CN1304540C - Fluorinated silicone lube oil synthetic method - Google Patents
Fluorinated silicone lube oil synthetic method Download PDFInfo
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- CN1304540C CN1304540C CNB03128910XA CN03128910A CN1304540C CN 1304540 C CN1304540 C CN 1304540C CN B03128910X A CNB03128910X A CN B03128910XA CN 03128910 A CN03128910 A CN 03128910A CN 1304540 C CN1304540 C CN 1304540C
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Abstract
The present invention relates to a synthetic method of fluorin-silicon lubricating oil. A multi-component hybrid ring siloxane intermediate containing fluorine, which is obtained by that a mixture of fluorine dichlorodecylmethylsilane containing the fluorine and dialkyl dichlorosilane is dechlorinated and synthesized by a metallic oxide, is used as a raw material, and polysiloxane containing the fluorine, which is directly obtained by that strong acid induces ring-opening polymerization, has the structural formula, wherein R1 is the alkyl and the phenyl of C<1 to 4>, R2 is phenyl and phenyl p=0, 1, 2, q is an integer from 3 to 20, X is 2 and 3, Y is an integer of 0 to 11, and R' is ethenyl, hydroxyl or trimethylsilyl. The number-average molar mass of the polysiloxane containing the fluorine obtained by the synthetic method is from 1500 to 8000, the fluorine content is from 10% to 60%, and the synthetic method is fluorin-silicon lubricating oil with high performance.
Description
Technical field
The present invention relates to a kind of fluorine silicon grease and synthetic method by fluorine-containing alkyl methyl dichlorosilane, prepare fluorine-containing mixed methylcyclosiloxane by fluorine-containing alkyl methyl dichlorosilane and dialkyl dichlorosilane mixture through the metal oxide dechlorination, with strong acid catalysis ring-opening polymerization, control molecular weight and molecular weight distribution obtain the fluorine silicon grease of high comprehensive performance again.
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 in the dimethyl-silicon oil molecule, replace part methyl, then can make the fluorine silicon grease that is used under high and low temperature and the high pressure to contain fluoroalkyl.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.And silicone oil inherent high temperature performance and viscosity temperature characteristic more make fluorosilicon oil become possibility as extraordinary high temperature grease.
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, the base catalysis balanced system gets in the presence of the end-capping reagent hexamethyldisiloxane again.The methyl that links to each other with silicon in the methyl cyclosiloxane has quickened the chain-breaking reaction of cyclosiloxane under the nucleophilic reagent effect after being replaced by trifluoro propyl.It is reported, 1,3,5-trimethylammonium-1,3,5-three (γ-trifluoro propyl) cyclotrisiloxane (D
3 F) than hexamethyl cyclotrisiloxane (D
3) almost fast 4~5 times of cationoid polymerisation speed, and than octamethylcyclotetrasiloxane (D
4) fast 400 times.The increase of this speed of response is because the big stress of fluorine-containing cyclosiloxane, and the inductive effect of fluoro substituents, makes Siliciumatom have more positive polarity and is subject in nucleophilic reagent attack, the ring siloxane bond fracture and reacts.D
3 FPolymerization velocity also relevant with catalyst system therefor character, as KOH, NaOH and LiOH the ratio of the catalyzed polymerization speed of this ring body is about 900: 20: 1, the shortcoming of this class catalyst system is: behind the highly basic initiated polymerization, the silicon alkoxide reactive terminal of existence is a labile factor, needs with weak acid, Me
3SiCl etc. remove.By comparison, but with reactive terminal thermal degradation after quaternary ammonium hydroxide and the season phosphonium salt catalyzed reaction and disappear, this makes aftertreatment very easy.
In recent years, the appearance that causes cyclosiloxane positively charged ion ring-opening polymerization method with strong acid makes silicone oil preparation technology more rich and varied, as H
2SO
4, CF
3COOH, HClO
4, CF
3SO
3H etc., wherein CF
3SO
3H causes particularly outstanding.CF
3SO
3The by force acid and reaction system consistency of H is good, and the efficiency of initiation height is so be usually used in the research of cyclosiloxane ring-opening polymerization mechanism.There are some researches show, with CF
3SO
3H causes D
3During ring-opening polymerization, reaction ends and records 75% CF
3SO
3H exists with the form of sulfonic acid silanol ester, and has only 25% free CF in the system
3SO
3H, this also makes troubles to aftertreatment.Such cationic catalyst that sees report also has Zeo-karb, acidic white earth etc.Wherein acidic white earth has high reactivity, lower concentration, stable storing, advantage cheap and easy to get, and is easy to remove from product, so its use range is the most extensive.
It is many to prepare the silicone oil reactions steps by the cyclosiloxane ring-opening polymerization of single structure, and by comparison, co-hydrolysis prepares silicone oil and uses more extensive.Co-hydrolysis promptly in the presence of end-capping reagent, is obtained the silicone oil product of certain molecular weight and molecular weight distribution by the cohydrolysis product polycondensation of mixed chlorosilane.This method has following shortcoming, and at first, the terminal hydroxy group in the cohydrolysis product generates a large amount of water in polycondensation, influences the catalytic efficiency of catalyzer; Secondly, the HCl that generates in the hydrolytic process can make part Si-C bond rupture, generates the three-functionality-degree chain link; And the component of the synthetic fluorosilicon oil product that obtains of hydrolytie polycondensation method disperses relatively, and wherein the existence of residual hydroxy groups influences the stability in storage of silicone oil product, so prepare at preparation high performance fluorine silicone oil or the fluorine-containing cyclosiloxane ring-opening polymerization of the appropriate to the occasion employing of trifluoropropyl siloxane.In addition, produce a large amount of strongly acid wastewaters during co-hydrolysis is produced, need neutralizing treatment.
When traditional co-hydrolysis is produced polysiloxane, the existence of hydroxyl influences the quality control and the production technique of product, produce polysiloxane by the cyclosiloxane ring-opening polymerization and then can overcome above shortcoming, but the cyclosiloxane that has is difficult to obtain, by the metal oxide dechlorination prepare hybrid ring siloxane again ring-opening polymerization produce the shortcoming that polysiloxane has then overcome preceding two kinds of methods simultaneously.
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.
A kind of ' fluorine-containing hybrid ring siloxane, preparation method and its usage ' Chinese patent of people such as Tang Songqing invention provides possibility for the synthetic fluorine silicon grease of the present invention.
Summary of the invention
The object of the invention provides a kind of fluorine silicon grease and synthetic method.
The fluorine silicon grease that the present invention provides has the fluorinated polysiloxane of following structural formula;
R wherein
1=C
1~4Alkyl or phenyl;
R
2=methyl or phenyl;
P=0,1 or 2; The integer of q=3~20;
X=2 or 3; The integer of Y=0~11;
R ' is vinyl or methyl.
The number-average molecular weight of described fluorinated polysiloxane is 1500~8000; Fluorine content is 10%~60%.
The inventive method is suitably a kind of with the metal oxide dechlorination, prepares fluorine-containing hybrid silicone by fluorine-containing dichlorosilane, dihydroxyl dichlorosilane mixture, prepares the new method of fluorine silicon grease again with strong acid catalysis ring-opening polymerization.
The fluorine-containing polynary mixed methylcyclosiloxane that makes after dechlorination reaction finished needn't be fractionated into certain single ring body, and is directly used in next step polyreaction, and reaction formula is as follows;
R wherein
1=C
1~4Alkyl or phenyl;
R
2=methyl or phenyl;
M=0,1 or 2; The integer of n=3~10;
P=0,1 or 2; The integer of q=3~20;
X=2 or 3; The integer of Y=0~11,
R ' is vinyl or methyl.
In the method for the present invention, adopting the fluorine-containing hybrid ring siloxane with following structural formula is raw material:
R wherein
1=C
1~4Alkyl, phenyl;
R
2=methyl or phenyl;
M=0,1 or 2; The integer of n=3~10;
X=2 or 3; The integer of Y=0~11.
The end-capping reagent that adopts in the method for the present invention can be hexamethyldisiloxane, divinyl tetramethyl disiloxane or tetramethyl-dichloro two silica silane.When R ' in the reaction product was vinyl or hydroxyl, polysiloxane still had reactivity, generated silicon rubber or the further condensation of terminal hydroxy group as vulcanizing.The weight ratio of end-capping reagent and hybrid ring siloxane is 0.03~0.30, is preferably 0.10~0.20: 1 of hybrid ring siloxane.
Adopting the strong acid as initiator in the method for the present invention is H
2SO
4, CF
3COOH, HClO
4, CF
3SO
3H etc.The weight ratio of strong acid and hybrid ring siloxane is 0.005~0.15: 1, is preferably 0.08~0.12: 1.
The ring-opening polymerization time is 5~50h in the method for the present invention, is preferably 16~24h.Temperature of reaction is 10 ℃~120 ℃, is preferably 20~90 ℃.
Use CF
3SO
3Efficiency of initiation height when H causes, consumption is few, only needs 0.2 ‰ of hybrid ring siloxane can reach good initiation effect, but considers reaction efficiency and aftertreatment etc., adopts 0.5~1.5 ‰ effect best.Reaction times is preferably 5~24h.Temperature of reaction is preferably 70~80 ℃.
Can add alkaline matter in the method for the present invention and come termination reaction, described alkaline matter can mineral alkali or organic bases, mineral alkali can be carbonate or oxyhydroxide, the ammoniacal liquor etc. of monovalence or divalent metal, and organic bases can be pyridine, triethylamine, diethylamine etc.CF
3SO
3When H causes because most of CF
3SO
3H exists with the form of sulfonic acid silanol ester, and adoptable alkaline matter preferably ammoniacal liquor comes termination reaction.The mol ratio of alkaline matter and hybrid ring siloxane is 0~10: 1, is recommended as 0.05~10: 1.Remove CF
3SO
3Outside the H, big during other strong acid catalysis owing to consumption, but the silanol ester amount that generates in the catalytic process is few, and aftertreatment adopts WATER-WASHING METHOD to remove.
The inventive method has been avoided the generation of a large amount of strongly acid wastewaters in the direct cohydrolysis method, and the existence of terminal hydroxy group in a large number in the cohydrolysis product, and the product property that obtains is stable, and aftertreatment is simple, and the reaction times is short.In the fluorosilicon oil building-up process, by containing the relative content of fluoroalkyl and methyl in the control fluorosilicon oil, make fluorosilicon oil have the excellent comprehensive performance, the fluorosilicon oil that can prepare high flash point (250~300 ℃), low condensation point (pour point) especially and can in-50~250 ℃ of broad temperature ranges, use, simultaneously, also help reducing the cost of fluorosilicon oil product.
Specific embodiment
The fluorine-containing polynary mixed methylcyclosiloxane that adopts among all embodiment is for to be made according to mol ratio dechlorination cyclisation in 1: 1 by two kinds of dichlorosilanes.
Embodiment 1
Three neck reaction flasks are equipped with induction stirring, reflux exchanger, thermometer and water-bath, with fluorine-containing hybrid ring siloxane (R
1, R
2Be methyl, X=2, Y=6) 16g, end-capping reagent divinyl tetramethyl disiloxane 2.4g (hybrid ring siloxane weight 15%) and 95% sulfuric acid 1.92g add in the reaction flask successively, are warming up to 30 ℃ after stirring 30min; Reaction 40h postcooling adds normal hexane 20ml to room temperature, is washed to neutrality, steams then to desolventize and low cut, gets fluorinated polysiloxane 13.5g, and productive rate is 73.5%.Product is a colourless transparent liquid, and viscosity (40 ℃) is 1536.6mm
2/ s, fluorine content are 44.3%.
Embodiment 2
Three neck reaction flasks are equipped with induction stirring, reflux exchanger, thermometer and water-bath, with fluorine-containing hybrid ring siloxane (R
1Be methyl, R
2Be ethyl, X=2, Y=0) 16g, end-capping reagent divinyl tetramethyl disiloxane 3.2g (hybrid ring siloxane weight 20%) and 0.8g perchloric acid add in the reaction flask successively, are warming up to 30 ℃ after stirring 30min; Reaction 30h postcooling adds normal hexane 20ml to room temperature, is washed to neutrality, steams then to desolventize and low cut, gets fluorinated polysiloxane 15.6g, and productive rate is 80.9%.Product viscosity (40 ℃) is 605.9mm
2/ s, fluorine content are 20.7%.
Embodiment 3
Three neck reaction flasks are equipped with induction stirring, reflux exchanger, thermometer and water-bath, with fluorine-containing hybrid ring siloxane (R
1, R
2Be methyl, X=2, Y=10) 20g, end-capping reagent divinyl tetramethyl disiloxane 3g and 0.8g95%H
2SO
4Add successively in the reaction flask, be warming up to 30 ℃ behind the stirring 30min; Reaction 30h postcooling adds normal hexane 20ml to room temperature, is washed to neutrality, steams then to desolventize and low cut, gets fluorinated polysiloxane solid 17g, and productive rate is 73.5%.Product fluorine content is 56.6%.
Embodiment 4
Three neck reaction flasks are equipped with induction stirring, reflux exchanger, thermometer and water-bath, with fluorine-containing hybrid ring siloxane (R
1, R
2Be methyl, X=2, Y=0) 750g, end-capping reagent hexamethyldisiloxane (MM) 113g (cyclosiloxane weight 15%) and 1.1gCF
3SO
3H adds in the reaction flask successively, is warming up to 70 ℃ behind the stirring 30min; Be cooled to 60 ℃ behind the reaction 20h, add 2.5mL25% ammoniacal liquor, continue to stir 2h, steam to remove low fraction in 200 ℃ (3mmHg), then by thin film column vacuum distilling further steam remove low fraction (207 ℃, 25pa), 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, physicochemical property data such as following table 1:
Table 1 fluorosilicon oil base oil stability in storage
Performance | Initial | Store 30 days | Store 60 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 |
Embodiment 5
Three neck reaction flasks are equipped with induction stirring, reflux exchanger, thermometer and water-bath, with fluorine-containing hybrid ring siloxane (R
1, R
2Be methyl, X=2, Y=0) 1586g, end-capping reagent hexamethyldisiloxane (MM) 206g and 2.38gCF
3SO
3H adds in the reaction flask successively, is warming up to 80 ℃ behind the stirring 30min; Be cooled to 60 ℃ behind the reaction 20h, add 8mL25% ammoniacal liquor, continue to stir 2h; Add the 1500ml normal hexane, washing 1000ml * 4 time are steamed then and are desolventized and low cut, at last fluorosilicon oil 1606g, productive rate (in hybrid ring siloxane) is 89.6%.The refining 30 days performances of fluorosilicon oil normal temperature sealed storage of gained are constant after again product further being removed low cut and high boiling material with the short-path distillation instrument, data such as following table 2:
The silica-based plinth oiliness of the fluorine that table 2 short-path distillation obtains energy
Performance | Initial | Store 30 days |
Fluorine content (F, %) | 20.8 | 20.81 |
Viscosity (100 ℃, mm 2/s) | 9.94 | 9.96 |
Viscosity (40 ℃, mm 2/s) | 909.8 | 884.0 |
Open flash point (℃) | 286 | 284 |
Claims (10)
1, a kind of fluorine silicon grease is characterized in that having the fluorinated polysiloxane of following structural formula:
R wherein
1=C
1~4Alkyl; R
2=methyl; P=0,1 or 2; The integer of q=3~10; X=2 or 3; The integer of Y=0~11; R ' is vinyl or methyl.
2, a kind of fluorine silicon grease as claimed in claim 1, the number-average molecular weight that it is characterized in that its described fluorinated polysiloxane is 1500~8000; Fluorine content is 10%~60%.
3, the synthetic method of a kind of fluorine silicon grease as claimed in claim 1, it is characterized in that described by fluorine-containing hybrid ring siloxane, end-capping reagent, strong acid and alkali substance reaction 5~50 hours, the weight ratio of wherein fluorine-containing hybrid ring siloxane, end-capping reagent, strong acid and alkaline matter is 1: 0.03~0.30: 0.005~0.15: 0~10, and described fluorine-containing hybrid ring siloxane has following structural formula:
Wherein, m=0,1 or 2, the integer of n=3~10, R
1, R
2, X and Y according to claim 1.
4, the synthetic method of a kind of fluorine silicon grease as claimed in claim 3 is characterized in that described end-capping reagent is hexamethyldisiloxane or divinyl tetramethyl disiloxane.
5, the synthetic method of a kind of fluorine silicon grease as claimed in claim 3 is characterized in that described strong acid is mineral acid or organic acid, and described alkaline matter is mineral alkali or organic bases.
6, the synthetic method of a kind of fluorine silicon grease as claimed in claim 3 is characterized in that described mineral alkali is the carbonate or the oxyhydroxide of ammoniacal liquor, monovalence or divalent metal, and described organic bases is pyridine, triethylamine or diethylamine.
7, the synthetic method of a kind of fluorine silicon grease as claimed in claim 3, the weight ratio that it is characterized in that described end-capping reagent and fluorine-containing hybrid ring siloxane is 0.10~0.20: 1.
8, the synthetic method of a kind of fluorine silicon grease as claimed in claim 3 is characterized in that the strong acid that is adopted is H
2SO
4, CF
3COOH or HClO
4The time, the weight ratio of above-mentioned acid and fluorine-containing hybrid ring siloxane is 0.08~0.12: 1.
9, the synthetic method of a kind of fluorine silicon grease as claimed in claim 3 is characterized in that the reaction times is 16~24 hours, and temperature of reaction is 20~90 ℃.
10, the synthetic method of a kind of fluorine silicon grease as claimed in claim 3 is characterized in that described strong acid is CF
3SO
3During H, its consumption is that the weight ratio of fluorine-containing hybrid ring siloxane is 0.5~1.5 ‰, and the mol ratio of alkaline matter and fluorine-containing hybrid ring siloxane is 0.05~10: 1, and the reaction times is 5~24 hours; Temperature of reaction is 70~80 ℃.
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Families Citing this family (12)
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CN100457803C (en) * | 2006-11-28 | 2009-02-04 | 苏州大学 | Fluoric alkoxyl propyl methyl silicone oil and its prepn process |
CN101402733B (en) * | 2008-10-28 | 2011-03-30 | 苏州大学 | Novel fluorine phenyl-containing silicone oil and method of producing the same |
CN101967229B (en) * | 2010-10-20 | 2012-08-15 | 苏州大学 | Fluorine-containing silicone oil and preparation method thereof |
CN104862029A (en) * | 2014-02-21 | 2015-08-26 | 上海云中化学有限公司 | Fluorine silicone grease composition |
CN105295052B (en) * | 2015-08-25 | 2019-01-29 | 浙江大学 | A kind of chain alkyl phenyl fluorosilicon oil and preparation method thereof |
CN105733754B (en) * | 2016-01-27 | 2020-01-21 | 深圳市旭生三益科技有限公司 | Insulating lubricating grease containing fluorosilicone oil and preparation method thereof |
CN106883410B (en) * | 2017-03-06 | 2020-02-04 | 宜昌科林硅材料有限公司 | Perfluoroether-based polysiloxane, and preparation method and application thereof |
CN109851787A (en) * | 2017-11-30 | 2019-06-07 | 深圳市冠恒新材料科技有限公司 | A kind of fluorine silicon rubber base glue and preparation method thereof |
CN108250441A (en) * | 2017-12-29 | 2018-07-06 | 美瑞新材料股份有限公司 | A kind of preparation method of the hydrogeneous fluorosilicon oil in end |
CN109337729B (en) * | 2018-09-29 | 2021-10-08 | 李旭东 | Fluorine-containing organosilicon lubricating oil base oil and preparation method thereof |
CN112552516B (en) * | 2020-12-17 | 2022-07-01 | 山东东岳高分子材料有限公司 | Modified polysiloxane containing fluorine ring bodies, preparation method and application thereof |
CN113476902B (en) * | 2021-07-05 | 2023-03-24 | 中国石油化工股份有限公司 | Dispersing method of fluorosilicone oil defoaming agent |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4652386A (en) * | 1984-10-03 | 1987-03-24 | Bayer Aktiengesellschaft | Lubricating oil preparations |
US5084196A (en) * | 1988-01-29 | 1992-01-28 | Idemitsu Kosan Company Limited | Lubricating oil composition for flon atmosphere comprising a polysiloxane having epoxy structure |
US5470504A (en) * | 1994-01-21 | 1995-11-28 | Bardahl Manufacturing Corporation | Siloxane polymer compositions |
JP2000087065A (en) * | 1998-09-10 | 2000-03-28 | Idemitsu Kosan Co Ltd | Lubricating oil composition |
JP2001049285A (en) * | 1999-08-06 | 2001-02-20 | Daikin Ind Ltd | Transparent lubricating film and lubricant composition |
-
2003
- 2003-05-28 CN CNB03128910XA patent/CN1304540C/en not_active Expired - Fee Related
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4652386A (en) * | 1984-10-03 | 1987-03-24 | Bayer Aktiengesellschaft | Lubricating oil preparations |
US5084196A (en) * | 1988-01-29 | 1992-01-28 | Idemitsu Kosan Company Limited | Lubricating oil composition for flon atmosphere comprising a polysiloxane having epoxy structure |
US5470504A (en) * | 1994-01-21 | 1995-11-28 | Bardahl Manufacturing Corporation | Siloxane polymer compositions |
JP2000087065A (en) * | 1998-09-10 | 2000-03-28 | Idemitsu Kosan Co Ltd | Lubricating oil composition |
JP2001049285A (en) * | 1999-08-06 | 2001-02-20 | Daikin Ind Ltd | Transparent lubricating film and lubricant composition |
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