CN1242388A - Polysiloxane having silazane structure on its main chain - Google Patents
Polysiloxane having silazane structure on its main chain Download PDFInfo
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- CN1242388A CN1242388A CN 98103244 CN98103244A CN1242388A CN 1242388 A CN1242388 A CN 1242388A CN 98103244 CN98103244 CN 98103244 CN 98103244 A CN98103244 A CN 98103244A CN 1242388 A CN1242388 A CN 1242388A
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- polysiloxane
- silazane
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Abstract
The present invention relates to a polysiloxane whose main chain contains cyclosilazane and its structural formula. It is prepared by using cyclosiloxane as monomer, cyclotrisilazane lithium salt as initiator, and making them implement polymerization reaction whose reaction temp. is 0 deg.C-150 deg.C and reaction time is 3-24 hr..
Description
The present invention relates to a kind of polysiloxane that contains the silazane structure, particularly a kind of main chain contains the polysiloxane that encircles silazane.
General organopolysiloxane, its heat resistance is no more than 200-300 ℃, synthesized a kind of silicon-nitrogen polymer among the patent ZL 93117929.7, in ZL 93117927.0 with above-mentioned silicon-nitrogen polymer as linking agent, can make the heat resistance of room temperature vulcanized silicone rubber bring up to 350 ℃, not contain the ring silazane structure but relate to polysiloxane backbone.
The invention provides a kind of polysiloxane of silazane structure on its main chain.
Contain the ring silazane structure in the polysiloxane backbone of the present invention, its structural formula is as follows:
Wherein: R represents alkyl, the phenyl of 1～6 C atom
R
1Represent alkyl, the phenyl of 2～6 C atoms
R
2Represent alkyl, the phenyl A of 1～6 C atom represent H or
B represent H or
N represents 10～5000 integer.The structural formula of the above-mentioned polysiloxane that contains the silazane structure can for:
Organopolysiloxane of the present invention is dissolved in organic solvent, and these solvents comprise: the alkane of 6～18 C atoms and derivative thereof, the aromatic hydrocarbon of 6～9 C atoms, tetrahydrofuran (THF), chloroform.
Organopolysiloxane of the present invention step in the following order is prepared:
1. preparation encircles the lithium salts of three silazane
Encircling three silazane and n-Butyl Lithium (mol ratio of encircling three silazane and n-Butyl Lithium is: 1: 1～1: 3) stirs in organic solvent and reacts; reacted 5-6 hour; after reaction finishes; removal of solvent under reduced pressure; under the secluding air condition, the lithium salts that makes is carried out thorough washing then, be neutral until elutant with normal hexane; removal of solvent under reduced pressure again, inflated with nitrogen is protected prepared lithium salts.Temperature of reaction is at-60～30 ℃.Solvent comprises: the aromatic hydrocarbon of the alkane of 6～12 C atoms, 6～9 C atoms, ether, tetrahydrofuran (THF), glycol dimethyl ether, dimethyl sulfoxide (DMSO) etc.
2. synthetic organopolysiloxane:
Make initiator by the ring three silazane lithium salts that step 1 obtains, under the effect of promotor, the cyclosiloxane monomer carries out body or solution polymerization, the mol ratio of cyclosiloxane monomer and initiator is: 10: 1～1000: 1, polymeric reaction temperature is at 0 ℃～150 ℃, and polymerization reaction time is 3 hours～24 hours.Above-mentioned cyclosiloxane monomer comprises: hexamethyl cyclotrisiloxane, octamethylcyclotetrasiloxane, hexaphenyl cyclotrisiloxane.Used promotor comprises: tetrahydrofuran (THF), glycol dimethyl ether, diethylene glycol dimethyl ether, dimethyl sulfoxide (DMSO), dimethyl formamide etc.If solution polymerization, then solvent comprises aromatic hydrocarbon, tetrahydrofuran (THF), glycol dimethyl ether of the alkane of 6～12 C atoms, 6～9 C atoms etc.
3. the processing of polymkeric substance
After promotor and solvent are removed in step 2 synthetic polymkeric substance decompression, add alkane solvent or aromatic solvent, as normal hexane or toluene, end-blocking or end-blocking not filter then, and filtrate is removal of solvent under reduced pressure again, obtains polymkeric substance.
Embodiment 1:
In there-necked flask, add hexamethyl cyclotrisiloxane 6.63g, hexaphenyl ring three silazane lithium salts 0.18g, glycol dimethyl ether 6.0ml, 90～100 ℃ of stirring reactions 5.5 hours, glycol dimethyl ether is removed in decompression then, adds the n-hexane dissolution after-filtration, filtrate decompression is removed normal hexane, obtains polymkeric substance.Polymkeric substance Mn=69469, Mw=138856, d (Mw/Mn)=1.999, intrinsic viscosity [η]=35.00ml/g.Embodiment 2:
In there-necked flask, add hexamethyl cyclotrisiloxane 6.00g, hexaphenyl ring three silazane lithium salts 0.23g, tetrahydrofuran (THF) 8.0ml, 90～100 ℃ were reacted 8 hours, and tetrahydrofuran (THF) is removed in decompression then, add the n-hexane dissolution after-filtration, filtrate decompression is removed normal hexane, obtains polymkeric substance.Polymkeric substance Mw=117728, intrinsic viscosity [η]=27.71ml/g.Embodiment 3:
In there-necked flask, add octamethylcyclotetrasiloxane 5.00g, hexaphenyl ring three silazane lithium salts 0.16g, diethylene glycol dimethyl ether 5.0ml, 140～150 ℃ of stirring reactions 24 hours, diethylene glycol dimethyl ether is removed in decompression then, adds the n-hexane dissolution after-filtration, filtrate decompression is removed normal hexane, obtains polymkeric substance.Polymkeric substance Mw=127815, intrinsic viscosity [η]=31.95ml/g.Embodiment 4:
In there-necked flask, add hexamethyl cyclotrisiloxane 7.60g, hexaphenyl ring three silazane lithium salts 0.10g, tetrahydrofuran (THF) 3.0ml, dimethyl sulfoxide (DMSO) 0.4ml, 30～40 ℃ of stirring reactions are after 5.0 hours, tetrahydrofuran (THF) and dimethyl sulfoxide (DMSO) are removed in decompression, add n-hexane dissolution and filter, filtrate decompression is removed normal hexane, obtains polymkeric substance.Polymkeric substance Mw=181477, intrinsic viscosity [η] 49.23ml/g.Embodiment 5:
In there-necked flask, add hexaphenyl cyclotrisiloxane 8.10g, hexaphenyl ring three silazane lithium salts 0.18g, toluene 30.0ml, dimethyl sulfoxide (DMSO) 0.4ml, 40～50 ℃ of stirring reactions are after 10 hours, toluene and dimethyl sulfoxide (DMSO) are removed in decompression, add n-hexane dissolution and filter, filtrate decompression is removed normal hexane, obtains polymkeric substance.Embodiment 6:
In there-necked flask, add hexamethyl cyclotrisiloxane 7.20g, trimethyl triphenyl ring three silazane lithium salts 0.34g, tetrahydrofuran (THF) 5.0ml, dimethyl formamide 0.6ml, 40～50 ℃ of stirring reactions are after 10 hours, tetrahydrofuran (THF) and dimethyl formamide are removed in decompression, add n-hexane dissolution and filter, filtrate decompression is removed normal hexane, obtains polymkeric substance.Embodiment 7:
In there-necked flask, add hexaphenyl cyclotrisiloxane 10.20g, trimethyl triphenyl ring three silazane lithium salts 0.14g, toluene 35.0ml, dimethyl sulfoxide (DMSO) 0.5ml, 40～50 ℃ of stirring reactions are after 10 hours, toluene and dimethyl sulfoxide (DMSO) are removed in decompression, add n-hexane dissolution and filter, filtrate decompression is removed normal hexane, obtains polymkeric substance.
Claims (6)
1. the polysiloxane of a silazane structure on its main chain is characterized in that described polysiloxane has following structural formula:
In the formula: R represents alkyl, the phenyl of 1～6 C atom
R
1Represent alkyl, the phenyl of 2～6 C atoms
R
2Represent alkyl, the phenyl of 1～6 C atom
N represents 10～5000 integer
2. the polysiloxane of a silazane structure on its main chain is characterized in that described polysiloxane has following structural formula:
In the formula: R represents alkyl, the phenyl of 1～6 C atom
R
1Represent alkyl, the phenyl of 2～6 C atoms
R
2Represent alkyl, the phenyl of 1～6 C atom
N represents 10～5000 integer
3. the polysiloxane of a silazane structure on its main chain is characterized in that described polysiloxane has following structural formula:
In the formula: R represents alkyl, the phenyl of 1～6 C atom
R
1Represent alkyl, the phenyl of 2～6 C atoms
R
2Represent alkyl, the phenyl of 1～6 C atom
N represents 10～5000 integer
4. the preparation method of the polysiloxane of a kind of silazane structure on its main chain according to claim 1 is characterized in that step is carried out in the following order:
1). the lithium salts of preparation ring three silazane reacted 5～6 hours for 30 ℃, obtained encircling the lithium salts of three silazane.
2). with the cyclosiloxane is monomer, is initiator with the lithium salts that encircles three silazane, and the mol ratio of cyclosiloxane monomer and initiator is: 10: 1～1000: 1, under 0 ℃～150 ℃, polymerization time was 3～24 hours, obtains polymkeric substance.
5. the preparation method of the polysiloxane of a kind of silazane structure on its main chain according to claim 4 is characterized in that described organic solvent is the mixed solvent of tetrahydrofuran (THF) or ether and normal hexane.
6. the preparation method of the polysiloxane of a kind of silazane structure on its main chain according to claim 4 is characterized in that described cyclosiloxane monomer is: hexamethyl cyclotrisiloxane, octamethylcyclotetrasiloxane or hexaphenyl cyclotrisiloxane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98103244A CN1088722C (en) | 1998-07-17 | 1998-07-17 | Polysiloxane having silazane structure on its main chain |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98103244A CN1088722C (en) | 1998-07-17 | 1998-07-17 | Polysiloxane having silazane structure on its main chain |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1242388A true CN1242388A (en) | 2000-01-26 |
| CN1088722C CN1088722C (en) | 2002-08-07 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98103244A Expired - Lifetime CN1088722C (en) | 1998-07-17 | 1998-07-17 | Polysiloxane having silazane structure on its main chain |
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| CN (1) | CN1088722C (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100347220C (en) * | 2006-02-14 | 2007-11-07 | 湘潭大学 | Preparation of novel composite initiator and copolymerization of epoxide and cyclic ether and homopolymerization of epoxide initiated by same |
| CN109988311A (en) * | 2017-12-29 | 2019-07-09 | 中国科学院化学研究所 | A kind of poly- silicon oxygen silazane and preparation method thereof |
| CN111662456A (en) * | 2019-03-05 | 2020-09-15 | 中国科学院化学研究所 | Preparation method of siloxane polymer |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU367713A1 (en) * | 1970-12-14 | 1979-09-15 | Ponomarev A I | Method of producing polyheterosiloxanes |
| SU559939A1 (en) * | 1975-06-11 | 1977-05-30 | Предприятие П/Я Г-4299 | Rubber compound based on vinyl-containing organosiloxane rubber |
| SU973553A1 (en) * | 1980-10-31 | 1982-11-15 | Казанский Филиал Всесоюзного Ордена Трудового Красного Знамени Научно-Исследовательского Института Синтетического Каучука Имени Акад. С.В.Лебедева | Process for producing alpha,omega-carboxypolyorganosiloxanes |
-
1998
- 1998-07-17 CN CN98103244A patent/CN1088722C/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100347220C (en) * | 2006-02-14 | 2007-11-07 | 湘潭大学 | Preparation of novel composite initiator and copolymerization of epoxide and cyclic ether and homopolymerization of epoxide initiated by same |
| CN109988311A (en) * | 2017-12-29 | 2019-07-09 | 中国科学院化学研究所 | A kind of poly- silicon oxygen silazane and preparation method thereof |
| CN111662456A (en) * | 2019-03-05 | 2020-09-15 | 中国科学院化学研究所 | Preparation method of siloxane polymer |
| CN111662456B (en) * | 2019-03-05 | 2021-08-03 | 中国科学院化学研究所 | Preparation method of siloxane polymer |
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| Publication number | Publication date |
|---|---|
| CN1088722C (en) | 2002-08-07 |
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