CN1303879A - Cyclosiloxane anion non-equilibrium ring-opening polymerization method - Google Patents
Cyclosiloxane anion non-equilibrium ring-opening polymerization method Download PDFInfo
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- CN1303879A CN1303879A CN 99123985 CN99123985A CN1303879A CN 1303879 A CN1303879 A CN 1303879A CN 99123985 CN99123985 CN 99123985 CN 99123985 A CN99123985 A CN 99123985A CN 1303879 A CN1303879 A CN 1303879A
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- cyclosiloxane
- opening polymerization
- monomer
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- initiator
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- 238000000034 method Methods 0.000 title claims abstract description 16
- 238000007151 ring opening polymerisation reaction Methods 0.000 title claims abstract description 15
- 150000001450 anions Chemical class 0.000 title description 6
- 239000000178 monomer Substances 0.000 claims abstract description 24
- -1 polysiloxane Polymers 0.000 claims abstract description 18
- 239000003999 initiator Substances 0.000 claims abstract description 14
- 125000000129 anionic group Chemical group 0.000 claims abstract description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- 229910003002 lithium salt Inorganic materials 0.000 claims description 22
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 16
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 14
- 159000000002 lithium salts Chemical class 0.000 claims description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 10
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 9
- HTDJPCNNEPUOOQ-UHFFFAOYSA-N hexamethylcyclotrisiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O1 HTDJPCNNEPUOOQ-UHFFFAOYSA-N 0.000 claims description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 claims description 6
- 238000010528 free radical solution polymerization reaction Methods 0.000 claims description 5
- VCYDUTCMKSROID-UHFFFAOYSA-N 2,2,4,4,6,6-hexakis-phenyl-1,3,5,2,4,6-trioxatrisilinane Chemical compound O1[Si](C=2C=CC=CC=2)(C=2C=CC=CC=2)O[Si](C=2C=CC=CC=2)(C=2C=CC=CC=2)O[Si]1(C=1C=CC=CC=1)C1=CC=CC=C1 VCYDUTCMKSROID-UHFFFAOYSA-N 0.000 claims description 3
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 3
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 claims description 3
- 238000012662 bulk polymerization Methods 0.000 claims description 2
- 150000003983 crown ethers Chemical class 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- VMAWODUEPLAHOE-UHFFFAOYSA-N 2,4,6,8-tetrakis(ethenyl)-2,4,6,8-tetramethyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical compound C=C[Si]1(C)O[Si](C)(C=C)O[Si](C)(C=C)O[Si](C)(C=C)O1 VMAWODUEPLAHOE-UHFFFAOYSA-N 0.000 claims 2
- XQQZRZQVBFHBHL-UHFFFAOYSA-N 12-crown-4 Chemical compound C1COCCOCCOCCO1 XQQZRZQVBFHBHL-UHFFFAOYSA-N 0.000 claims 1
- FGZFESWHQXSPJU-UHFFFAOYSA-N 2-methyl-2-(3,3,3-trifluoropropyl)-1,3,5,2,4,6-trioxatrisilinane Chemical compound FC(F)(F)CC[Si]1(C)O[SiH2]O[SiH2]O1 FGZFESWHQXSPJU-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 19
- 229920001296 polysiloxane Polymers 0.000 abstract description 11
- 229920002379 silicone rubber Polymers 0.000 abstract description 4
- YNESATAKKCNGOF-UHFFFAOYSA-N lithium bis(trimethylsilyl)amide Chemical compound [Li+].C[Si](C)(C)[N-][Si](C)(C)C YNESATAKKCNGOF-UHFFFAOYSA-N 0.000 abstract 1
- 239000004945 silicone rubber Substances 0.000 abstract 1
- 238000006116 polymerization reaction Methods 0.000 description 15
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical class [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 10
- 238000006392 deoxygenation reaction Methods 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 238000010907 mechanical stirring Methods 0.000 description 7
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 6
- 238000005133 29Si NMR spectroscopy Methods 0.000 description 4
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000012653 anionic ring-opening polymerization Methods 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000005051 trimethylchlorosilane Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- XSDCTSITJJJDPY-UHFFFAOYSA-N chloro-ethenyl-dimethylsilane Chemical compound C[Si](C)(Cl)C=C XSDCTSITJJJDPY-UHFFFAOYSA-N 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WTQAKAPKTROVFY-UHFFFAOYSA-N C[SiH]1O[Si](O[Si](O1)(CCC)F)(F)F Chemical compound C[SiH]1O[Si](O[Si](O1)(CCC)F)(F)F WTQAKAPKTROVFY-UHFFFAOYSA-N 0.000 description 1
- 239000005046 Chlorosilane Substances 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- ZPCHCIABIAQKQB-UHFFFAOYSA-M [OH-].C(CCC)[N+](CCCC)(CCCC)CCCC.[P] Chemical compound [OH-].C(CCC)[N+](CCCC)(CCCC)CCCC.[P] ZPCHCIABIAQKQB-UHFFFAOYSA-M 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000012676 equilibrium polymerization Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- Silicon Polymers (AREA)
Abstract
本发明一种环硅氧烷阴离子非平衡开环聚合的方法,是采用六甲基二硅氮烷锂盐为引发剂,引发环硅氧烷进行本体或溶液的阴离子非平衡开环聚合的方法,来制备聚硅氧烷。以该方法制备的聚硅氧烷单体转化率可达95－100%。所得高纯度的聚硅氧烷适合于在需要高纯度硅橡胶的领域应用,如航天、高性能电子产品领域。The invention discloses a method for anionic non-equilibrium ring-opening polymerization of cyclosiloxane, which uses hexamethyldisilazane lithium salt as an initiator to trigger cyclosiloxane to perform anionic non-equilibrium ring-opening polymerization in bulk or in solution , to prepare polysiloxane. The conversion rate of the polysiloxane monomer prepared by the method can reach 95-100%. The obtained high-purity polysiloxane is suitable for applications in fields requiring high-purity silicone rubber, such as aerospace and high-performance electronic products.
Description
The present invention relates to the method that a kind of cyclosiloxane carries out the anion non-equilibrium ring-opening polymerization.
The anionic ring-opening polymerization of general cyclosiloxane is an initiator with potassium hydroxide, sodium hydroxide, Tetramethylammonium hydroxide and tetrabutylammonium hydroxide phosphorus etc., and polyreaction is an equilibrium process, contains 14% siloxanes ring body in the polymerisate.The existence of balanced reaction not only makes the polymerisation conversion of raw material low (～86%), and for the field that needs high purity silicon rubber such as space with and high-performance electronic product silicon rubber, need carry out numerous and diverse operation and remove the siloxanes ring body and just can reach requirement.And the cyclic siloxane anion non-equilibrium polymerization can reduce or eliminate the balanced reaction in the cyclosiloxane polymerization process, and what make the monomer high conversion changes polysiloxane (＞95%) into.Therefore, to the research of the anion non-equilibrium ring-opening polymerization of cyclosiloxane, report to some extent successively since 1967 mainly is that research is that initiator causes cyclosiloxane and carries out anionic ring-opening polymerization with the lithium salts.Since lithium salts to anionic activity a little less than, do not interrupt the siloxane bond in the silica chain, thereby there is not balanced reaction in polymerization process.But the cyclic siloxane anion non-equilibrium polymeric research that lithium salts causes is mainly concentrated on active higher hexamethyl cyclotrisiloxane (D
3) monomeric polymerization, and at the lower octamethylcyclotetrasiloxane (D of the activity of the industrial extensive application of organosilicon
4) monomeric polymerization studies then seldom.
This laboratory is once caused cyclosiloxane with the lithium salts of six organic basic ring three silazane and is carried out anionic ring-opening polymerization and prepare star polysiloxane [Chinese patent, application number 98103244.3], but do not relate to lithium salts with the industrial hexamethyldisilazane that obtains easily as initiator, cause the method that cyclosiloxane carries out the anion non-equilibrium ring-opening polymerization.
The present invention has overcome in the prior art when preparing polysiloxane with equilibrium process, and monomer conversion is low, the defective of 14% siloxanes ring body is arranged in polymerisate, and a kind of lithium salts (MM with hexamethyldisilazane is provided
NLi) be initiator, cause the method that the cyclosiloxane ring-opening polymerization prepares high monomer transformation efficiency, highly purified polysiloxane with non-equilibrium polymeric approach, particularly cause octamethylcyclotetrasiloxane (D
4) polymerization have good effect.
Cyclosiloxane ring-opening polymerization among the present invention step is in the following order carried out:
1. prepare MM
NLiThe lithium salts initiator
With MM
NHWith n-Butyl Lithium be in molar ratio: got MM at-60～30 ℃ of following stirring reaction 5-6 hours in 1: 1～1: 1.2
NLiLithium salts, removal of solvent under reduced pressure under the secluding air condition, is carried out thorough washing with normal hexane to the lithium salts that makes, and is neutral until elutant, removal of solvent under reduced pressure again, inflated with nitrogen is protected prepared lithium salts.
Above-mentioned MM
NLiThe lithium salts initiator has following structure:
2. cyclosiloxane anion non-equilibrium ring-opening polymerization:
Add above-mentioned MM in the cyclosiloxane monomer
NLiThe promotor of 2～10 times of molar weights of lithium salts initiator and above-mentioned initiator is carried out body or solution polymerization, and the mol ratio of monomer and initiator is: 10: 1～2000: 1,0 ℃～160 ℃ polyreactions 2～24 hours, obtain polymerisate.
Above-mentioned cyclosiloxane monomer comprises: hexamethyl cyclotrisiloxane (D
3), octamethylcyclotetrasiloxane (D
4), hexaphenyl cyclotrisiloxane (D
3 Ph), tetramethyl-tetrem thiazolinyl cyclotetrasiloxane (D
4 Vi), methyl trifluoro propyl cyclotrisiloxane (D
3 F) or above-mentioned monomeric mixture.
Used promotor comprises: tetrahydrofuran (THF), glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dme, dimethyl sulfoxide (DMSO), dimethyl formamide, hexamethylphosphorictriamide, crown ether, cave ether etc.
The solvent of above-mentioned solution polymerization comprises normal hexane, toluene, the tetrahydrochysene furan food in one's mouth, glycol dimethyl ether etc.
3. functional group's end-blocking of polymkeric substance
The polymerisate of above-mentioned mass polymerization is with normal hexane or toluene dissolving, and adding and initiator equimolar amount or excessive end-capping reagent carry out end-blocking simultaneously.Then can directly add end-capping reagent for solution polymerization and carry out end-blocking, filter after the end capping, filtrate is removal of solvent under reduced pressure again, obtains the polysiloxane product.
Above-mentioned end-capping reagent can be: water, methyl iodide, trimethylchlorosilane, dimethyl vinyl chlorosilane and dimethyl amine alkyl chlorosilane etc.
Polysiloxane with method preparation of the present invention dissolves in organic solvent, and these solvents comprise: alkane, aromatic hydrocarbon, tetrahydrofuran (THF), chloroform.
Silicone monomers transformation efficiency with this method preparation can reach 95-100%; Polymerisate does not contain or only contains a spot of cyclosiloxane, and the highly purified polysiloxane of gained is suitable for using in the field that needs high purity silicon rubber, as space flight, high-performance electronic product scope.
Embodiment
Embodiment 1: in there-necked flask, and logical N
2The deoxygenation dehumidifying.Add hexamethyl cyclotrisiloxane (D
3) 26g, MM
NLiLithium salts 0.01g, tetrahydrofuran (THF) 6ml, 70～80 ℃ of mechanical stirring polymerizations.Finish reaction after 6 hours.
29Si NMR detects D
3100% transforms.With the dissolving of 30ml toluene, carry out end-blocking with 0.5ml water.Filter removal of solvent under reduced pressure, polymkeric substance [η]=43.8ml/g.
Embodiment 2:
In there-necked flask, logical N
2The deoxygenation dehumidifying.Add D
3/ D
4(6%mol.D
3) 15.3g, MM
NLiLithium salts 0.02g, 0.5ml exsiccant N, dinethylformamide are promotor, 100 ℃ of mechanical stirring polymerizations.Viscosity increases after 1 hour, after 4 hours
29Si NMR detects monomer conversion monomer conversion monomer 100% conversion after 95%, 24 hour after 78%, 11 hour.With the dissolving of 20ml toluene, carry out end-blocking with the 1.5ml methyl iodide.Filter removal of solvent under reduced pressure, polymkeric substance [η]=32.06ml/g.
Embodiment 3:
In there-necked flask, logical N
2The deoxygenation dehumidifying.Add D
419.6g, MM
NLiLithium salts 0.02g, 0.5ml exsiccant dimethyl sulfoxide (DMSO) is a promotor, 100 ℃ of mechanical stirring polymerizations.Viscosity obviously increases after 2 hours, after 11 hours
29SiNMR detects monomer conversion and reaches 95%.With the dissolving of 20ml toluene, carry out end-blocking with the 1.5ml trimethylchlorosilane.Filter removal of solvent under reduced pressure, polymkeric substance [η]=82ml/g.
Embodiment 4:
In there-necked flask, logical N
2The deoxygenation dehumidifying.Add D
419.95g, MM
NLiLithium salts 0.08g, 0.5ml exsiccant diethylene glycol dimethyl ether is a promotor, 160 ℃ of mechanical stirring polymerizations.Viscosity obviously increases after 1 hour.After 15 hours
29Si NMR detects monomer conversion 100%.Polymkeric substance [η]=41.87ml/g.
Embodiment 5:
In there-necked flask, logical N
2The deoxygenation dehumidifying.Add D
417.4g, MM
NLiLithium salts 0.87g, 2ml exsiccant triethylene glycol dme is a promotor, 100 ℃ of mechanical stirring polymerizations.Viscosity increases after 2 hours, after 4 hours
29Monomer conversion reached 95% after Si NMR detection monomer conversion reached 91%, 10 hour.Add 20ml toluene dissolve polymer, 1.2ml dimethyl vinyl chlorosilane end-blocking, 25 ℃ were reacted 4 hours, filtered removal of solvent under reduced pressure.Polymkeric substance [η]=9.17ml/g.Embodiment 6:
In there-necked flask, logical N
2The deoxygenation dehumidifying.Add D
4 Vi6.89g, D
45.91g, MM
NLiLithium salts 0.1g, the 12-crown-4 crown ether of 0.5g is a promotor, 60 ℃ of induction stirring polymerizations 20 hours, is warming up to 100 ℃ of polymerizations 10 hours,
29Si NMR detects monomer conversion and reaches 100%.
Embodiment 7:
In there-necked flask, logical N
2The deoxygenation dehumidifying.Add D
3 Ph10.2g, D
33.8gMM
NLiLithium salts 0.05g, 0.1ml exsiccant hexamethylphosphorictriamide is a promotor, and the 30ml normal hexane 40-50 ℃ of induction stirring polymerization 20 hours, filters, and removal of solvent under reduced pressure obtains polymkeric substance.
Embodiment 8:
In there-necked flask, logical N
2The deoxygenation dehumidifying.Add D
3 F12g, MM
NLiLithium salts 0.02g, 20ml exsiccant glycol dimethyl ether is promotor and solvent, 0 ℃ of mechanical stirring polymerization 2 hours, carries out end-blocking with the 1.0ml trimethylchlorosilane.Filter, removal of solvent under reduced pressure obtains polymkeric substance.
Embodiment 9:
In there-necked flask, logical N
2The deoxygenation dehumidifying.Add D
3/ D
4(1%mol.D
3) 15.3g, MM
NLiLithium salts 0.02g, 0.5ml exsiccant dimethyl sulfoxide (DMSO) is a promotor, 100 ℃ of mechanical stirring polymerizations.Monomer conversion monomer 100% conversion after 95%, 24 hour after 11 hours.With the dissolving of 20ml toluene, carry out end-blocking with the 1.5ml methyl iodide.Filter, removal of solvent under reduced pressure obtains polymkeric substance.
Claims (5)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 99123985 CN1129629C (en) | 1999-11-23 | 1999-11-23 | Cyclosiloxane anion non-equilibrium ring-opening polymerization method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 99123985 CN1129629C (en) | 1999-11-23 | 1999-11-23 | Cyclosiloxane anion non-equilibrium ring-opening polymerization method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1303879A true CN1303879A (en) | 2001-07-18 |
| CN1129629C CN1129629C (en) | 2003-12-03 |
Family
ID=5283088
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 99123985 Expired - Lifetime CN1129629C (en) | 1999-11-23 | 1999-11-23 | Cyclosiloxane anion non-equilibrium ring-opening polymerization method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1129629C (en) |
Cited By (11)
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| CN101838393A (en) * | 2010-04-29 | 2010-09-22 | 山东大学 | Method for synthesizing high-molecular-weight ethyl polysiloxane |
| CN101245146B (en) * | 2007-02-12 | 2011-12-07 | 浙江省化工研究院有限公司 | Method for producing high molecular weight fluorine silicon raw rubber |
| CN104829838A (en) * | 2015-05-06 | 2015-08-12 | 青岛科技大学 | Preparation method of hydroxyl terminated polyfluorosiloxane |
| CN104072775B (en) * | 2014-06-13 | 2017-01-25 | 王金明 | Preparation technique of medium/high-viscosity dimethyl silicone oil |
| CN109265684A (en) * | 2018-09-10 | 2019-01-25 | 航天材料及工艺研究所 | Silicon rubber, phenol aldehyde modified silicone rubber resina and preparation method thereof |
| CN109776803A (en) * | 2018-12-21 | 2019-05-21 | 中科院广州化学有限公司南雄材料生产基地 | A kind of preparation method of regulating and controlling poly(dimethylsiloxane-co-methylvinylsiloxane) molecular weight and its distribution |
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| CN112062966A (en) * | 2020-06-23 | 2020-12-11 | 西南科技大学 | Preparation method of high-electrostriction silicone rubber dielectric elastomer |
| CN114044905A (en) * | 2021-10-06 | 2022-02-15 | 复旦大学 | Preparation method of end group functionalized polydimethylsiloxane |
| CN116217933A (en) * | 2022-11-21 | 2023-06-06 | 浙江开化合成材料有限公司 | A kind of polymethylphenylsiloxane oligomer, preparation method and low oil dissociation heat conduction silicone grease |
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| CN100506889C (en) * | 2006-01-23 | 2009-07-01 | 中国科学院化学研究所 | Dipotassium silanol salt-induced anionic non-equilibrium polymerization of cyclosiloxane to prepare bifunctional end-group polysiloxane |
-
1999
- 1999-11-23 CN CN 99123985 patent/CN1129629C/en not_active Expired - Lifetime
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|---|---|---|---|---|
| CN101245146B (en) * | 2007-02-12 | 2011-12-07 | 浙江省化工研究院有限公司 | Method for producing high molecular weight fluorine silicon raw rubber |
| CN101838393A (en) * | 2010-04-29 | 2010-09-22 | 山东大学 | Method for synthesizing high-molecular-weight ethyl polysiloxane |
| CN101838393B (en) * | 2010-04-29 | 2012-04-04 | 山东大学 | A kind of synthetic method of high molecular weight ethylpolysiloxane |
| CN104072775B (en) * | 2014-06-13 | 2017-01-25 | 王金明 | Preparation technique of medium/high-viscosity dimethyl silicone oil |
| CN104829838A (en) * | 2015-05-06 | 2015-08-12 | 青岛科技大学 | Preparation method of hydroxyl terminated polyfluorosiloxane |
| CN104829838B (en) * | 2015-05-06 | 2017-04-05 | 青岛科技大学 | A kind of preparation method of hydroxy-end capped poly- fluorosilicone |
| US11254790B2 (en) * | 2018-09-10 | 2022-02-22 | Aerospace Research Institute Of Materials & Processing Technology | Silicone rubber and phenolic modified silicone rubber and methods for preparing the same |
| CN109265684A (en) * | 2018-09-10 | 2019-01-25 | 航天材料及工艺研究所 | Silicon rubber, phenol aldehyde modified silicone rubber resina and preparation method thereof |
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Assignee: Qiangli Chemical Co., Ltd., Huangshan City Assignor: Institute of Chemistry, Chinese Academy of Sciences Contract record no.: 2011340000373 Denomination of invention: Cyclosiloxane anion non-equilibrium ring-opening polymerization method Granted publication date: 20031203 License type: Exclusive License Open date: 20010718 Record date: 20110830 |
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