GB2301589A - fluorinated polysiloxane and cyclosiloxane oils - Google Patents
fluorinated polysiloxane and cyclosiloxane oils Download PDFInfo
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- GB2301589A GB2301589A GB9510866A GB9510866A GB2301589A GB 2301589 A GB2301589 A GB 2301589A GB 9510866 A GB9510866 A GB 9510866A GB 9510866 A GB9510866 A GB 9510866A GB 2301589 A GB2301589 A GB 2301589A
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- oil
- rfzch2si
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- 239000003921 oil Substances 0.000 title claims abstract description 10
- -1 polysiloxane Polymers 0.000 title claims description 18
- 229920001296 polysiloxane Polymers 0.000 title claims description 16
- 239000000203 mixture Substances 0.000 claims abstract description 23
- 239000012530 fluid Substances 0.000 claims abstract description 10
- 150000001875 compounds Chemical class 0.000 claims description 43
- 238000000034 method Methods 0.000 claims description 15
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 claims description 10
- 239000010702 perfluoropolyether Substances 0.000 claims description 9
- 125000004122 cyclic group Chemical group 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 7
- 150000001336 alkenes Chemical class 0.000 claims description 6
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 claims description 6
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- NXPHGHWWQRMDIA-UHFFFAOYSA-M magnesium;carbanide;bromide Chemical compound [CH3-].[Mg+2].[Br-] NXPHGHWWQRMDIA-UHFFFAOYSA-M 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- 239000007790 solid phase Substances 0.000 claims description 4
- 239000007818 Grignard reagent Substances 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 150000004795 grignard reagents Chemical class 0.000 claims description 3
- 229910003002 lithium salt Inorganic materials 0.000 claims description 3
- 159000000002 lithium salts Chemical group 0.000 claims description 3
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 claims description 3
- 229920002845 Poly(methacrylic acid) Polymers 0.000 claims description 2
- 229920002472 Starch Polymers 0.000 claims description 2
- 230000018044 dehydration Effects 0.000 claims description 2
- 238000006297 dehydration reaction Methods 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 229920000554 ionomer Polymers 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 claims description 2
- 239000010457 zeolite Substances 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims 1
- 150000003926 acrylamides Chemical class 0.000 claims 1
- 229920013822 aminosilicone Polymers 0.000 claims 1
- 230000003301 hydrolyzing effect Effects 0.000 claims 1
- 229910021653 sulphate ion Inorganic materials 0.000 claims 1
- 239000002199 base oil Substances 0.000 abstract description 16
- 239000004721 Polyphenylene oxide Substances 0.000 abstract 1
- 229920000570 polyether Polymers 0.000 abstract 1
- 238000004821 distillation Methods 0.000 description 5
- 239000005046 Chlorosilane Substances 0.000 description 4
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- KTQYJQFGNYHXMB-UHFFFAOYSA-N dichloro(methyl)silicon Chemical compound C[Si](Cl)Cl KTQYJQFGNYHXMB-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000005048 methyldichlorosilane Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical class FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229910002621 H2PtCl6 Inorganic materials 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- 229920001774 Perfluoroether Polymers 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000005376 alkyl siloxane group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 235000011148 calcium chloride Nutrition 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000003709 fluoroalkyl group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000000413 hydrolysate Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
- C08G77/385—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing halogens
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0834—Compounds having one or more O-Si linkage
- C07F7/0838—Compounds with one or more Si-O-Si sequences
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/21—Cyclic compounds having at least one ring containing silicon, but no carbon in the ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/045—Polysiloxanes containing less than 25 silicon atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/24—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing groups
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M171/00—Lubricating compositions characterised by purely physical criteria, e.g. containing as base-material, thickener or additive, ingredients which are characterised exclusively by their numerically specified physical properties, i.e. containing ingredients which are physically well-defined but for which the chemical nature is either unspecified or only very vaguely indicated
- C10M171/001—Electrorheological fluids; smart fluids
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Lubricants (AREA)
Abstract
Oils of formula I and II wherein at least one X is a specified polyfluoropolyether moiety and any other is H, are usable as base oils for electro-rheological fluid compositions. In (I) and II: m is 1 to 6 n is 3 to 7 X is Z - R f where Z is CH 2 , CH(CH 3 ), CH 2 CH 2 or CH 2 CH 2 -O-CO- and R f is a fluorinated polyether moiety end-stopped by CF 3 .
Description
OTLS This invention relates to electro-rheological fluid (ERF) compositions, to base oils for use in such compositions, to fluorinated polysiloxane compounds for use as or in such base oils, and to the preparation of such compounds.
ERF compositions have been known and used for many years.
They comprise fine dielectric particles suspended in electrically non-conductive base oil, the viscosity of the composition changing markedly, rapidly and reversibly in response to changes of applied electric field. These properties have led to ERF compositions being used in various electro-mechanical devices, including clutches, shock absorbers, propeller shafts, vibrators, dampers etc. Numerous materials have been used as the particulate dielectric solid phase, including zeolites, silica gel, starches, and various polymers and ionomers. A number of different materials have been used or proposed as base oil, e.g. fluorosilicones these are compounds which have the fluorine in propyl (or higher alkyl) chains attached to silicon atoms of polysiloxane backbones, for example as in
where x is 2 or ore.
Evidence on the usefulness of fluorosilicone compounds as base oils for -R fluids is widely known from, for example,
EP-A-0284268, and GB-A-2210893.
We have found it extremely difficult to manufacture such compounds, wherein simple fluorinated alkyl groups are attached to a silicone chain or ring, of the density and low viscosity acknowledged in this prior art to be necessary for useful ER fluid base materials. EP-A-0284268 establishes a useful limit of molecular weight of such a polymer as being 200 to 700; we find that these fluorosilicones are of too low density unless the alkyl chains are longer than propyl, and in the latter case the viscosity can become too high to be ideal as an ER fluid base oil usable at working temperature.
The current invention teaches the attachment of perfluoropolyether chains, instead of the more usual simple fluoroalkyl chains, to the silicone chain or cyclic ring.
Such novel perfluoropolyether silicone compounds can be manufactured that have a molecular weight of above 600
(normally in the 700 to 2000 range or higher) whilst having low viscosity at 20 C of around 15 cps and achieving a density of around 1.40; in ERF compositions it is important to match fluid density with that of the solid materials - such as lithium salt of polymethacrylic acid, which is taught in prior documents mentioned above as being useful as the particulate component in ERF compositions.
As the manufacturing process will produce a mixture of various compounds of varying chain length and ring size which are controllable by adjustments to the manufacturing process, a feature of the invention is that both viscosity and density can be varied within quite wide ranges without the need to add other liquids, e.g. heavy perfluorocarbon or CTFE compounds or lighter alkyl siloxanes. Variations of viscosity and density can also be achieved by appropriate choice of molecular weight for the perfluoropolyether side chains.
The invention provides at least one compound selected from those of formulae I and II
wherein each X is selected independently from H and ZRf but in each formula at least one X is not H, and wherein
m is an integer of 1 to 6;
n is an integer of 3 to 7;
the or each Z is selected independently from -CH2-, -CH(CH3)-, -CH2CH2-, and
the or each Rf is selected independently from CF3O(CF2O)p (CF2CF2O)q CF2- and CF3O(CF2O)p(CF2CF(CF3)O)qCF2- and
CF30 (CFO)p(CF(CF2)CF2O)qCF-; p is an integer of 1 to 7; and
q is zero, 1 or 2.
Preferably, in formula I, each X is selected independently from H and CF3 (CF2O)pCF2CH (CH3) - and at least one
X is not H; p can for example be 5.
The present invention also provides a base oil for an ERF composition, which base oil comprises at least one compound selected from perfluoropolyether derivatives of linear and cyclic polysiloxanes. The base oil preferably comprises at least one perfluoropolyether derivative of a cyclic polysiloxane and at least one perfluoropolyether derivative of a linear polysiloxane. The invention also provides an ERF composition containing base oil according to the invention.
The base oil of the invention preferably has a density of from 1.3 to 1.6 g/cm and a viscosity less than 25 cps. Preferred base oils of the invention comprise at least one compound selected from those of formulae I and II above, most preferably a combination of at least one compound of formula
I and at least one compound of formula II.
The base oil according to the invention may include a minor amount (preferably less than 5 vol.%) of cyclic and/or linear polysiloxane of low molecular weight to reduce the overall viscosity to the required value. Such polysiloxane may for example be of sufficiently short chain or small ring as to have a viscosity below 10 cps at 20 C. The base oil may additionally or instead include high density non-conducting liquid (e.g. chlorotrifluoroethylene) to increase overall density. The density of the base oil should ideally be the same as that of the solid dielectric particles with which it is to be used in an ERF composition.
The preferred particulate dielectric solid phase for use in ERF compositions according to the invention is polymethylacrylic acid lithium salt, but others (including those mentioned above) could be used additionally or instead.
The dielectric particles are suitably of particle size in the 1-50 micron ran, and may be present in an amount of 5 to 60 volume % of the ERr composition; minimum amount is preferably 20 volume ; and the maximum amount is preferably 40 volume
The perfLloropolyether compounds according to the invention can be obtained by the following procedures.
A first method comprises rydrolysing a mixture of dichlorodimethylsilane and dichlorosilane of formula RfZCH2Si(CH3)CI2, blocking of end groups using hexamethyldisilazane (CH3)3SiNHSi(CH3)3 as chain terminator, and distilling the product with catalytic depolymerisation to obtain a compound or mixture of compounds of formula I/II.
Suitably the RfZCH2Si(CH3)Cl2 starting material for the above method is prepared by catalytic reaction of CH3SiHCl2 with olefinic compound RfZ1=CH2 where Z'= is -CH=, -C(CH3)= or -CH2CH=. Olefin RfZl=CH2 can be prepared by several routes.
When -Z' is C(CH3)=, RfC(CH3)=CH2 olefin can be prepared by dehydration of alcohol of formula RfC(CH3)2OH. The alcohol RfC(CH3)2OH can be prepared by reacting ester of formula
RfCOOCH3 with Grignard reagent CH3MgBr. In general, the
RfZCH2Si(CH3)Cl starting material is suitably made using fluoroorganic compound RfCOY where Y is F, Cl, OH, OCH3, OC2Hs. For example, if z is -CH(CH3)- a suitable route is
-RfCH (CH3) CH2Si (OH3) C.
if Z is -CH2-, a suitable route is
-RfCH2CH2Si (CH3) CQ2; if Z is -CH2CH2-, a suitable route is
RfCH2-CH=CH2-RfCH2CH2CH2Si (CM3) CQ2; This first method produces predominantly cyclic polysiloxanes of general formula I.
A second method comprises preparing at least one compound selected from those of formulae III and IV
wherein B is selected independently from H and -CH2CH2CX but in each formula at least one B is not H, and m and n are as defined hereinbefore, by co-hydrolysis of dimethyldichlorosilane (CH3)2SiCÇ2 with methyl-ychloropropyl dichlorosilane CH2ClCH2CH2Si(CH3)Cl2, reacting said chlorosiloxane(s) with perfluoro compound RfCOOM where M is Li, Na or K, and separating out resultant compound or mixture of compounds of formula I/II.
Compound RfCOOM may be obtained from compound RfCOY above.
This method produces predominantly linear polysiloxanes of general formula II.
In these methods, Rf is of course as defined hereinbefore. RfCO- is suitably CF30(CF20)sCF2CO-, with
Y being for example OCH3 (especially in the first method above) or OH (especially in the second method).
An Example of the above first method for obtaining a perfluoroether compound according to the invention will now be described in detail: E X A M P L E (a) Synthesis of chlorosilane RfZCH2Si(CH3)Cl2 using fluoroorganic polymer RfCOY where Y is OCH3, Rf is CF30(CF2O)sCF2-, and Z is -CH(CH3)-.
[i] Alcohol RfC (CH3)2OH is synthesised by adding 2253 g
(4.3 mol) of RfCOOCH3 to 3 liters of 3M Grignard reagent
CH3MgBr solution in THF at 5-10 C while stirring intensively for 3 hours,neutralising excess CH3MgBr with n-butanol (50 ml),removal of THF by vaccuum distillation and neutralisation of any THF residue by 10% HCl up to pH=3 while cooling; followed by separation of the organic layer from the water-salt fraction, washing it with water and drying using anhydrous Na2SO4, and extraction of alcohol of formula RfC (CH3)2OH by distillation.
Yield - 2028 g (90%); b.p. @ 5 mm Hg - 80 to 8100 IR spectrum - [OH] - 3400 cm-1; [CH3] - 3000 cm-1
[ii] synthesis of olefin RfC(CH3)=CH2 by reacting 1572 g of the alcohol obtained in [i] above with 470 g of P2Os at 100-140 C using an oil bath and stirring until the exothermic reaction is completed, and extraction of the olefin RfC(CH,)=CH2 by distillation at 0 to -1 atm. The olefin is further purified using a column of not less than 20 theoretical plates to take the 460C fraction.
Yield - 1290 g (85%), b.p. - 46 C at 10 mm Hg; IRspectrum: [OH3 - OH2] - 3000 2900 cm-1; [C=C] - 1760 cm-1 [iii] synthesis of chlorosilane RfZCN2S (OH3) Cl3 by catalytic reaction of the olefin obtained in [ii] above with methyldichlorosilane OH3SiHCl2; 316 g of methyldichlorosilane CH3SiHCl2 is placed into a reactor fitted with a stirrer and reverse refrigeration facilities and 5.5 ml of catalyst [0.1M solution of
H2PtCl6 in (CH3)2CHOH] is added dropwise to secure stable boiling of the methyldichlorosilane. In two hours 1265 g of RfC(CH3)=CH2 is added gradually, resulting in the chlorosilane RfZCH2Si(CH3)Cl2 being obtained by rectification at 900C and 11 mm Hg. Yield - 1382 g (89%).
(b) Co-hydrolysis of the chlorosilane obtained in (a) above with dimethyldichlorosilane (CH3)2SiCl2 is effected by adding gradually 932 g (1.5 mol) of RfZCH2Si(CH3)Cl2 and 1072 g (0.83 mol) of (CH3)2SiCl2 to 460 ml of water with stirring over one hour at below 400C leaving, the mixture still for 2 hours until two layers separate; isolating the lower layer and washing it with water until the pH is between 7 and 6, and drying over CaCl2. Yield - 940 g.
(c) Blockage of end groups with hexamethyldisilazane is effected by mixing 900 g of the co-hydrolysate obtained in (b) above with 36 g (0.22 mol) of hexamethyldisilazane at 1000C, and removal of ammonia and excess hexamethyldisilazane by vaccuum evaporation.
(d) Distillation combined with catalytic depolymerisation is performed by heating the mixture obtained in (c) above gradually to 250-320 C over 4-5 hours in the presence of catalyst (KOH) at 2 to 5 mm Hg, distillation to separate the fraction with b.p. of 180 to 230 C at 1 to 2 mm Hg, treating the distillate with Al203
(1% by weight) over 48 hours, and filtering through a dense ashless filter.
The product compound was of density 1.385 - 1.395, viscosity 15 cps, and average molecular weight 2000.
This product was a mixture of formula I (majority) and formula II (minority) compounds wherein X is CF30 (CF2Q)5CF2CH(CH3) -.
Claims (20)
1. At least one compound selected from those of formulae I and II
wherein each X is selected independently from H and ZRf but in each formula at least one X is not H, and wherein
m is an integer of 1 to 6;
n is an integer of 3 to 7;
the or each Z is selected independently from -CH2-, -CH(CH3)-, -CH2CH2-, and
the or each Rf is selected independently from CF30(CF20)p(CF2CF20)q CF2 CF30(CF20)p(CF2CF(CF3)0)q CF2- and
CF3O(CF2O)p(CF(CF3)CF2O)qCF2-;
p is an integer of 1 to 7; and
q is zero, 1 or 2.
2. At least one compound according to claim 1 selected from those of formula I wherein each X is selected independently from H and CF3(CF20)pCF2CH(CH3) and at least one X is not H.
3. At least one compound according to claim 1 or 2 of average molecular weight of at least 700.
4. An oil for use as the liquid component of an electro-rheological fluid, the oil comprising at least one compound selected from perfluoropolyether derivatives of linear and cyclic polysiloxanes.
5. An oil according to claim 4 comprising at least one perfluoropolyether derivative of a cyclic polysiloxane and at least one perfluoropolyether derivative of a linear polysiloxane.
6. An oil according to claim 4 comprising at least one compound according to claim 1 or 2 or 3.
7. An oil according to claim 6 comprising at least one compound of formula I and at least one compound of formula II.
8. An oil according to any of claims 4 to 7 having at 200C a density of from 1.3 to 1.6 g/cm3 and a viscosity less than 25 cps.
9. An oil according to any of claims 4 to 8 containing
[a] linear and/or cyclic polysiloxane to reduce overall viscosity, and/or [b] high density liquid to increase overall density.
10. An electro-rheological fluid having a liquid component according to any of claims 4 to 9.
11. A fluid according to claim 10 wherein the solid phase is selected from polymers, starches, zeolites, acrylamides and aminosilicone sulphate ionomers.
12. A fluid according to claim 10 wherein the solid phase is lithium salt of polymethacrylic acid.
13. A method of preparing a compound or compounds according to claim 1 which comprises hydrolysing a mixture of dimethyldichlorosilane and dichlorosilane of formula RfZCH2Si(CH3)Ct2, by blockage of end groups with hexamethyldisilazane as chain terminator, and distilling the product combined with catalytic depolymerisation to obtain a compound or mixture of compounds according to claim 1, Rf and Z being as defined in claim 1.
14. A method according to claim 13 wherein the RfZCH2Si(CH3)Ct2 is prepared by catalytic reaction of CH3SiHCB2 with olefinic compound RfZl=CH2 where Z'= is -CH=, -C(CH;)=, or -CH2CH=.
15. A method according to claim 14 wherein the olefin RfC (CH3) =CH2 is prepared by dehydration of alcohol of formula RO(CH3)OH.
16. A method according to claim 15 wherein the alcohol RfC (CH3) 2OH is prepared by reacting ester of formula RfCOOCH3 with Grignard reagent CH3MgBr.
17. A method of preparing a compound or compounds according to claim 1 where Z is -CH2-CH2-O-C- which
0 comprises preparing at least one compound selected from those of formulae III and IV
wherein B is -CH2CH2Cf and m and n are as defined in claim 1, reacting said chlorosiloxane(s) with perfluoro compound RfCOOM where M is Li, Na or K and Rf is as defined in claim 1, and separating out resultant compound or mixture of compounds according to claim 1.
18. Use of a compound of formula RfCOY wherein Rf is as defined in claim 1 and Y is F, C, OH, OCH3,OC2Hs in making a compound of formula RfZCH2Si(CH3)C22 wherein Z is as defined in claim 1.
19. Use of a compound of formula RfCOY wherein Rf is as defined in claim 1 and Y is F, CQ, OH, OCH3,OC2Hs, OLi, ONa or OK in making a compound according to claim 1, 2 or 3.
20. A compound of formula RfCOY wherein Rf is as defined in claim 1 and Y is Ct, OH, OCH3,OC2Hs, OLi, ONa, OK.
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB9510866A GB2301589A (en) | 1995-05-30 | 1995-05-30 | fluorinated polysiloxane and cyclosiloxane oils |
AU58409/96A AU5840996A (en) | 1995-05-30 | 1996-05-30 | Fluorinated polysiloxanes, their preparation and use in elec tro-rheological fluids |
PCT/GB1996/001301 WO1996038454A1 (en) | 1995-05-30 | 1996-05-30 | Fluorinated polysiloxanes, their preparation and use in electro-rheological fluids |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB9510866A GB2301589A (en) | 1995-05-30 | 1995-05-30 | fluorinated polysiloxane and cyclosiloxane oils |
Publications (2)
Publication Number | Publication Date |
---|---|
GB9510866D0 GB9510866D0 (en) | 1995-07-26 |
GB2301589A true GB2301589A (en) | 1996-12-11 |
Family
ID=10775219
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
GB9510866A Withdrawn GB2301589A (en) | 1995-05-30 | 1995-05-30 | fluorinated polysiloxane and cyclosiloxane oils |
Country Status (3)
Country | Link |
---|---|
AU (1) | AU5840996A (en) |
GB (1) | GB2301589A (en) |
WO (1) | WO1996038454A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107667125A (en) * | 2015-06-18 | 2018-02-06 | 陶氏环球技术有限责任公司 | Method for ERF to be made |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0384730A2 (en) * | 1989-02-21 | 1990-08-29 | Shin-Etsu Chemical Co., Ltd. | Process for preparing a fluoroorganopolysiloxane |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR1537922A (en) * | 1966-07-11 | 1968-08-30 | Montedison Spa | Derivatives of perfluorinated ethers and polyethers |
FR1545639A (en) * | 1966-07-12 | 1968-11-15 | Montedison Spa | Polyoxyperfluoromethylene compounds and method of preparation |
JPH0662647B2 (en) * | 1988-02-12 | 1994-08-17 | 信越化学工業株式会社 | Fluorine-containing organosilicon compound |
GB9114102D0 (en) * | 1991-06-29 | 1991-08-14 | Dow Corning | Electrorheological fluid containing a fluorohexylalkyl functional polysiloxane copolymer |
DE69311241T2 (en) * | 1992-09-21 | 1998-01-15 | Dow Corning | Improved electrorheological liquid preparations containing organosiloxanes |
-
1995
- 1995-05-30 GB GB9510866A patent/GB2301589A/en not_active Withdrawn
-
1996
- 1996-05-30 WO PCT/GB1996/001301 patent/WO1996038454A1/en active Application Filing
- 1996-05-30 AU AU58409/96A patent/AU5840996A/en not_active Abandoned
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0384730A2 (en) * | 1989-02-21 | 1990-08-29 | Shin-Etsu Chemical Co., Ltd. | Process for preparing a fluoroorganopolysiloxane |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107667125A (en) * | 2015-06-18 | 2018-02-06 | 陶氏环球技术有限责任公司 | Method for ERF to be made |
Also Published As
Publication number | Publication date |
---|---|
WO1996038454A1 (en) | 1996-12-05 |
GB9510866D0 (en) | 1995-07-26 |
AU5840996A (en) | 1996-12-18 |
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