CN1032947A - The preparation method of modified room-temperature-cured silicone rubber - Google Patents
The preparation method of modified room-temperature-cured silicone rubber Download PDFInfo
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- CN1032947A CN1032947A CN 88105519 CN88105519A CN1032947A CN 1032947 A CN1032947 A CN 1032947A CN 88105519 CN88105519 CN 88105519 CN 88105519 A CN88105519 A CN 88105519A CN 1032947 A CN1032947 A CN 1032947A
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Abstract
The preparation method of modified room-temperature-cured silicone rubber of the present invention, it is the polymkeric substance trimethylsilyl polysilicates that the part trimethylsilyl by positive silicon ester partial hydrolysis and hydrolyzate thereof forms, control its molecular weight, get molecular weight less than 1500 fraction or full fraction, with end group is that the polydialkysiloxane of hydroxyl mixes, add catalyzer, be solidified into high transparent or opaque modified silicon rubber.This glue has advantageous properties such as high strength, high rigidity, weathering resistance and non-corrosiveness, is photosensor ideal joint sealant, also can be used as the insulation-encapsulated material of electric elements.
Description
The present invention is the preparation method who belongs to silicon rubber.Further saying, is the preparation method about modified room-temperature-cured silicone rubber.It is the trimethylsilyl polysilicates that the part trimethylsilyl by positive silicon ester partial hydrolysis and hydrolyzate thereof forms, control reaction product molecular weight, get its molecular weight less than 1500 fraction or get its full fraction, is it and end group that the polydialkysiloxane of hydroxyl is mixed, add catalyzer, form high transparent or opaque modified silicon rubber in self-vulcanizing (i.e. sulfuration).
Modified silicon rubber is applicable to the joint sealant of making photosensor, also can be used for the insulation-encapsulated of wireless, electric elements, semiconductor element or high-voltage power supply transformer, the coated of intensive element circuitry plate, papery adhesive tape release agent, releasing agent and binding agent etc.
The preparation method of room temperature vulcanized silicone rubber reports a lot.According to United States Patent (USP) (us 2857356), positive silicon ester and trimethylchlorosilane are under hydrochloric acid catalysis, carrying out all-hydrolytic and prepare trimethylsilyl resinous copolymeric siloxane thing, is that mixed curing of high molecular line style polydialkysiloxane of hydroxyl forms silicon rubber with it and end group.Again according to United States Patent (USP) (us 4490500), in trimethylsilyl resinous copolymeric siloxane thing and polydialkysiloxane mixture, add catalyzer and carry out crosslinking reaction as the autohension additive and prepare silicon rubber with the silane of amino-contained.Because trimethylsilyl resinous copolymeric siloxane thing is the all-hydrolytic product, the molecular weight height, resin product must be preserved with solvent cut resin solution, to avoid taking place gelatin phenomenon, therefore will use a large amount of solvents, and toxicity is big.Desolvate when further adding need remove again man-hour, complex process, and make additive with the silane of amino-contained, equipment is corrosive.
The present invention seeks to silicon rubber is carried out modification, it is simple to seek a technology, and non-corrosiveness has the preparation method of the modified room-temperature-cured silicone rubber of advantageous properties such as higher transparency, intensity, hardness, photostabilization and water tolerance than silicon rubber.
The preparation method of modified room-temperature-cured silicone rubber of the present invention comprises synthetic trimethylsilyl polysilicates and to be that the polydialkysiloxane of hydroxyl is mixed with end group solidify two parts.
Synthetic trimethylsilyl polysilicates of the present invention is that partly hydrolysis and hydrolyzate thereof carry out part trimethylsilyl with silylation reagent and form the trimethylsilyl polysilicates (basic and (CH of OR wherein by positive silicon ester
3)
3SiO
The mol ratio of base is 3-6), control reaction product molecular weight is got its molecular weight less than 1500 fraction or get its full fraction, as a component of modified room-temperature-cured silicone rubber preparation.
Positive silicon ester molecular formula is si(OR)
4, wherein R is an alkyl, the best is an ethyl.Silylation reagent can be hexamethyldisiloxane.
Water droplet is added to contains positive silicon ester of monomer and hexamethyldisiloxane, in the mixing solutions of hydrolyst storng-acid cation exchange resin (exchange capacity＞4 milligramequivalent/grams) and solvent, under agitation be hydrolyzed.Temperature of reaction is 20-80 ℃, stirred 10-40 hour, cooling, remove by filter Zeo-karb, distillation removes desolvates and low-boiling-point substance, directly gets the full fraction of residue in the bottle, or can further reduce pressure steam molecular weight less than 1500 polymkeric substance fraction, promptly be the trimethylsilyl polysilicates, its viscosity is the 1-50 centipoise.
The mole ratio of two reactant monomer hexamethyldisiloxanes and positive silicon ester is 0.1-2, and amount of water is 0.1-1.8 with the mole ratio of positive silicon ester.
Reaction solvent can adopt the benzene class, as benzene,toluene,xylene, and alcohols, as methyl alcohol, ethanol, propyl alcohol, Virahol, the ester class is as vinyl acetic monomer, N-BUTYL ACETATE, ethers etc.
In synthetic trimethylsilyl polysilicates reaction, under the mol ratio situation of above-mentioned two reactant monomer, regulate the consumption of solvent and hydrolyst storng-acid cation exchange resin, may command molecular weight of product component.Select appropriate consumption, can make molecular weight obtain the yield of satisfaction less than 1500 product.When solvent and two monomer sum weight ratios are 0.05-1, when the weight ratio of storng-acid cation exchange resin and two monomer sums was 0.05-0.70, molecular weight reached 40-80% less than 1500 trimethylsilyl polysilicates yield.
Trimethylsilyl polysilicates of the present invention is the partial hydrolysate by positive silicon ester, adopt neutral silylation reagent hexamethyldisiloxane and cation exchange resin as catalyst, thereby must be as doing to remove acid treatment with tart silylation reagent or with the acid as catalyst situation, just directly can obtain neutral trimethylsilyl polysilicates, technology is simple, product is stable, does not need other solubilizing agent dilution during storage.The room temperature storage phase reached more than 2 years.
The trimethylsilyl polysilicates is that end group is the effective interlinkage toughener of polydialkysiloxane of hydroxyl.Trimethylsilyl polysilicates of the present invention and end group are that the mixed curing of the polydialkysiloxane of hydroxyl is, (viscosity is the 100-15000 centipoise 25 ℃ the time with 10-90 part molecular weight polydialkysiloxane that is hydroxyl less than 1500 trimethylsilyl polysilicates and 100 parts of end groups, alkyl the best is a methyl) mixed, add 0.3-2 part metallic salt, the for example octylate of lead, zinc, zirconium, antimony, cadmium, tin, barium, calcium, lauroleate, acetate, hexanoate etc. or amine, for example polyethylene polyamine, quadrol etc. are as catalyzer.At room temperature placed two hours, surface skining can be solidified into high transparent modified silicon rubber, and heat and can quicken its curing in 1-3 days.This glue has high light transmittance, and its transmittance reaches 94-95%(c φ-10 spectrophotometric determination, wavelength region 400-750nm).Also have tensile strength and the hardness more than 1 times doubly, improve photostabilization and the water tolerance of 15-25% than the high 5-9 of original silicon rubber.(4 * 4cm) apart from 15 centimetres of 300w mercury lamps, and after 500 hours irradiation (being equivalent at 1.5 years at sunshine), sample glue transmittance still has 85-90%, and embrittlement does not chap for one pat glue.In addition, viscosity also has decline significantly, also has the surface of good slickness, thereby dustproof effect is preferably arranged.Good levelling property and processing performance are arranged, non-corrosiveness, metallic glass etc. there is sticking power preferably, therefore this high transparent silicon rubber is photosensor ideal joint sealant, as be used for the face seal glue of photosensors such as Cadmium Sulfide silicon photocell, also can be used for the sealing of long-term exposure between the solar cell under the strong sunlight and its cover glass sheet.
Along with trimethylsilyl polysilicates add-on increases, the tensile strength and the hardness of high transparent silicon rubber also increase, when add-on reaches 90% when above of polydialkysiloxane, the tensile strength of high transparent silicon rubber descends on the contrary, glue takes place obviously to shrink simultaneously, therefore trimethylsilyl polysilicates add-on adopts 10-90%, can get high strength, high transparent modified silicon rubber.
Also can adopt the trimethylsilyl polysilicates and the polydialkysiloxane that end group is hydroxyl of full fraction of same proportioning mixed, add catalyzer, self-vulcanizing becomes opaque glue, the intensity of the more above-mentioned high transparent adhesive tape of its intensity is poor slightly, but doubly than the still high 4-5 of original silicon rubber, and surface flatness is good, can be used for the coated of intensive element circuitry plate, but and toolability is arranged.Owing to adopt the full fraction of trimethylsilyl polysilicates, can save one step of distillation, so technology is simpler, cost is also lower.
Modified room-temperature-cured silicone rubber of the present invention had both kept elasticity, temperature tolerance and the insulativity of original silicon rubber, also have high light transmittance, weathering resistance, high strength and high rigidity, have good levelling property and manufacturability, surface of good slickness, non-corrosiveness, glass and metal there is good sticking power, thereby be photosensor ideal joint sealant, substitute the complicated technology that the original joint sealant that adopts adds cover glass, it is simple to have technology, easy and simple to handle, reduce cost and advantage such as weight reduction.
In order to understand the present invention better, now be exemplified below:
Example 1
18 gram water are splashed into by 208 gram tetraethoxys, 162 gram hexamethyldisiloxanes, 200 gram strongly acidic styrenes are in the mixing solutions of 732 type Zeo-karbs (exchange capacity 5.2 milligramequivalent/grams) and 200 gram ethanol compositions, stirred 14 hours in 50 ℃, cooling, leach Zeo-karb, steaming desolventizes and low-boiling-point substance.In 1-2 mmhg decompression down, steam molecular weight, be the trimethylsilyl ethyl polysilicate less than 1500 fraction.
20 parts of trimethylsilyl ethyl polysilicates and the 100 parts of end groups polydimethylsiloxane that is hydroxyl (viscosity 25 ℃ time be the 100-15000 centipoise) is mixed, add 1 part of dibutyl tin laurate, be poured into the photosensor surface after stirring evenly, placed one day, can be solidified into high transparent adhesive tape.
Example 2
18 gram water are splashed into by 208 gram tetraethoxys, 312 gram hexamethyldisiloxanes, 200 gram strongly acidic styrenes are in the mixing solutions of 732 type Zeo-karbs (exchange capacity 5.2 milligramequivalent/grams) and 200 gram toluene, in 60 ℃ of stirrings 10 hours, cooling leached Zeo-karb, steaming desolventizes and low-boiling-point substance, in 1-2 mmhg decompression down, steam molecular weight, be the trimethylsilyl ethyl polysilicate less than 1500 fraction.
70 parts of trimethylsilyl ethyl polysilicates and the 100 parts of end groups polydimethylsiloxane that is hydroxyl (viscosity 25 ℃ time be the 100-15000 centipoise) is mixed, add 1 part of zinc octoate, after stirring evenly, be poured into the photosensor surface, placed one day, and can be solidified into high transparent adhesive tape.
Example 3
23 gram water are splashed into by 208 gram tetraethoxys, 160 gram hexamethyldisiloxanes, 120 gram strongly acidic styrenes are in the mixing solutions of 732 type Zeo-karbs (exchange capacity 5.2 milligramequivalent/grams) and 200 gram N-BUTYL ACETATEs, stirred 20 hours in 70 ℃, cooling leaches Zeo-karb, steams to desolventize and low-boiling-point substance, get the full fraction of residue in its bottle, be the trimethylsilyl ethyl polysilicate.
80 parts of trimethylsilyl ethyl polysilicates and the 100 parts of end groups polydimethylsiloxane that is hydroxyl (viscosity 25 ℃ time be the 100-15000 centipoise) is mixed, add 0.3 part of triethylene tetramine, after stirring evenly, be cast in the electric elements surface, placed one day, and can be solidified into opaque glue.
Claims (9)
1, a kind of preparation method of modified room-temperature-cured silicone rubber is characterized in that following three kinds of components are mixed, in self-vulcanizing:
A.10-90 part trimethylsilyl polysilicates, it is to carry out the polymkeric substance that the part trimethylsilyl forms by positive silicon ester partial hydrolysis and hydrolyzate thereof with silylation reagent, control the molecular weight of its reaction product, get its molecular weight less than 1500 fraction or get its full fraction
The molecular formula of positive silicon ester is Si (OR)
4, wherein R is an alkyl, the best is an ethyl,
B.100 a part end group is the polydialkysiloxane (viscosity is the 100-15000 centipoise in the time of 25 ℃) of hydroxyl, and alkyl the best is a methyl.
C.0.3-2 part catalyzer, the octylate of lead, zinc, zirconium, antimony, cadmium, tin, barium, calcium, lauroleate, acetate, hexanoate or polyethylene polyamine, quadrol etc.
2,, it is characterized in that in the building-up reactions of trimethylsilyl polysilicates, silylation reagent is hexamethyldisiloxane according to the preparation method of claim (1).
3, according to the preparation method of claim (1), it is characterized in that in the building-up reactions of trimethylsilyl polysilicates hexamethyldisiloxane is 0.1-2 with the mole ratio of positive silicon ester, water is 0.1-1.8 with the mole ratio of positive silicon ester.
4,, it is characterized in that in the building-up reactions of trimethylsilyl polysilicates the hydrolyst of positive silicon ester is storng-acid cation exchange resin (exchange capacity＞4 milligramequivalent/grams) according to the preparation method of claim (1).
5,, it is characterized in that in the building-up reactions of trimethylsilyl polysilicates reaction solvent is the benzene class according to the preparation method of claim (1), as benzene,toluene,xylene, alcohols is as methyl alcohol, ethanol, propyl alcohol, Virahol, the ester class is as vinyl acetic monomer, N-BUTYL ACETATE, ethers etc.
6,, it is characterized in that in the building-up reactions of trimethylsilyl polysilicates the weight ratio of storng-acid cation exchange resin and two positive silicon ester of monomer and hexamethyldisiloxane sum is 0.05-0.70 according to the preparation method of claim (1).
7,, it is characterized in that in the building-up reactions of trimethylsilyl polysilicates the weight ratio of solvent and two positive silicon ester of monomer and hexamethyldisiloxane sum is 0.05-1 according to the preparation method of claim (1).
8,, it is characterized in that in the building-up reactions of trimethylsilyl polysilicates temperature of reaction is 20-80 ℃ according to the preparation method of claim (1).
9, according to the preparation method of claim (1), it is characterized in that in the building-up reactions of trimethylsilyl polysilicates, stirred 10-40 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 88105519 CN1024353C (en) | 1988-05-10 | 1988-05-10 | Method of preparation of the modified room-temperature-cured silicone rubber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 88105519 CN1024353C (en) | 1988-05-10 | 1988-05-10 | Method of preparation of the modified room-temperature-cured silicone rubber |
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| Publication Number | Publication Date |
|---|---|
| CN1032947A true CN1032947A (en) | 1989-05-17 |
| CN1024353C CN1024353C (en) | 1994-04-27 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 88105519 Expired - Fee Related CN1024353C (en) | 1988-05-10 | 1988-05-10 | Method of preparation of the modified room-temperature-cured silicone rubber |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100362395C (en) * | 2004-07-16 | 2008-01-16 | 大恒新纪元科技股份有限公司光学薄膜中心 | Application method of silicone rubber adhesive in optical variation welding goggles adhesion |
| CN100577712C (en) * | 2006-10-16 | 2010-01-06 | 中国科学院化学研究所 | Preparation method of room temperature silicon disulfide rubber enhanced by sol-gel method |
| CN1629209B (en) * | 2003-12-17 | 2010-04-28 | 北京三辰化工有限公司 | Method for preparing electronic-grade single-component dealcoholizing-type room temperature cured silicon rubber by non-high-temperature vacuum dewatering method |
| CN1970675B (en) * | 2005-10-27 | 2011-06-15 | 信越化学工业株式会社 | Resin composition for sealing optical device , its cured product and method of sealing semiconductor element |
| CN104049655A (en) * | 2014-05-21 | 2014-09-17 | 南防集团上海安智电气发展有限公司 | Electronic temperature controller special for nuclear motor |
-
1988
- 1988-05-10 CN CN 88105519 patent/CN1024353C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1629209B (en) * | 2003-12-17 | 2010-04-28 | 北京三辰化工有限公司 | Method for preparing electronic-grade single-component dealcoholizing-type room temperature cured silicon rubber by non-high-temperature vacuum dewatering method |
| CN100362395C (en) * | 2004-07-16 | 2008-01-16 | 大恒新纪元科技股份有限公司光学薄膜中心 | Application method of silicone rubber adhesive in optical variation welding goggles adhesion |
| CN1970675B (en) * | 2005-10-27 | 2011-06-15 | 信越化学工业株式会社 | Resin composition for sealing optical device , its cured product and method of sealing semiconductor element |
| CN100577712C (en) * | 2006-10-16 | 2010-01-06 | 中国科学院化学研究所 | Preparation method of room temperature silicon disulfide rubber enhanced by sol-gel method |
| CN104049655A (en) * | 2014-05-21 | 2014-09-17 | 南防集团上海安智电气发展有限公司 | Electronic temperature controller special for nuclear motor |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1024353C (en) | 1994-04-27 |
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