CN1181081C - Mixed fluorinated cyclosiloxane, preparing method and use thereof - Google Patents
Mixed fluorinated cyclosiloxane, preparing method and use thereof Download PDFInfo
- Publication number
- CN1181081C CN1181081C CNB031289096A CN03128909A CN1181081C CN 1181081 C CN1181081 C CN 1181081C CN B031289096 A CNB031289096 A CN B031289096A CN 03128909 A CN03128909 A CN 03128909A CN 1181081 C CN1181081 C CN 1181081C
- Authority
- CN
- China
- Prior art keywords
- fluorine
- dichlorosilane
- hybrid ring
- oxide
- ring siloxane
- 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.)
- Expired - Fee Related
Links
Landscapes
- Silicon Polymers (AREA)
Abstract
The present invention relates to fluorine-containing mixed cyclosiloxane, a preparation method and an application thereof. Mixed raw materials of fluorine-containing alkyl dichloromethylsilane and dialkyl dichlorosilane react with metallic oxide or alkali carbonate, and the fluorine-containing mixed cyclosiloxane is directly prepared by dechlorination. The compound has a structural formula as above, wherein R1 is an alkyl group or a phenyl group of C1 to C4, R2 is a methyl group or the phenyl group, m is 0, or 1 or 2, n is an integral number from 3 to 10, X is 2 or 3, and Y is an integral number from 0 to 11. The compound can be used for synthesizing fluorine-containing polysiloxane and preparing fluorin-silicon lubricating oil, fluorosilicone rubber, hydroxyl-fluoro silicone oil, etc.
Description
Technical field
The present invention relates to a kind of fluorine-containing hybrid ring siloxane, preparation method and its usage.Directly prepare fluorine-containing hybrid ring siloxane with fluorine-containing alkyl methyl dichlorosilane and dialkyl dichlorosilane mixing raw material and metal oxide, alkaline carbonate dechlorination.This compound can be used for synthetic fluorinated polysiloxane as the fluorine silicon grease.
Background technology
Ucon oil is that the method by chemosynthesis prepares lubricating oil, its development is from World War II, the France and the Japan that lacked petroleum resources at that time develop this series products for the urgent regardless of expense that needs of war, because its synthetic cost is far above the mineral oil of a large amount of uses, so only limit to some particular service requirement use down that mineral lubricating oils can not satisfy service requirements at present.Along with the development of chemical industry, the ucon oil price reduces gradually, and improves performance by mix and add additive with mineral lubricating oils, can be developed into the efficient lubricant oil of durable energy saving life, and this makes the range of application of ucon oil day by day enlarge.And the needs of Aeronautics and Astronautics technology develop rapidly more make the kind of ucon oil constantly increase in recent years, and consumption constantly enlarges.
At present, the extraordinary high temperature grease of abroad having developed that can satisfy 200～400 ℃ of scopes uses is various in style, as polybenzoate, carbonic ether, halo polysiloxane etc.By contrast, less input in this respect in China, can the long-term lubricating oil kind of using still belong to blank between-50～250 ℃.
In dimethyl silicone oil, introduce the lubricity that chlorophenyl can significantly improve silicone oil, but less stable.If replace part methyl to contain fluoroalkyl, then can make the fluorine silicon grease that is used under high and low temperature and the high pressure.In the fluorine silicon grease, with trifluoro propyl methyl-silicone oil over-all properties the best, it has solvent resistance, chemical stability and the excellent lubrication of height.Generally, the trifluoro propyl methyl-silicone oil is to make the trifluoro propyl dimethyl dichlorosilane (DMCS) by trifluoro propene and the addition of methyl dichloro hydrogen silane, and hydrolysis then, cracking make three ring body D
3 F, ring-opening polymerization makes in the presence of the end-capping reagent hexamethyldisiloxane again.In preparation process, D
3 FBe prepared as gordian technique.
As everyone knows, fluorine has the strongest electronegativity in all elements, often is combined into key consumingly with other atom and attracts the electronics of bonding.Particularly the fluorine atom in the C-F key demonstrates the intensive electrophilic as substituting group, and the electron density around making descends, and this makes and after by the fluorine replacement oxidation is blocked near the position that might be subjected to attack such as oxidation or its.This provides theoretical foundation for selecting to introduce fluorine atom in cyclosiloxane and even the silicone oil side chain substituents.
As far back as nineteen sixty, people such as Takiguchi (T.Takiguchi, M.Sakurai, T.Kishi, et al, Preparation of hexaphenylcyclotrisiloxane by the reaction of diphenyldichlorosilanewith zinc oxide.J.Org.Chem.1960,25,311) promptly reported the method for preparing cyclotrisiloxane by dialkyldichlorosilan,s with the metal oxide dechlorination.The people such as Wu of the U.S. in 1975 (T.C.Wu and M.Mass, Cyclotrisiloxane containing silicon-bonded fluoroalkoxyalkyl groups.USP3876677) make fluorine-containing alkoxyalkyl methyl cyclotrisiloxane with the dechlorination that this method is used for fluorine-containing alkoxyalkyl dimethyl dichlorosilane (DMCS).That at first the metal oxide dechlorination is used to prepare polysiloxane is the YamaguchiKoichi (Y.Koichi of Japan, K.Hirobumi, K.Nobuyuki, Manufacture of linearfluorine-containing organopolysiloxane.JP 0803,318.1996), utilize trifluoro propyl dimethyl dichlorosilane (DMCS) and α, the direct condensation of ω-dichloro (gathering) siloxanes dechlorination has obtained linear polysiloxane, but it is a block polymer.
In sum, adopt fluorine-containing cyclosiloxane ring-opening polymerization to prepare high performance fluorine silicone oil or trifluoropropyl siloxane usually, fluorine-containing cyclosiloxane is a kind of important intermediate, explores inexpensive new intermediate and prepares high performance fluorine silicone oil and be still important problem.
Summary of the invention
The purpose of this invention is to provide a kind of fluorine-containing hybrid ring siloxane.
Another object of the present invention provides the method for the above-mentioned fluorine-containing hybrid ring siloxane of preparation, and is specifically a kind of with the metal oxide dechlorination, by containing the method that fluoroalkyl dichlorosilane, dialkyl dichlorosilane mixture prepare fluorine-containing hybrid ring siloxane.
Purpose of the present invention also provides the purposes of fluorine-containing hybrid ring siloxane, directly can prepare fluorine silicon grease or trifluoropropyl siloxane by this mixed methylcyclosiloxane with strong acid catalysis ring-opening polymerization.
Fluorine-containing hybrid ring siloxane of the present invention has following structural formula:
R wherein
1=C
1～4Alkyl, phenyl; R
2=methyl, phenyl; M=0,1,2; The integer of n=3～10; X=2,3; The integer of Y=0～11.
In the method for the present invention, the fluorine content of the fluorine-containing hybrid ring siloxane of gained is 10%～60%.
The preparation method of fluorine-containing hybrid ring siloxane of the present invention is in organic solvent and under-20 ℃～80 ℃ temperature, with fluorine-containing alkyl methyl dichlorosilane and dialkyl dichlorosilane mixing raw material, with metal oxide or alkaline carbonate dechlorination, reacted 0.1～10 hour, and can directly make fluorine-containing hybrid ring siloxane.The mol ratio of above-mentioned fluorine-containing alkyl methyl dichlorosilane, dialkyl dichlorosilane and metal oxide or alkaline carbonate is followed successively by 0.1～5: 1: 0.5～5, and the mol ratio of fluorine-containing alkyl methyl dichlorosilane and dialkyl dichlorosilane is preferably 0.2～3: 1.The described fluoroalkyl dichlorosilane molecular formula that contains is F
3C (CF
2)
Y(CH
2)
XSi (CH
3) Cl
2, dialkyl dichlorosilane molecular formula is R
1R
2SiCl
2, wherein, R
1It is the alkyl or phenyl of C1～4 that comprise methyl or ethyl; R
2=methyl, phenyl; X=2,3; Y=0～11;
Described metal oxide is zinc oxide, barium oxide, calcium oxide, magnesium oxide, cupric oxide, Manganse Dioxide or plumbic oxide etc., and described alkaline carbonate is yellow soda ash, salt of wormwood etc.Be preferably zinc oxide.
The used organic solvent of the present invention can be ethyl acetate, methyl acetate, sherwood oil, normal hexane, hexanaphthene, benzene, toluene or methylene dichloride etc., is preferably ethyl acetate, methyl acetate.
It is to carry out under 0 ℃～30 ℃ that dechlorination cyclization of the present invention is preferably in.
What prepared by the metal oxide dechlorination is fluorine-containing hybrid ring siloxane, directly prepare fluorosilicone and by trifluoro propyl dimethyl dichlorosilane (DMCS) and α with its ring-opening polymerization, the direct condensation prepared polysiloxane of ω-dichloro (gathering) siloxanes dechlorination is compared, and the present invention has the following advantages.The first, the raw material that uses among the present invention is easy to get for mixing dichlorosilane; The second, earlier synthetic fluorine-containing hybrid ring siloxane needn't separate and directly be used for preparing the fluorine silicon grease with strong acid catalysis ring-opening polymerization, helps reducing cost and is easy to control the molecular weight and the molecular weight distribution of fluorosilicon oil; The 3rd, the fluorine-containing hybrid ring siloxane molecular weight that obtains is relatively little, and technology is easier to realize; The 4th, avoided directly by α, the block copolymerization tendency in the direct condensation prepared polysiloxane of ω-dichloro (gathering) the siloxanes dechlorination process, thus the easier fluoroalkyl uniform distribution on silicon-oxygen backbone that makes makes the fluorosilicon oil molecular structure more reasonable; The 5th, the fluorosilicon oil that is useful for fluorine-containing dichlorosilane and dialkyl dichlorosilane arbitrary proportion is synthetic, the fluorine content of easier control fluorosilicon oil; The 6th, the gained fluorinated polysiloxane is owing to the introducing of fluorine element has the good heat endurance energy.
Fluorine-containing hybrid ring siloxane of the present invention is simple synthetic method not only, and can be used for fluorosilicon oil, the hydroxyl fluorosilicon oil of synthetic excellent property and close trifluoropropyl siloxane etc.
Embodiment
Following examples help to understand the present invention, but are not limited to content of the present invention.
Embodiment 1
Three neck reaction flasks are equipped with induction stirring, reflux exchanger, thermometer and feed hopper, with stirring into suspension in calcium oxide 0.35mol and the 150ml ethyl acetate adding reaction flask, drip the 0.15mol F that is pre-mixed under 20 ℃ of water-baths coolings
3C (CF
2)
Y(CH
2)
XSi (CH
3) Cl
2(X=2; Y=0) and 0.2mol dimethyldichlorosilane(DMCS) mixture; Continue reaction 1h after adding the dichlorosilane mixture; Behind the insoluble calcium salt of elimination, filtrate washing 100ml * 2 time again with distillation washing 100ml * 2 time; With the anhydrous sodium sulfate drying after-filtration, steaming removes ethyl acetate and obtains fluorine-containing hybrid ring siloxane 28.5g, and productive rate (by the dichlorosilane total amount) is 79.4%.Product
19F NMR (δ)-70.57ppm, fluorine content are 21.18%.
Embodiment 2
Three neck reaction flasks are equipped with induction stirring, reflux exchanger, thermometer and feed hopper, with stirring into suspension in magnesium oxide 0.35mol and the 150ml ethyl acetate adding reaction flask, drip the 0.15mol F that is pre-mixed under 20 ℃ of water-baths coolings
3C (CF
2)
Y(CH
2)
XSi (CH
3) Cl
2(X=2; Y=0) and 0.2mol dimethyldichlorosilane(DMCS) mixture; Continue reaction 1h after adding the dichlorosilane mixture; Behind the insoluble magnesium salts of elimination, filtrate washing 100ml * 2 time again with distillation washing 100ml * 2 time; With the anhydrous sodium sulfate drying after-filtration, steaming removes ethyl acetate and obtains fluorine-containing hybrid ring siloxane 24.5g, and productive rate (by the dichlorosilane total amount) is 68.8%.Product
19F NMR (CDCl
3, δ) :-70.59ppm, fluorine content are 21.21%.
Embodiment 3
Three neck reaction flasks are equipped with induction stirring, reflux exchanger, thermometer and feed hopper, with stirring into suspension in zinc oxide 0.6mol and the 250ml ethyl acetate adding reaction flask, drip the 0.1mol F that is pre-mixed under 20 ℃ of water-baths coolings
3C (CF
2)
Y(CH
2)
XSi (CH
3) Cl
2(X=2; Y=10) and 0.5mol ethyl-methyl dichlorosilane mixture; Continue reaction 2h after adding the dichlorosilane mixture; Behind reaction solution washing 150ml * 2 time again with distillation washing 150ml * 2 time; With the anhydrous sodium sulfate drying after-filtration, steaming removes ethyl acetate and obtains fluorine-containing hybrid ring siloxane 82.2g, and productive rate (by the dichlorosilane total amount) is 71.0%.Product fluorine content is 34.26%.
Embodiment 4
Three neck reaction flasks are equipped with induction stirring, reflux exchanger, thermometer and feed hopper, with stirring into suspension in zinc oxide 0.5mol and the 200ml ethyl acetate adding reaction flask, drip the 0.1mol F that is pre-mixed under 20 ℃ of water-baths coolings
3C (CF
2)
Y(CH
2)
XSi (CH
3) Cl
2(X=2; Y=6) and 0.4mol ethyl-methyl dichlorosilane mixture; Continue reaction 2h after adding the dichlorosilane mixture; Behind reaction solution washing 150ml * 2 time again with distillation washing 150ml * 2 time; With the anhydrous sodium sulfate drying after-filtration, steaming removes ethyl acetate and obtains fluorine-containing hybrid ring siloxane 48.1g, and productive rate (by the dichlorosilane total amount) is 63.4%.Product fluorine content is 32.33%.
Embodiment 5
10L three neck reaction flasks are equipped with induction stirring, reflux exchanger, thermometer and feed hopper, with stirring into suspension in zinc oxide 583 (7.2mol) g and the 6L ethyl acetate adding reaction flask, under 20 ℃ of ice-water baths coolings, drip 675g (3.2mol) F that is pre-mixed
3C (CF
2)
Y(CH
2)
XSi (CH
3) Cl
2(X=2; Y=0) and 516g (4mol) dimethyldichlorosilane(DMCS) mixture, control reaction temperature is lower than 20 ℃; Continue reaction 2h after adding the dichlorosilane mixture; Behind reaction solution washing 1L * 3 time again with distillation washing 1L * 2 time; With the dry after-filtration of anhydrous sodium sulphate 100g, steaming removes ethyl acetate and obtains fluorine-containing hybrid ring siloxane 753g, and productive rate is 94.7%.Product fluorine content is 21.08%.
Embodiment 6
10L three neck reaction flasks are equipped with induction stirring, reflux exchanger, thermometer and feed hopper, with stirring into suspension in 1166 (14.4mol) g zinc oxide and the 8L ethyl acetate adding reaction flask, under 20 ℃ of ice-water baths coolings, drip 1350g (6.4mol) F that is pre-mixed
3C (CF
2)
Y(CH
2)
XSi (CH
3) Cl
2(X=2; Y=0) and 1030g (8mol) dimethyldichlorosilane(DMCS) mixture, control reaction temperature is lower than 15 ℃; Continue reaction 1h after adding the dichlorosilane mixture; Behind reaction solution washing 2L * 2 time again with distillation washing 2L * 2 time; With the anhydrous sodium sulfate drying after-filtration, steaming removes ethyl acetate and obtains fluorine-containing hybrid ring siloxane 1586g.Product fluorine content is 21.22%.
Embodiment 7
1L there-necked flask configuration induction stirring, nitrogen protection, reflux condensation mode (connecing drying tube), with fluorine-containing hybrid ring siloxane (R=methyl, X=2, Y=0) 750g, hexamethyldisiloxane (MM) 113g (cyclosiloxane weight 15%) and 1.1g trifluoromethanesulfonic acid are warming up to 70 ℃ after stirring 30min; Be cooled to 60 ℃ behind the reaction 20h, add 2.5mL25% ammoniacal liquor, continue to stir 2h, steam except that low fraction in 200 ℃ (3mmHg), then by thin film column vacuum distilling (207 ℃ 25pa) are further steamed except that low cut, get fluorosilicon oil 553g at last, productive rate (in hybrid ring siloxane) is 63.9%.
60 days performances of gained fluorosilicon oil normal temperature sealed storage are constant substantially, data such as following table 1:
Table 1 fluorosilicon oil base oil storge quality
| Performance | Initial storage stored 60 days in 30 days |
| Fluorine content (F, %) | 20.52 20.55 20.55 |
| Viscosity (100 ℃, mm 2/s) | 8.16 8.07 8.10 |
| Viscosity (40 ℃, mm 2/s) | 647.03 656.05 654.97 |
| Open flash point (℃) | 254 254 252 |
Claims (8)
1, a kind of fluorine-containing hybrid ring siloxane, it has following structural formula:
R wherein
1=C
1～4Alkyl, phenyl; R
2=methyl, phenyl; M=0,1,2; The integer of n=3～10; X=2,3; The integer of Y=0～11.
2, a kind of fluorine-containing hybrid ring siloxane as claimed in claim 1 is characterized in that the described fluorine content that contains the fluoroalkyl dichlorosilane is 10%～60%.
3, a kind of preparation method of fluorine-containing hybrid ring siloxane as claimed in claim 1, it is characterized in that in organic solvent and under-20 ℃～80 ℃ temperature, with fluorine-containing alkyl methyl dichlorosilane and dialkyl dichlorosilane mixing raw material, with metal oxide or alkaline carbonate dechlorination, reacted 0.1～5 hour; The mol ratio of described fluorine-containing alkyl methyl dichlorosilane, dialkyl dichlorosilane and alkalimetal oxide or alkaline carbonate is followed successively by 0.1～5: 1: 0.5～5; The described fluoroalkyl dichlorosilane molecular formula that contains is F
3C (CF
2) Y (CH
2)
XSi (CH
3) Cl
2Described dialkyl dichlorosilane molecular formula is R
1R
2SiCl
2, wherein, R
1Alkyl or phenyl for C1～4; R
2=methyl, phenyl; X=2,3; The integer of Y=0～11.
4, the preparation method of a kind of fluorine-containing hybrid ring siloxane as claimed in claim 1 is characterized in that described metal oxide is zinc oxide, barium oxide, calcium oxide, magnesium oxide, cupric oxide, Manganse Dioxide or plumbic oxide; Described alkaline carbonate is yellow soda ash, salt of wormwood.
5, the preparation method of a kind of fluorine-containing hybrid ring siloxane as claimed in claim 2 is characterized in that described organic solvent is ethyl acetate, methyl acetate, sherwood oil, normal hexane, hexanaphthene, benzene, toluene or methylene dichloride.
6, the preparation method of a kind of fluorine-containing hybrid ring siloxane as claimed in claim 2 is characterized in that described fluorine-containing alkyl methyl dichlorosilane and dialkyl dichlorosilane mole are 0.2～3: 1.
7, the preparation method of a kind of fluorine-containing hybrid ring siloxane as claimed in claim 2 is characterized in that described temperature of reaction is to be 0 ℃～30 ℃.
8, a kind of purposes of fluorine-containing hybrid ring siloxane as claimed in claim 1 is characterized in that being used for synthetic fluorosilicon oil, hydroxyl fluorosilicon oil and fluorine silicon rubber.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031289096A CN1181081C (en) | 2003-05-28 | 2003-05-28 | Mixed fluorinated cyclosiloxane, preparing method and use thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031289096A CN1181081C (en) | 2003-05-28 | 2003-05-28 | Mixed fluorinated cyclosiloxane, preparing method and use thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1456564A CN1456564A (en) | 2003-11-19 |
| CN1181081C true CN1181081C (en) | 2004-12-22 |
Family
ID=29411705
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB031289096A Expired - Fee Related CN1181081C (en) | 2003-05-28 | 2003-05-28 | Mixed fluorinated cyclosiloxane, preparing method and use thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1181081C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10364327B2 (en) | 2016-02-01 | 2019-07-30 | Lg Chem, Ltd. | Polyorganosiloxane and copolycarbonate prepared by using the same |
Families Citing this family (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100386362C (en) * | 2005-06-13 | 2008-05-07 | 上海三爱富新材料股份有限公司 | Catalyst composition and preparation method of fluorine silicon contained polymer |
| CN100371369C (en) * | 2005-07-07 | 2008-02-27 | 中国科学院广州化学研究所 | Aqueous silicon fluoro polymer and its preparation method and water dispersion of said polymer |
| CN100457803C (en) * | 2006-11-28 | 2009-02-04 | 苏州大学 | Fluoric alkoxyl propyl methyl silicone oil and its prepn process |
| CN101684125B (en) * | 2008-09-26 | 2012-02-29 | 中国科学院兰州化学物理研究所 | Fluorine-containing silicon carbon hydrogen compound and preparation method thereof |
| CN101402733B (en) * | 2008-10-28 | 2011-03-30 | 苏州大学 | Novel fluorine phenyl-containing silicone oil and method of producing the same |
| WO2010129758A1 (en) * | 2009-05-06 | 2010-11-11 | 3M Innovative Properties Company | Medicinal inhalation devices and components thereof |
| CN101780385B (en) * | 2009-12-07 | 2012-05-09 | 江苏赛欧信越消泡剂有限公司 | Preparation method of fluorosilicone oil with efficient defoaming performance |
| CN101948481A (en) * | 2010-10-08 | 2011-01-19 | 威海新元化工有限公司 | Method for synthesizing low molecular weight hydroxy-terminated fluorine silicon oil |
| CN102220014B (en) * | 2011-06-01 | 2013-04-03 | 山东大学 | High-strength fluorinated silicone rubber gross rubber and preparation method thereof |
| CN102225997B (en) * | 2011-06-02 | 2012-11-28 | 山东大学 | Preparation method of raw fluorinated silicone rubber with high molecular weight |
| CN104829839B (en) * | 2015-05-12 | 2017-07-18 | 傅筠 | A kind of fluoro organosilicon polymer and preparation method thereof |
| CN105295052B (en) * | 2015-08-25 | 2019-01-29 | 浙江大学 | A kind of chain alkyl phenyl fluorosilicon oil and preparation method thereof |
| CN105085567B (en) * | 2015-08-25 | 2018-04-20 | 浙江大学 | Cyclosiloxane that polyfunctional group substitutes altogether, ring siloxane mixture and its preparation method and application |
| CN106085557B (en) * | 2016-06-08 | 2018-12-18 | 中国科学院上海有机化学研究所 | A kind of environmental-friendly high-performance lubricating grease |
| CN109337729B (en) * | 2018-09-29 | 2021-10-08 | 李旭东 | Fluorine-containing organosilicon lubricating oil base oil and preparation method thereof |
| CN109518303B (en) * | 2018-11-27 | 2021-06-11 | 华峰化学股份有限公司 | Sheath-core alkali-washing-resistant high-temperature-resistant elastic fiber and preparation method thereof |
| CN110156826B (en) * | 2019-06-20 | 2021-08-31 | 威海新元化工有限公司 | Diphenyl cyclotrisiloxane and preparation method and application thereof |
| CN113004522B (en) * | 2021-03-05 | 2022-03-15 | 无锡龙驰氟硅新材料有限公司 | Low-surface-energy fluorine-silicon additive for epoxy resin and preparation method thereof |
| CN113616973B (en) * | 2021-08-19 | 2022-05-13 | 四川大学 | Catalytic cracking method of waste perfluoropolyether lubricating oil |
-
2003
- 2003-05-28 CN CNB031289096A patent/CN1181081C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10364327B2 (en) | 2016-02-01 | 2019-07-30 | Lg Chem, Ltd. | Polyorganosiloxane and copolycarbonate prepared by using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1456564A (en) | 2003-11-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1181081C (en) | Mixed fluorinated cyclosiloxane, preparing method and use thereof | |
| CN105295052B (en) | A kind of chain alkyl phenyl fluorosilicon oil and preparation method thereof | |
| JP5283553B2 (en) | Thermally conductive silicone grease composition | |
| US6818600B2 (en) | Heat-dissipating silicone grease composition | |
| US7838614B2 (en) | Siloxane containing block copolymers, process for their preparation and their use for lubricants | |
| CN1349993A (en) | Preparation of amino-functional silicone | |
| CN1304540C (en) | Fluorinated silicone lube oil synthetic method | |
| CN1974633A (en) | Fluoric alkoxyl propyl methyl silicone oil and its prepn process | |
| US5026893A (en) | Polysilahydrocarbon lubricants | |
| US4788312A (en) | Trisilahydrocarbon lubricants | |
| CN101402733B (en) | Novel fluorine phenyl-containing silicone oil and method of producing the same | |
| CN103642046B (en) | A kind of preparation method of end-vinyl fluorosilicon oil | |
| CN108586747B (en) | Preparation method of methyl phenyl silicone oil with medium and high phenyl content | |
| EP0919583B1 (en) | Method of producing branched silicone oil | |
| CN1252141C (en) | Method for production of hydroxyalkyl polysiloxanes | |
| CN109337729B (en) | Fluorine-containing organosilicon lubricating oil base oil and preparation method thereof | |
| US5445751A (en) | Fluorosilicone lubricant compositions | |
| CN1633458A (en) | Aminomethylene-functional siloxanes | |
| CN105085567A (en) | Multiple functional groups co-substituted cyclosiloxane, cyclosiloxane mixture, and preparation method and application of cyclosiloxane mixture | |
| CN109535427A (en) | A kind of preparation method of ethenyl blocking fluorosilicon oil | |
| CN108676604A (en) | A kind of phenyl-fluoride silicon grease and preparation method thereof | |
| CN115028839A (en) | Preparation method of methyl phenoxy silicone oil | |
| CN1308365C (en) | Production of Redix with siloxane structural unit | |
| CN111333843B (en) | Preparation method of alkoxy-terminated polysiloxane | |
| US20070197757A1 (en) | Continuous production of aminofunctional siloxanes |
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 | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20041222 Termination date: 20100528 |