CN1432590A - Prepn of phenyl sesquisiloxane prepolymer - Google Patents
Prepn of phenyl sesquisiloxane prepolymer Download PDFInfo
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- CN1432590A CN1432590A CN 02100231 CN02100231A CN1432590A CN 1432590 A CN1432590 A CN 1432590A CN 02100231 CN02100231 CN 02100231 CN 02100231 A CN02100231 A CN 02100231A CN 1432590 A CN1432590 A CN 1432590A
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- phenyl
- prepolymer
- solvent
- sesquisiloxane
- monomer
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Abstract
The present invention relates to a preparation process of phenyl sesquisiloxane prepolymer. Phenyl trioxethyl silane or phynyl silane trichloride momomer, hydrochloric acid, water and solvent in the molar ratio of 1 to 0.03-0.07 to 0.5-3 to 5-20 constituting material liquid are hydrolyzed at 70-90 deg.c to obtain triphenylsilanol, and triphenylsilanol and tetraethyl ammonium hydroxide monomer in the molar ratio of 1 to 0.002-0.006 are polymerized catalytically at 70-90 deg.c to obtain phenyl sesquisiloxane prepolymer. The prepolymer thus prepared has good adhesion performance, high temperature resistance and compatibility with fixing liquid.
Description
Technical field
The invention relates to a kind of preparation method of phenyl sesquisiloxane prepolymer.
Background technology
Polysilsesquioxane is by repeating unit (R-SiO
1.5) constitute, shown in the following structural formula.R wherein can be methyl, ethyl, phenyl or other organic group.
In fact the polysilsesquioxane compounds is meant that oxygen silicon is than the organopolysiloxane that is 1.5 in the structural formula, and the polysilsesquioxane that has ladder structure in this compounds is good thermally-stabilised silicone resin.Be used as the primary insulation material of metal protection material, insulating protective film and unicircuit widely.When using in above-mentioned field, polysilsesquioxane must stand 400 ℃-500 ℃ high temperature, therefore illustrates that this material has high resistance to elevated temperatures, under hot conditions with adhesiveproperties and the wet fastness and the resistance to cracking energy of matrix.
The molecular structure of phenyl sesquisiloxane is mainly based on siloxane bond, and the substituting group phenyl directly combines with Siliciumatom, and its structure is trapezoidal, and end group is a hydroxyl.It can with the metallic substance mortise, have high heat decomposition temperature again.Thermal weight loss in air 500 ℃ the time is less than 1%, and therefore, the phenyl sesquisiloxane polymer is the first-selected material of metal column inside pipe wall mould material.
Technology contents
Up to now, do not see the preparation method of the phenyl sesquisiloxane prepolymer that can be applied to chromatographic grade metal column pipe internal surface
The preparation method who the purpose of this invention is to provide a kind of phenyl sesquisiloxane prepolymer, the phenyl silsesquioxane performed polymer for preparing through this method can be applied to chromatographic grade metal column pipe internal surface.
The preparation method of phenyl sesquisiloxane prepolymer provided by the invention is to be 1 with monomer, hydrochloric acid, water and solvent mol ratio: (0.03-0.07): (0.5-3): after feed liquid (5-20) is that 70-90 ℃ of hydrolysis obtains the phenyl silanetriol, warp is 0.002-0.006 with monomer mole ratio again: 1 tetraethyl ammonium hydroxide obtains oligopolymer at 70-90 ℃ of catalyzed polymerization, said monomer is selected from phenyl triethoxysilane or phenyl-trichloro-silicane, and said solvent is selected from benzene or toluene.
In the preparation performed polymer method provided by the invention, the preferred phenyl triethoxysilane of used monomer is selected for use phenyl-trichloro-silicane also can obtain the reaction intermediate of hydroxyl, but because of the phenyl-trichloro-silicane activity is too strong, is reacted wayward.
In the preparation performed polymer method provided by the invention, the said solvent of water is selected from benzene or toluene, and preferred benzene is solvent.
In the method for preparing performed polymer provided by the invention, the add-on of water can change to some extent, but can only change in measures range, promptly can only must not surpass the metering mol ratio less than metering numerical value, and is preferably reinforced with variable.
In the method for preparing performed polymer provided by the invention, hydrolysis temperature is 70-90 ℃, azeotropic point temperature with solvent and water when hydrolysis begins is optimal selection, after the interface that exists in the question response system disappears, the ethanol of generation in the reaction and not reacted water are steamed, can finish hydrolytic process, in the product that generate this moment, not necessarily simple polymerization precursor phenyl silanol may have the small molecules performed polymer and produce.In this system, add suitable catalyzer and add certain amount of solvent benzene and can carry out further polyreaction.
The phenyl sesquisiloxane prepolymer of method provided by the invention preparation can at room temperature be preserved the long period, can prolonged preservation at low temperature, can be dissolved in acetone, and benzene, ether, methylene dichloride is in the low boiling point organic solvents such as chloroform.
In addition, the phenyl sesquisiloxane prepolymer of the inventive method preparation has following characteristics:
(1) better with the adhesiveproperties of metal species material.For example it is poured into film respectively with 10%, 15%, 20% diluent that is made in acetone on 304 stainless steel substrates and sheet glass, room temperature vapors away behind the solvent in baking oven in 80 ℃ of heating after 1-4 hour, ℃ stopped 1 hour with the heat-up rate temperature programming to 200 of 3 ℃/min, temperature programming to 300 ℃ stop is 1 hour again, final program is warmed up to 400 ℃, stopped 1 hour, make performed polymer aggregate into reticulated structure, forming the silica membrane that one deck organic group is modified on the stainless steel substrates and on the sheet glass respectively.Place microscopically to observe stainless steel substrates and can find this moment, and the smooth light of the film that is coated with is converted into curved shape less than an angle of 90 degrees with this stainless steel substrates, and film does not fall down.
(2) test result of infrared spectra is presented at 1030cm
-1The strong absorption occur, show that the superpolymer that ladder structure is arranged forms; And hot analytical results when being presented at 540 ℃ its thermal weight loss show that less than 5% it has resistance to elevated temperatures.
(3) the prepared performed polymer of the inventive method takes off material alive as the metal column jecket, and the consistency of it and stationary liquid is fine.For example on the film that it is formed during the dichloromethane solution of the stationary liquid of opposed polarities such as drop OV-101, SE-52, OV-275, OV-225, OV-7, find that these stationary liquids can sprawl equably on sheet glass, do not have drop to form.
Embodiment
Below by example the present invention is described, but the present invention is not limited to this.
Example 1
In the 100mL three-necked flask, add phenyl triethoxysilane (Acros company, organics) 62.4mmol and equimolar water and 50mL top grade purified petroleum benzin, add 2.6mmol hydrochloric acid as catalyzer, under 80 ℃ of induction stirring, react 10h, steam the ethanol and the partial solvent of generation then.Tetraethyl-aqua ammonia (Chang Ling catalyst plant) 0.12mL and 50mL in 75 ℃ of addings 30.9% analyze purified petroleum benzin, change reflux into water that distillation limit coronite steams the reaction generation behind 80 ℃ of reaction 3h, obtain the viscosity transparent liquid.Decompression is removed wherein, and solvent is phenyl sesquisiloxane prepolymer.
Example 2
In 100mL three footpath flasks, add water and the 50mL chemistry purified petroleum benzin of phenyl triethoxysilane 62.4mmol and 156mmol, add 4.1mmol hydrochloric acid, under 80 ℃ of induction stirring, react 10h, steam the ethanol and the partial solvent of generation then as catalyzer.Tetraethyl-aqua ammonia 0.08mL and 50mL chemistry purified petroleum benzin in 75 ℃ of addings 30.9% change reflux into water distilling apparatus behind 85 ℃ of reaction 10h and steam the water that reaction generates, and obtain the viscosity transparent liquid.The solvent that decompression is removed wherein is phenyl sesquisiloxane prepolymer.
Example 3
In 100mL three footpath flasks, add water and the 50mL chemistry purified petroleum benzin of phenyl triethoxysilane 62.4mmol and 48.8mmol, add 3.1mmol hydrochloric acid, under 80 ℃ of induction stirring, react 10h, steam the ethanol and the partial solvent of generation then as catalyzer.Tetraethyl-aqua ammonia 0.18mL and 50mL chemistry purified petroleum benzin in 75 ℃ of addings 30.9% change reflux into water distilling apparatus behind 85 ℃ of reaction 10h and steam the water that reaction generates, and obtain the viscosity transparent liquid.The solvent that decompression is removed wherein is phenyl sesquisiloxane prepolymer.
Example 4
The film forming properties of material alive on stainless steel plate taken off in the evaluation of this example.
With top prepared performed polymer at acetone (analytical pure, the Beijing Chemical Plant) weighs % with 10 in, 15 heavy %, the diluent that 20 heavy % are made into pours into film respectively on 304 stainless steel substrates and sheet glass, room temperature heated 4 hours in 80 ℃ in baking oven after vaporing away solvent, ℃ stopped one hour with the heat-up rate temperature programming to 200 of 3 ℃/min, temperature programming to 300 ℃ stop is one hour again, final program is warmed up to 400 ℃, stopped one hour, make performed polymer aggregate into reticulated structure, forming the silica membrane that one deck organic group is modified on the stainless steel substrates and on the sheet glass respectively.Place microscopically to observe stainless steel substrates and can find this moment, the smooth light of the film that is coated with, be converted into curved shape less than an angle of 90 degrees with scribbling the film stainless steel substrates, film does not come off, and illustrates that the adhesiveproperties of superpolymer that this performed polymer generates after last polymerization and metal species material is better.
The thick film that makes on the sheet glass carefully scrapes the test of carrying out infrared spectra and thermography with scraper.Infrared spectra at 1030cm
-1The strong absorption occur, show that last polymerization stage has formed the superpolymer with ladder structure.And the thermal weight loss of prepolymer solution in the time of 594 ℃ that hot analytical results shows example 1 preparation weightlessness 1.2% during less than 13%, 490 ℃; Weightlessness 0.2% when the thermal weight loss after the prepolymer solution film forming of example 2 preparations in the time of 601 ℃ is 13.7%, 488 ℃; Thermal weight loss after the prepolymer solution film forming of example 3 preparation in the time of 560 ℃ weightlessness 0.02% during less than 7%, 465 ℃, more than this material of explanation has high resistance to elevated temperatures.
Example 5
The film that the prepared performed polymer of this example explanation forms and the consistency of high temperature resistant stationary liquid.
All of the present invention's preparation are taken off the dichloromethane solution of material alive stationary liquid of opposed polarities such as drop OV-101, SE-52, OV-275, OV-225, OV-7 on the film that sheet glass is made, find that these stationary liquids can sprawl equably on the film that forms with phenyl methyl polysilsesquioxane material, do not have drop to form.The consistency that this material and these stationary liquids are described is fine.
Claims (3)
1, a kind of preparation method of polysilsesquioxane has following structural formula, and R is-C in the formula
6H
5Phenyl, it is characterized in that with monomer, hydrochloric acid, water and solvent mol ratio be 1: (0.03-0.07): (0.5-3): after feed liquid (5-20) is that 70-90 ℃ of hydrolysis obtains the phenyl silanetriol, warp is 0.002-0.006 with monomer mole ratio again: 1 tetraethyl ammonium hydroxide obtains oligopolymer at 70-90 ℃ of catalyzed polymerization, said monomer is selected from phenyl triethoxysilane or phenyl-trichloro-silicane, and said solvent is selected from benzene or toluene.
2, in accordance with the method for claim 1, it is characterized in that said monomer is a phenyl triethoxysilane.
3, in accordance with the method for claim 1, it is characterized in that said solvent is a benzene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02100231 CN1230463C (en) | 2002-01-10 | 2002-01-10 | Prepn of phenyl sesquisiloxane prepolymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02100231 CN1230463C (en) | 2002-01-10 | 2002-01-10 | Prepn of phenyl sesquisiloxane prepolymer |
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| Publication Number | Publication Date |
|---|---|
| CN1432590A true CN1432590A (en) | 2003-07-30 |
| CN1230463C CN1230463C (en) | 2005-12-07 |
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ID=27627028
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 02100231 Expired - Lifetime CN1230463C (en) | 2002-01-10 | 2002-01-10 | Prepn of phenyl sesquisiloxane prepolymer |
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| CN (1) | CN1230463C (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100396715C (en) * | 2006-04-17 | 2008-06-25 | 广州天赐有机硅科技有限公司 | Branched benzene siliconic oil |
| CN100471897C (en) * | 2006-11-30 | 2009-03-25 | 南京大学 | Preparing method of cage anilino methyl sesquisiloxane octamer |
| CN100532432C (en) * | 2004-04-12 | 2009-08-26 | 陶氏康宁公司 | Silsesquioxane resin wax |
| CN101072896B (en) * | 2004-12-17 | 2010-05-05 | 陶氏康宁公司 | Method for forming anti-reflective coating |
| CN101665571B (en) * | 2009-10-18 | 2012-04-11 | 山东宏艺科技股份有限公司 | Polyphenyl methylsiloxane modified epoxy resin and manufacturing method of high performance electronic packaging material thereof |
| CN102532187A (en) * | 2011-12-15 | 2012-07-04 | 北京理工大学 | Method for preparing octaphenyl polyhedral oligomeric silsesquioxane |
| CN103435806A (en) * | 2013-07-17 | 2013-12-11 | 烟台德邦先进硅材料有限公司 | Branched chain type phenyl silicone oil and preparation methods thereof |
| CN107349792A (en) * | 2016-05-10 | 2017-11-17 | 中国科学院宁波材料技术与工程研究所 | One kind regeneration membrane module and its manufacture method |
| CN111636240A (en) * | 2020-06-05 | 2020-09-08 | 西南大学 | Preparation method of phenyl-polysilsesquioxane modified meta-aramid insulation paper |
-
2002
- 2002-01-10 CN CN 02100231 patent/CN1230463C/en not_active Expired - Lifetime
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100532432C (en) * | 2004-04-12 | 2009-08-26 | 陶氏康宁公司 | Silsesquioxane resin wax |
| CN101072896B (en) * | 2004-12-17 | 2010-05-05 | 陶氏康宁公司 | Method for forming anti-reflective coating |
| CN100396715C (en) * | 2006-04-17 | 2008-06-25 | 广州天赐有机硅科技有限公司 | Branched benzene siliconic oil |
| CN100471897C (en) * | 2006-11-30 | 2009-03-25 | 南京大学 | Preparing method of cage anilino methyl sesquisiloxane octamer |
| CN101665571B (en) * | 2009-10-18 | 2012-04-11 | 山东宏艺科技股份有限公司 | Polyphenyl methylsiloxane modified epoxy resin and manufacturing method of high performance electronic packaging material thereof |
| CN102532187A (en) * | 2011-12-15 | 2012-07-04 | 北京理工大学 | Method for preparing octaphenyl polyhedral oligomeric silsesquioxane |
| CN103435806A (en) * | 2013-07-17 | 2013-12-11 | 烟台德邦先进硅材料有限公司 | Branched chain type phenyl silicone oil and preparation methods thereof |
| CN103435806B (en) * | 2013-07-17 | 2015-09-02 | 烟台德邦先进硅材料有限公司 | A kind of branched chain type phenyl silicone oil and preparation method thereof |
| CN107349792A (en) * | 2016-05-10 | 2017-11-17 | 中国科学院宁波材料技术与工程研究所 | One kind regeneration membrane module and its manufacture method |
| CN107349792B (en) * | 2016-05-10 | 2019-12-17 | 中国科学院宁波材料技术与工程研究所 | regenerated film device and manufacturing method thereof |
| CN111636240A (en) * | 2020-06-05 | 2020-09-08 | 西南大学 | Preparation method of phenyl-polysilsesquioxane modified meta-aramid insulation paper |
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| Publication number | Publication date |
|---|---|
| CN1230463C (en) | 2005-12-07 |
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Granted publication date: 20051207 |