 | 2023-10-03 | 哈尔滨工业大学 | Preparation method and application of silicone resin suitable for hot-melt presoaking |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5527873A (en) * | 1994-02-18 | 1996-06-18 | Dow Corning Toray Silicone Co., Ltd. | Method for the preparation of silicone resins |
| CN1114070C (en) * | 1998-06-29 | 2003-07-09 | 周承禧 | Energy-saving air interchanger |
| WO2004072149A1 (en) * | 2003-02-05 | 2004-08-26 | Rhodia Chimie | Method for the production of polymethylvinylsiloxane resins with recycling of volatile oligoorganosiloxanes |
| CN1683467A (en) * | 2005-03-03 | 2005-10-19 | 武汉理工大学 | Water-proof and oil-repelling agent of colorless organic silicon resin for asphalt road surface |
| CN1227312C (en) * | 2000-02-28 | 2005-11-16 | 阿德西尔公司 | Silane-based coating compositions, coated articles obtained therefrom and methods of using same |
-
2006
- 2006-02-27 CN CNB2006100203618A patent/CN100396714C/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5527873A (en) * | 1994-02-18 | 1996-06-18 | Dow Corning Toray Silicone Co., Ltd. | Method for the preparation of silicone resins |
| CN1114070C (en) * | 1998-06-29 | 2003-07-09 | 周承禧 | Energy-saving air interchanger |
| CN1227312C (en) * | 2000-02-28 | 2005-11-16 | 阿德西尔公司 | Silane-based coating compositions, coated articles obtained therefrom and methods of using same |
| WO2004072149A1 (en) * | 2003-02-05 | 2004-08-26 | Rhodia Chimie | Method for the production of polymethylvinylsiloxane resins with recycling of volatile oligoorganosiloxanes |
| CN1683467A (en) * | 2005-03-03 | 2005-10-19 | 武汉理工大学 | Water-proof and oil-repelling agent of colorless organic silicon resin for asphalt road surface |
Non-Patent Citations (4)
| Title |
|---|
| 有机硅硬质涂料的制备. 邵月刚.有机硅材料，第18卷第3期. 2004 |
| 有机硅硬质涂料的制备. 邵月刚.有机硅材料，第18卷第3期. 2004 * |
| 硅聚合物耐热耐水涂料. 孔荣贵.塑料工业，第2期. 1995 |
| 硅聚合物耐热耐水涂料. 孔荣贵.塑料工业，第2期. 1995 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1810858A (en) | 2006-08-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100396714C (en) | Synthesis of organosilicon resin | |
| CN102212246B (en) | Epoxy composition and manufacture method thereof for optical semiconductor sealing, and hardening thing | |
| US2398672A (en) | Method of preparing organopolysiloxanes | |
| CN103087556B (en) | Surface treatment method and application of heat-conducting packing | |
| KR101125845B1 (en) | SILICONE BASED TWO LIQUID TYPE ORGANIC·INORGANIC HYBRID COATINGS AND MANUFACTURAL METHODS | |
| CN105906810A (en) | Preparation method of organopolysiloxane resin | |
| CN103819679B (en) | A kind of preparation method of one pack system POSS/ add-on type silicones nano composite material | |
| US5051467A (en) | Silicone rubber compositions | |
| US4929691A (en) | Liquid silicone resin compositions | |
| CN109642079A (en) | Dealcoholized cold curing organopolysiloxane composition and the article sealed with the solidfied material of the composition | |
| WO2012094450A1 (en) | Polyheterosiloxanes for high refractive index materials | |
| CN106554500A (en) | A kind of hydrophobically modified epoxy resin and preparation method thereof | |
| US2698314A (en) | Reaction of alkoxy silanes with silane hydrolysis products | |
| CN105348899B (en) | A kind of coupling agent | |
| CN103145992A (en) | Vinyl silicon material as well as preparation method and application of vinyl silicon material in preparation of solventless insulating paint of high-temperature motor | |
| US5166293A (en) | Silicone rubber compositions and cured products thereof | |
| CN105968325A (en) | Organosilicone modified polyester epoxy resin with high temperature yellowing resistance | |
| US4141926A (en) | Method for preparing epoxy-modified silicon resins | |
| CN102675648A (en) | High-temperature resistant zirconium silicon resin containing zirconium in frame structure and preparation method thereof | |
| US4085084A (en) | Silicone resins having good thermal stability | |
| CN103450481A (en) | Preparation method of methyl phenyl vinyl silicone | |
| US2562953A (en) | Organo-silicon copolymers and process of making same | |
| CN111019138A (en) | Preparation method and application of acrylic acid and polyester modified organic silicon resin | |
| CN101872832A (en) | Packaging material applied to light-emitting diode (LED) and preparation method and using method thereof | |
| CN101463223B (en) | Epoxy enhanced tough organosilicon coating |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Owner name: BLUE STAR (CHENGDU) NEW MATERIALS CO., LTD. Free format text: FORMER OWNER: ZHONGLAN CHENGUANG CHEMICAL INST. Effective date: 20100818 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| COR | Change of bibliographic data |
Free format text: CORRECT: ADDRESS; FROM: 610041 NO.30, SECTION 4 OF RENMIN SOUTH ROAD, CHENGDU CITY, SICHUAN PROVINCE TO: 611430 AREA B, XINJIN INDUSTRIAL PARK, CHENGDU CITY, SICHUAN PROVINCE |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20100818 Address after: 611430 B District, Xinjin Industrial Park, Sichuan, Chengdu Patentee after: LAN-STAR (Chengdu) new material Co., Ltd. Address before: 610041 No. four, South Renmin Road, Sichuan, Chengdu province 30 Patentee before: Zhonglan Chenguang Chemical Inst. |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20190801 Address after: 610000 No. 30, 4th Section of Renmin South Road, Chengdu City, Sichuan Province Patentee after: China Bluestar Chengrand Research Institute of Chemical Industry Co., Ltd. Address before: 611430 B District, Xinjin Industrial Park, Sichuan, Chengdu Patentee before: LAN-STAR (Chengdu) new material Co., Ltd. |
|
| TR01 | Transfer of patent right |