WO2009112578A1 - Process for the purification of polyol pfpe derivative - Google Patents
Process for the purification of polyol pfpe derivative Download PDFInfo
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- WO2009112578A1 WO2009112578A1 PCT/EP2009/052999 EP2009052999W WO2009112578A1 WO 2009112578 A1 WO2009112578 A1 WO 2009112578A1 EP 2009052999 W EP2009052999 W EP 2009052999W WO 2009112578 A1 WO2009112578 A1 WO 2009112578A1
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- WO
- WIPO (PCT)
- Prior art keywords
- mixture
- tetraol
- derivatives
- protected
- formula
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 50
- 230000008569 process Effects 0.000 title claims abstract description 22
- 238000000746 purification Methods 0.000 title claims abstract description 9
- 229920005862 polyol Polymers 0.000 title description 4
- 150000003077 polyols Chemical class 0.000 title description 4
- 239000000203 mixture Substances 0.000 claims abstract description 121
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 67
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 22
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims abstract description 15
- 150000002576 ketones Chemical class 0.000 claims abstract description 10
- 150000001299 aldehydes Chemical class 0.000 claims abstract description 9
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 8
- 238000004508 fractional distillation Methods 0.000 claims abstract description 6
- 230000004048 modification Effects 0.000 claims abstract description 6
- 238000012986 modification Methods 0.000 claims abstract description 6
- -1 cyclic acetal Chemical class 0.000 claims abstract description 5
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 3
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims abstract description 3
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 3
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 claims abstract 4
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 229910052731 fluorine Inorganic materials 0.000 claims description 16
- 239000010409 thin film Substances 0.000 claims description 16
- 125000002915 carbonyl group Chemical class [*:2]C([*:1])=O 0.000 claims description 14
- 229910052801 chlorine Inorganic materials 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 13
- 238000004821 distillation Methods 0.000 claims description 12
- 150000002148 esters Chemical group 0.000 claims description 6
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- 150000007513 acids Chemical class 0.000 claims description 2
- 150000001266 acyl halides Chemical class 0.000 claims description 2
- 150000008064 anhydrides Chemical class 0.000 claims description 2
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 2
- 229930195729 fatty acid Natural products 0.000 claims description 2
- 239000000194 fatty acid Substances 0.000 claims description 2
- 150000004665 fatty acids Chemical class 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 125000000524 functional group Chemical group 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical group FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 claims description 2
- 238000004458 analytical method Methods 0.000 description 37
- 239000000047 product Substances 0.000 description 30
- 150000001263 acyl chlorides Chemical class 0.000 description 21
- 238000005886 esterification reaction Methods 0.000 description 21
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 18
- QAEDZJGFFMLHHQ-UHFFFAOYSA-N trifluoroacetic anhydride Chemical compound FC(F)(F)C(=O)OC(=O)C(F)(F)F QAEDZJGFFMLHHQ-UHFFFAOYSA-N 0.000 description 18
- 238000005481 NMR spectroscopy Methods 0.000 description 16
- 239000000314 lubricant Substances 0.000 description 16
- 230000032050 esterification Effects 0.000 description 13
- 238000004293 19F NMR spectroscopy Methods 0.000 description 12
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 10
- 238000005160 1H NMR spectroscopy Methods 0.000 description 8
- 229920002521 macromolecule Polymers 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000010702 perfluoropolyether Substances 0.000 description 8
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 7
- 150000001241 acetals Chemical class 0.000 description 7
- 239000003208 petroleum Substances 0.000 description 7
- 238000011084 recovery Methods 0.000 description 7
- 150000001805 chlorine compounds Chemical class 0.000 description 6
- 238000001212 derivatisation Methods 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000001117 sulphuric acid Substances 0.000 description 6
- 235000011149 sulphuric acid Nutrition 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 5
- OKKJLVBELUTLKV-MZCSYVLQSA-N Deuterated methanol Chemical compound [2H]OC([2H])([2H])[2H] OKKJLVBELUTLKV-MZCSYVLQSA-N 0.000 description 4
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 4
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 4
- 150000002009 diols Chemical group 0.000 description 4
- 238000000806 fluorine-19 nuclear magnetic resonance spectrum Methods 0.000 description 4
- XDOFQFKRPWOURC-UHFFFAOYSA-N iso-octadecanoic acid Natural products CC(C)CCCCCCCCCCCCCCC(O)=O XDOFQFKRPWOURC-UHFFFAOYSA-N 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000013459 approach Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000001632 sodium acetate Substances 0.000 description 3
- 235000017281 sodium acetate Nutrition 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000004566 IR spectroscopy Methods 0.000 description 2
- 241000124960 Turris Species 0.000 description 2
- 235000010724 Wisteria floribunda Nutrition 0.000 description 2
- 150000001265 acyl fluorides Chemical class 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000010511 deprotection reaction Methods 0.000 description 2
- 125000004989 dicarbonyl group Chemical group 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical group C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 2
- 238000005461 lubrication Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000000466 oxiranyl group Chemical group 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 0 *C1(*)O*(*O*N)*O1 Chemical compound *C1(*)O*(*O*N)*O1 0.000 description 1
- PBBJBFOOHLPWOV-UHFFFAOYSA-N 1,1'-biphenyl;carbonic acid Chemical compound OC(O)=O.C1=CC=CC=C1C1=CC=CC=C1 PBBJBFOOHLPWOV-UHFFFAOYSA-N 0.000 description 1
- XMIIGOLPHOKFCH-UHFFFAOYSA-N 3-phenylpropionic acid Chemical compound OC(=O)CCC1=CC=CC=C1 XMIIGOLPHOKFCH-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 241001481828 Glyptocephalus cynoglossus Species 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000010933 acylation Effects 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 229940040526 anhydrous sodium acetate Drugs 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- FRCHCYFLGZRELU-UHFFFAOYSA-N butan-2-one;cyclohexanone Chemical compound CCC(C)=O.O=C1CCCCC1 FRCHCYFLGZRELU-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000000994 depressogenic effect Effects 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 239000012039 electrophile Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- CBOIHMRHGLHBPB-UHFFFAOYSA-N hydroxymethyl Chemical compound O[CH2] CBOIHMRHGLHBPB-UHFFFAOYSA-N 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000002924 oxiranes Chemical group 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000000452 restraining effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003815 supercritical carbon dioxide extraction Methods 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/30—Post-polymerisation treatment, e.g. recovery, purification, drying
-
- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/002—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds
- C08G65/005—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens
- C08G65/007—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens containing fluorine
-
- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
- C08G65/22—Cyclic ethers having at least one atom other than carbon and hydrogen outside 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
- C08G65/22—Cyclic ethers having at least one atom other than carbon and hydrogen outside the ring
- C08G65/24—Epihalohydrins
Definitions
- the invention pertains to a process for the purification of polyol PFPE compounds useful as lubricants for magnetic media.
- magnetic recording apparatus is divided into those using a magnetic disk as the medium on which to record data and those using magnetic tape as such medium. Because the former type of recording apparatus using a magnetic disk (hereinafter referred to as magnetic disk drives) is prevailing, the following description focuses on magnetic disk drives as an example of the magnetic recording apparatus.
- a lubricant layer is formed on a carbon overcoat on the surface of a magnetic disk for use in the disk drive.
- the main material of the lubricant layer usually, fluoropolyether, which is a chemically stable fluorinated organic compound, is widely used.
- fluoropolyether lubricants based on fluoropolyethers as the backbone and having hydroxyl functional groups as their end groups have shown best performances.
- a class of compounds which have been found to plenty fulfil requirements for being use as magnetic media lubricant are fluoropolyether tetraols of general formula: HO-CH 2 -CH(OH)-CH 2 -O-CH 2 -CF 2 -R f -CF 2 CH 2 O-CH 2 -CH(OH)-CH 2 OH, comprising a fluoropolyoxyalkene chain (R f ) having at its end two diols groups.
- Such materials can be notably manufacture by reaction of epihalohydrins with perfluoropolyether derivatives having two hydroxyl end-group (see Scheme 1 here below), as taught in TURRI, Stefano, et al. End Group Chemistry of Fluoro-Oligomers: Highly Selective Synthese of Diepoxy, Diallyl, and Tetraol Derivatives. (A) J. polym. sci., A, Polym. chem.. 1996, vol.34, p.3263-3275. Scheme 1
- PFPE hydroxyl derivatives can open the oxirane ring of the targeted compound, yielding materials comprising more than one PFPE chain block, and/or, more frequently, a further glycidol molecule can react with the epoxide ring of above mentioned targeted epoxy-substituted intermediate, so that different species are formed.
- Mixtures obtained from processes of the prior art are thus generally complex compositions comprising unreacted precursors, targeted polyol derivatives and polymeric material comprising several PFPE chain blocks and/or several ex-glycidol molecules moieties.
- the broad molecular weight distribution of the starting perfluoropolyether diol mixture used for manufacturing corresponding tetraol derivatives by reaction with glycidol and/or epihalohydrins as above detailed makes it even more difficult to separate materials based on their respective volatility, as this parameter is both affected by the molecular weight and the functionality degree of the end chains.
- R f represents a fluoropolyoxyalkene chain (chain R f ), i.e. a fluorocarbon segment comprising ether linkages in main chain, from a mixture of hydroxyl (per)fluoropolyether derivatives [mixture (M)], said mixture comprising said tetraol (T) and at least one hydroxyl
- step 1 reacting the mixture (M) with ketones and/or aldehydes so as to selectively protect couples of hydroxyl groups on vicinal carbon atoms by forming corresponding cyclic ketal/acetal derivatives, so as to yield a protected mixture [mixture (P)]; step 2: reacting residual hydroxyl groups of the mixture (P) with suitable functionalizing agents enabling substantial volatility modification, so as to obtain a functionalized protected mixture [mixture (P f )]; step 3: fractional distillation of the mixture (P f ) so as to isolate the cyclic acetal/ketal derivatives of tetraol (T); step 4: hydrolyzing the acetal/ketal derivatives of tetraol (T) so as to recover pure tetraol (T). [0020]
- Mixture (M) generally comprises a mixture of hydroxyl (per)fluoropolyether derivative(s) and tetraol (T) complying with formula:
- R f is a fluoropolyoxyalkene chain
- T 1 and T 2 are selected among the following groups: (t1) -CF 2 -CH 2 O-CH 2 -CH(OH)-CH 2 OH;
- composition of mixture (M), as determined notably by 1 H-NMR on corresponding derivative obtained from derivatization with trifluoroacetic anhydride, is such that the mixture (M) comprises:
- the fluoropolyoxyalkene chain (R f ) of the PFPE (OH) and of the tetraol (T), equal or different from each other and at each occurrence, is preferably a chain comprising repeating units R°, said repeating units being chosen among the group consisting of : (i) -CFXO-, wherein X is F or CF 3 ,
- the mixture (M) preferably comprises hydroxyl (per)fluoropolyether derivatives and tetraols (T) complying with formula here below: T 2 -O-(CFX 1 O) C1 (CFX 2 CFX 3 O) C2 (CF 2 CF 2 CF 2 O) C3 (CF 2 CF 2 CF 2 O) C4 -T 1 wherein
- - X 1 , X 2 , X 3 equal or different from each other and at each occurrence are independently -F, -CF 3 ;
- - c1 , c2 , c3, and c4 are independently integers >0, such that and c1+c2+c3+c4 is in the range 5 to 2000, preferably between 10 and 500; should at least two of c1 , c2, c3 and c4 be different from zero, the different recurring units are generally statistically distributed along the chain.
- Mixture (M) can be notably manufactured by reaction of perfluoropolyether derivatives having two hydroxyl end-group with epihalohydrins, as taught in TURRI, Stefano, et al. End Group Chemistry of Fluoro-Oligomers: Highly Selective Synthese of Diepoxy, Diallyl, and Tetraol Derivatives.
- A J. polym. sci., A, Polym. chem.. 1996, vol.34, p.3263-3275. or with glycidol of formula:
- Step 1 is advantageously carried out by contacting the mixture (M) with an aldehyde or a ketone in the presence of a protic acid.
- the choice of the aldehyde or ketone is not critical, provided that it selectively reacts with vicinal hydroxyl groups for providing corresponding cyclic acetal/ketal.
- aldehydes and ketones mention can be made of acetone, methyl ethyl ketone cyclohexanone, phenylmethylketone, acetaldehyde.
- protic acid mention can be notably made of p-toluensulfonic acid, of acetic acid, or sulphuric acid.
- the reaction is advantageously carried out in the presence of a suitable solvent able to at least partially solubilise both the mixture (M), the aldehyde or ketone and the protic acid.
- ketones examples include ketones, esters, aprotic polar solvents, hydrocarbons, aromatics or their mixtures. Examples of these are acetone, methyl ethyl ketone, butyl acetate, dimethylformamide
- the protected mixture or mixture (P) generally comprises a mixture of at least partially protected hydroxyl (per)fluoropolyether derivatives and protected tetraols (T) complying with formula: TVO-R f -T 2 wherein:
- R f is a fluoropolyoxyalkene chain, as above detailed.
- T 1 and T 2 are selected among the following groups: (Pt1 )
- step 2 residual hydroxyl groups of the mixture (P) are made to react with suitable functionalizing agents enabling substantial volatility modification, so as to obtain a functionalized protected mixture [mixture (P f
- step 2 reactivity of end groups t2 and pt3 of mixture (P) as above detailed yields functionalized or hemi-functionalized end-groups for compounds different from tetraol (T), while group pt1 remains unreacted in same conditions, as detailed in following scheme:
- the functionalized protected mixture or mixture (P f ) generally comprises a mixture of functionalized, optionally partially protected, hydroxyl (per)fluoropolyether derivatives and protected tetraols (T) complying with formula: T 1 -O-R f -T 2 wherein:
- R f is a fluoropolyoxyalkene chain, as above detailed.
- T 1 and T 2 are selected among the following groups: (pt1 )
- esterification reactions reactions with carbonate monomers (like for example, biphenyl carbonate or dimethyl carbonate) to yield corresponding mono-, bis- or poly-carbonates, or reactions with substrates able to act as electrophiles in Williamson-like reactions (ether linkage formation), e.g. with ⁇ - ⁇ -dihaloalkanes, to yield corresponding di- or poly-ether compounds.
- carbonate monomers like for example, biphenyl carbonate or dimethyl carbonate
- substrates able to act as electrophiles in Williamson-like reactions e.g. with ⁇ - ⁇ -dihaloalkanes
- carbonyl derivative is not particularly limited. Preferred will be those carbonyl derivatives able to provide esters having high thermal stability, in particular able to withstand temperatures as high as 200-250°C, such as those applied during fractional distillation in step 3.
- dicarbonyl derivatives in particular those having remote (alpha, omega) carbonyl groups.
- X' is F or CF 3
- R and R' equal or different from each other are chosen independently among F, Cl, Br
- n ranges from 1 to 25, with m/n being from 0.01 to 0.5, recurring units being statistically distributed along the chain;
- diesters are formed having bound thereto two residues derived from a partially protected hydroxyl (per)fluoropolyether or an unprotected hydroxyl (per)fluoropolyether.
- step 3 the functionalized protected mixture [mixture (P f )] is submitted to a fractional distillation.
- the functionalization step 2 advantageously substantially modifies the relative volatility of different components of protected mixture (P), so that those components of formula TVO-RrT 2 as above detailed, having at least one Of T 1 and T 2 different from pt1 , thus bearing a functionalized group G f , have a substantially modified, generally strongly depressed, volatility with respect to protected tetraols (T) having both end groups of formula pt1 , as above detailed.
- Light fraction generally consists essentially of cyclic ketal/acetal derivatives of the tetraol (T), while heavy residue generally consists essentially of a mixtures of derivatives of formula T 1 -O-R f -T 2 as above detailed, having at least one Of T 1 and T 2 different from pt1 , i.e. comprising at least one group G f .
- step 4 the cyclic ketal/acetal derivatives of the tetraol (T), as recovered in high purity from step 3, are submitted to hydrolysis so as to yield pure tetraol (T).
- Hydrolysis conditions are not particularly limited and are generally chosen as a function of ketal/acetal derivative.
- hydrolysis is carried out under acid catalysis.
- an aqueous or aqueous alcoholic solution of a strong acid e.g. HCI, H 2 SO 4 , CH 3 COOH
- a strong acid e.g. HCI, H 2 SO 4 , CH 3 COOH
- T cyclic ketal/acetal derivatives of the tetraol
- Tetraol (T) is finally recovered with high purity from this latter step.
- each of above mentioned step proceeds with quantitative conversion and high selectivity, even when the mixture (M) comprises a tetraol (T) having broad molecular weight distribution, so as to obtain in high yields highly pure tetraol (T), which can be used as such in highly demanding lubricating applications, e.g. in magnetic media lubrication.
- a mixture (M 1 ) comprising a tetraol PFPE derivative and other hydroxyl derivatives and having an average molecular weight of 2000 was submitted to NMR analysis as such and after derivatization with trifluoroacetic anhydride.
- M 1 tetraol PFPE derivative and other hydroxyl derivatives and having an average molecular weight of 2000
- 5 g of mixture were treated with 10 g of trifluoroacetic anhydride so as to convert hydroxyl groups into trifluoacetate groups.
- the excess trifluoroacetic anhydride was removed by distillation under reduced pressure. Results are summarized here below:
- Step 1. 1 Protection of vicinal hydroxy! groups
- Step 1.2 Esterification with a PFPE diacid
- the reaction mixture was stirred at 60°C for 4 hours, then cooled at room temperature.
- the heavy fluorinated phase was separated and dried at reduced pressure at 60°C.
- a low viscous clear liquid (404 g) was obtained.
- the 19 F-NMR analysis confirmed quantitative acylation of the diacid Z-DIAC, as monitored by the pre-terminal shift. IR analysis further confirmed the fully conversion of the fluorinated reagent so as to yield the corresponding PFPE-diacyl chloride.
- step 1 In a three-necked 500 ml flask, equipped with a mechanical stirrer and a dropping funnel, 250 g of the product obtained in the step 1 (containing 0.06 moles of free OH groups) and 16 g (0.123 moles) of N-ethyldiisopropylamine were introduced under nitrogen.
- the PFPE-diacyl chloride (60 g, 0.03 mol) from step 2a) was then added over a period of 1 hour at 40 0 C, and allowed to react for 1 hour at 80 0 C.
- reaction product recovered after distillation under reduced pressure of the excess of amine and filtration of ammonium salts, was a viscous light yellow liquid, which was characterized by IR and 19 F NMR analysis. Both techniques confirmed the formation of the expected fully esterified derivatives.
- - esters between acyl chloride and PFPE macromolecules containing a -CF 2 CH 2 OH and/or -CF 2 CH 2 O-CH 2 CH(OH)-CH 2 O-CH 2 -CH(OH)-CH 2 OH end group with ketal protected vicinal hydroxyls, having ⁇ M n > 6000; 53% w/w
- Step 1.3 Thin film distillation of the product obtained in the step 2
- Step 1.4 Deorotection of Tetraol-ketal
- Step 2. 1 Protection of vicinal hydroxy! groups
- step 1.1 Ex. 1
- step 1.1 same procedure as detailed in step 1.1 (ex. 1) was followed, but using 600 g (0.30 moles) of mixture (M 2 ), 220 g (280 ml, 3.8 moles) of acetone, 280 ml of petroleum ether and 0.24 g of sulphuric acid, as well as 1.2 g of sodium acetate. 590 g of protected ketal mixture were isolated and characterized.
- Step 2.2 Esterification with a PFPE diacid
- step 1.2a Same procedure as detailed in step 1.2a) were followed, but using 840 g of same Z-DIAC perfluoropolyether diacid derivative, 300 g (2.55 moles) of thionyl chloride and 10 ml of pyridine. 808 g of Z-DIAC acyl chloride derivative were obtained and characterized by NMR and IR spectroscopy.
- step 1.2b) Same procedure as detailed in step 1.2b) (Ex. 1) was followed, but using 500 g of the product from step 2.1 (containing 0.12 moles of free OH groups), 32 g (0.245 moles) of N-Ethyldiisopropylamine and 120 g (0.06 mol) of Z-DIAC acyl chloride from step 2.2a).
- a viscous light yellow liquid (588 g) was isolated and found to have the following composition by IR and 19 F-NMR analysis:
- - esters between acyl chloride and PFPE macromolecules containing a -CF 2 CH 2 OH and/or -CF 2 CH 2 O-CH 2 CH(OH)-CH 2 O-CH 2 -CH(OH)-CH 2 OH end group with ketal protected vicinal hydroxyls, having ⁇ M n > 6000; 53% w/w.
- Step 2.3 Thin film distillation of the product obtained in the step 2.2
- 428 g of the product obtained in the step 2.2 were purified in a thin film distiller at 250°C at 7x10 ⁇ 3 mBar. Two fractions were collected, a heavy residue (58% weight) and a light fraction (42%). The IR and NMR analysis of the distilled light fraction confirmed that the isolated product is the protected tetraol derivative that didn't undergo esterification ( ⁇ 1 %) via same characteristic absorption bands/peaks as detailed in step 1.3.
- Step 2.4 Deorotection of Tetraol-ketal
- step 1.4 Same procedure as detailed in step 1.4 was applied to 108 g of light fraction from step 2.3, obtaining 100 g of pure tetraol, whose structure was confirmed by 19 F-NMR analysis, as detailed in 1.4 here above.
- the overall recovery yield of the pure tetraol was found to be 89%, while purity of said tetraol was 99%.
- Step 3. 1 Protection of vicinal hydroxy! groups
- step 1.1 (ex. 1) was followed, but using 300 g (0.30 moles) of mixture (M 3 ), 220 g (280 ml, 3.8 moles) of acetone, 280 ml of petroleum ether and 0.24 g of sulphuric acid, as well as 1.2 g of sodium acetate. 320 g of protected ketal mixture were isolated and characterized.
- Step 3.2 Esterification with a PFPE diacid
- step 1.2b) Same procedure as detailed in step 1.2b) (Ex. 1) was followed, but using 250 g of the product from step 3.1 (containing 0.12 moles of free OH groups), 32 g (0.245 moles) of N-Ethyldiisopropylamine and 120 g (0.06 mol) of Z-DIAC acyl chloride from step 2.2a).
- a viscous light yellow liquid (351 g) was isolated and found to have the following composition by IR and 19 F-NMR analysis
- - esters between acyl chloride and PFPE macromolecules containing a -CF 2 CH 2 OH and/or -CF 2 CH 2 O-CH 2 CH(OH)-CH 2 O-CH 2 -CH(OH)-CH 2 OH end group with ketal protected vicinal hydroxyls, having ⁇ M n > 4000; 63% w/w.
- Step 3.3 Thin film distillation of the product obtained in the step 3.2
- step 1.4 Same procedure as detailed in step 1.4 was applied to 58 g of light fraction from step 3.3, obtaining 50 g of pure tetraol, whose structure was confirmed by 19 F-NMR analysis, as detailed in 1.4 here above.
- the overall recovery yield of the pure tetraol was found to be 88.7%, while purity of said tetraol was 99%.
- Step 4. 1 Protection of vicinal hydroxy! groups
- Step 4.2 Esterification with a fatty diacid
- step 1.2a Same procedure as detailed in step 1.2a) were followed, but using 51.6 g (0.43 moles) of thionyl chloride, 1 ml of pyridine, and 28 g (0.12 moles) of dodecandioic acid of formula: HO-C(O)-(CH 2 ) 10 -C(O)-OH.
- - esters between acyl chloride and PFPE macromolecules containing a -CF 2 CH 2 OH and/or -CF 2 CH 2 O-CH 2 CH(OH)-CH 2 O-CH 2 -CH(OH)-CH 2 OH end group with ketal protected vicinal hydroxyls, having ⁇ M n > 4300; 39% w/w .
- Step 4.3 Thin film distillation of the product obtained in the step 4.2
- step 1.4 Same procedure as detailed in step 1.4 was applied to 107 g of light fraction from step 4.3, obtaining 100 g of pure tetraol, whose structure was confirmed by 19 F-NMR analysis, as detailed in 1.4 here above.
- the overall recovery yield of the pure tetraol was found to be 90%, while purity of said tetraol was 99%.
- Step 5. 1 Protection of vicinal hydroxy! groups
- step 1.1 Ex. 1
- 150 g (0.30 moles) of mixture (M 5 ) 110 g (140 ml, 1.9 moles) of acetone, 140 ml of petroleum ether and 0.12 g of sulphuric acid, as well as 0.6 g of sodium acetate. 160 g of protected ketal mixture were isolated and characterized.
- step 1.2b Same procedure as detailed in step 1.2b) was followed, but using 125 g of the product from step 5.1 (containing 0.06 moles of free OH groups), 16 g (0.123 moles) of N-Ethyldiisopropylamine and 30 g (0.03 mol) of Z-DIAC acyl chloride from step 5.2a).
- a viscous light yellow liquid (142 g) was isolated and found to have the following composition by IR and 19 F-NMR analysis:
- - esters between acyl chloride and PFPE macromolecules containing a -CF 2 CH 2 OH and/or -CF 2 CH 2 O-CH 2 CH(OH)-CH 2 O-CH 2 -CH(OH)-CH 2 OH end group with ketal protected vicinal hydroxyls, having ⁇ M n > 3000; 53% w/w.
- Step 5.3 Thin film distillation of the product obtained in the step 5.2
- step 1.4 Same procedure as detailed in step 1.4 was applied to 47 g of light fraction from step 5.3, obtaining 43 g of pure tetraol, whose structure was confirmed by 19 F-NMR analysis, as detailed in 1.4 here above.
- the overall recovery yield of the pure tetraol was found to be 93.6%, while purity of said tetraol was 99%.
- Step 6. 1 Protection of vicinal hydroxy! groups
- step 1.1 Vicinal groups in mixture (M 6 ) were protected following procedure detailed in step 1.1 (Ex. 1), using 150 g of mixture (M 6 ), 110 g (140 ml, 1.9 moles) of acetone, 140 ml of low boiling petroleum ether and 0.12 g sulphuric acid.
- Step 6.2 Esterification with a fattv acid
- Step 6.2a Preparation ofacyl chloride derivative of isostearic acid
- step 1.2a Same procedure as detailed in step 1.2a) were followed, but using 152 g (1.28 moles) of thionyl chloride, 5 ml of pyridine, and 59.7 g (0.21 moles) of isostearic acid of formula: (H 3 C) 2 CH(CH 2 ) I4 -C(O)-OH.
- a low viscous dark liquid (63.1 g) was obtained, which was found to be by IR analysis corresponding acyl chloride derivative. IR showed following absorption bands: acid moieties: 1720 cm "1 (carbonyl stretching); acyl chloride moieties: 1800 cm "1 (carbonyl stretching).
- step 1.2b Same procedure as detailed in step 1.2b) was followed, but using 125 g of the product from step 6.1 (containing 0.06 moles of free OH groups), 16 g (0.123 moles) of N-Ethyldiisopropylamine and 18 g (0.05 mol) of the acyl chloride from step 6.2a).
- esters between isostearic acyl chloride and PFPE macromolecules containing a -CF 2 CH 2 OH and/or -CF 2 CH 2 O-CH 2 CH(OH)-CH 2 O-CH 2 -CH(OH)-CH 2 OH end group with ketal protected vicinal hydroxyls, having ⁇ M n > 1300; 48% w/w .
- Step 6.3 Thin film distillation of the product obtained in the step 6.2
- step 1.4 Same procedure as detailed in step 1.4 was applied to 37 g of light fraction from step 6.3, obtaining 33 g of pure tetraol, whose structure was confirmed by 19 F-NMR analysis, as detailed in 1.4 here above. The overall recovery yield of the pure tetraol was found to be 90%, while purity of said tetraol was 99%.
- EXAMPLE 7 Tetraol 1000 narrow MWD+ Krytox ® 3000
- Step 7. 1 Protection of vicinal hydroxy! groups
- Step 7.2 Esterification with a PFPE diacid
- step 1.2b) Same procedure as detailed in step 1.2b) (Ex. 1) was followed, but using 125 g of the product from step 6.1 (containing 0.06 moles of free OH groups), 16 g (0.123 moles) of N-Ethyldiisopropylamine and 180 g (0.06 moles) of KRYTOX ® perfluoropolyether acyl fluoride (commercially available from DuPont) of formula CF 3 CF 2 CF 2 O-(CF(CFs)-CF 2 O) n -CF(CF 3 )-C(O)F, with n being an integer such that the average molecular weight is 3000.
- KRYTOX ® perfluoropolyether acyl fluoride commercially available from DuPont
- a viscous light yellow liquid (274 g) was isolated and found to have the following composition by IR and 19 F-NMR analysis:
- Step 7.3 Thin film distillation of the product obtained in the step 7.2
- step 1.4 Same procedure as detailed in step 1.4 was applied to 50 g of light fraction from step 7.3, obtaining 44.5 g of pure tetraol, whose structure was confirmed by 19 F-NMR analysis, as detailed in 1.4 here above.
- the overall recovery yield of the pure tetraol was found to be 98%, while purity of said tetraol was 99%.
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Abstract
The invention pertains to a process for the purification of a tetraol PFPE derivative [tetraol (T)] of formula (I): HO-CH2-CH(OH)-CH2-O-CH2-CF2-O-Rf-CF2-CH2O-CH2-CH(OH)-CH2OH (I), wherein Rf represents a fluoropolyoxyalkene chain (chain Rf), i.e. a fluorocarbon segment comprising ether linkages in main chain, from a mixture of hydroxyl (per)fluoropolyether derivatives [mixture (M)], said mixture comprising said tetraol (T) and at least one hydroxyl (per)fluoropolyether [PFPE (OH)] comprising a chain Rf terminated with at least one end group of formula: -CF2CH2OH) -CF2CH2O-CH(OH)-CH2-O-CH2-CH(OH)-CH2OH; said process comprising: step 1 : reacting the mixture (M) with ketones and/or aldehydes so as to selectively protect couples of hydroxyl groups on vicinal carbon atoms by forming corresponding cyclic ketal/acetal derivatives, so as to yield a protected mixture [mixture (P)]; step 2: reacting residual hydroxyl groups of the mixture (P) with suitable functionalizing agents enabling substantial volatility modification, so as to obtain a functionalized protected mixture [mixture (Pf)]; step 3: fractional distillation of the mixture (Pf) so as to isolate the cyclic acetal/ketal derivatives of tetraol (T); step 4. hydrolyzing the acetal/ketal derivatives of tetraol (T) so as to recover pure tetraol (T).
Description
Description
Process for the purification of polyol PFPE derivative Technical Field
[0001] The invention pertains to a process for the purification of polyol PFPE compounds useful as lubricants for magnetic media.
Background Art
[0002] As well known, magnetic recording apparatus is divided into those using a magnetic disk as the medium on which to record data and those using magnetic tape as such medium. Because the former type of recording apparatus using a magnetic disk (hereinafter referred to as magnetic disk drives) is prevailing, the following description focuses on magnetic disk drives as an example of the magnetic recording apparatus.
[0003] As the capacity enlargement of magnetic disk drives has been pursued for recent years, the fly height of the magnetic head has been lowered rapidly down to below 30 nm, and, consequently, there is increasing need for reliability in terms of resistance to sliding friction.
[0004] Also, there is strong need to enhance the data processing speed with more disk capacity. In particular, in a Redundant Array of Independent Disks (RAID) system, a magnetic disk drive that operates at a disk revolving speed of 10,000 rmp or higher is required.
[0005] In order to ensure the reliability of a magnetic disk drive, generally, a lubricant layer is formed on a carbon overcoat on the surface of a magnetic disk for use in the disk drive. As the main material of the lubricant layer, usually, fluoropolyether, which is a chemically stable fluorinated organic compound, is widely used.
[0006] Actually, in order to assure reliability of the magnetic disk drive, it is mandatory to efficiently preserve suitable lubricant distribution on the surface of said magnetic disk drive for long operating times. When magnetic disk drives operate, said disk revolves at a high speed and the lubricant might be spun off by the combined action of the air shear due to the air flow on the surface of the disk as the disk revolves, and of the centrifugal force directly exerted on the lubricant. As a consequence, it is often observed that the quantity of the lubricant on the surface of the disk
gradually decreases. Also, evaporation phenomena of the lubricant into the atmosphere inside the magnetic drive may take place.
[0007] To overcome this problem of the lubricant loss by being spun off during disk revolution and natural evaporation, approaches have heretofore been proposed. Thus, a method for restraining the lubricant from being spun off and evaporated has been proposed in which the adhesion force of the lubricant to the disk protecting layer is made stronger by increasing the polarity of the functional end groups in the lubricant. Said polar end groups are believed to improve adherence of the lubricant to the surface of the magnetic media.
[0008] Within this approach, fluoropolyether lubricants based on fluoropolyethers as the backbone and having hydroxyl functional groups as their end groups have shown best performances.
[0009] A class of compounds which have been found to plenty fulfil requirements for being use as magnetic media lubricant are fluoropolyether tetraols of general formula: HO-CH2-CH(OH)-CH2-O-CH2-CF2-Rf-CF2CH2O-CH2 -CH(OH)-CH2OH, comprising a fluoropolyoxyalkene chain (Rf) having at its end two diols groups.
[0010] Such materials can be notably manufacture by reaction of epihalohydrins with perfluoropolyether derivatives having two hydroxyl end-group (see Scheme 1 here below), as taught in TURRI, Stefano, et al. End Group Chemistry of Fluoro-Oligomers: Highly Selective Synthese of Diepoxy, Diallyl, and Tetraol Derivatives. (A) J. polym. sci., A, Polym. chem.. 1996, vol.34, p.3263-3275. Scheme 1
PFPE
Nevertheless, side reactions are likely to occur during nucleophilic
substitution on the epihalohydrin, involving e.g. reactions of oxirane ring with further PFPE hydroxyl derivatives, yielding materials comprising more than one PFPE chain block. Final material thus fails to comply with the expected stoichiometry and fails to possess the targeted anchoring diol functions as end-chains.
[0011] Similarly, reaction of perfluoropolyether derivatives having two hydroxyl end-group with glycidol of formula:
HO — Z o
, as described in SCHICCHITANO, Massimo, et al. Synthesis and characterization of low-viscosity fluoropolyether-based segmented oligomers. Die Angewandte Makromoleculare Chemie. 1995, vol.231 , no.4000, p.47-60. , yields, in addition to the expected epoxy-substituted derivatives (which can be further converted in corresponding diols), a large range of side-products. As an example, PFPE hydroxyl derivatives can open the oxirane ring of the targeted compound, yielding materials comprising more than one PFPE chain block, and/or, more frequently, a further glycidol molecule can react with the epoxide ring of above mentioned targeted epoxy-substituted intermediate, so that different species are formed.
[0012] Mixtures obtained from processes of the prior art are thus generally complex compositions comprising unreacted precursors, targeted polyol derivatives and polymeric material comprising several PFPE chain blocks and/or several ex-glycidol molecules moieties.
[0013] Also, the broad molecular weight distribution of the starting perfluoropolyether diol mixture used for manufacturing corresponding tetraol derivatives by reaction with glycidol and/or epihalohydrins as above detailed makes it even more difficult to separate materials based on their respective volatility, as this parameter is both affected by the molecular weight and the functionality degree of the end chains.
[0014] Complex purification procedures, based e.g. on supercritical carbon dioxide extraction techniques are thus required for purifying target material, so as to achieve the expected chemical structure and level of
functionality at the end groups.
[0015] Approaches of this type are described, for instance, in US 2004092406 (FUJI ELECTRIC CO LTD (JP) ) 13.05.2004 , in US 2003100454 (FUJI ELECTRIC CO LTD (JP) ) 29.05.2003 and EP 1372141 A (HITACHI LTD (JP) ) 17.12.2003 .
[0016] Efficiency of these processes is relatively low and waste of highly costly material non negligible. Also said purification steps generate additional burden on manufacturers or users of products obtained as above detailed.
[0017] Due to the extreme wear conditions wherein said lubricants are to be used in particular for hard disks lubrication, it is essential to use absolutely pure compounds, which have homogeneous behaviour and do not undergo risks of evaporative loss.
[0018] The need was thus felt in the art for a process for the purification of hydroxyl functional perfluoropolyether derivatives having improved yield towards targeted compounds having two vicinal hydroxyl groups, lower energy consumption and simpler operations, which could provide high purity (per)fluoropolyether tetraols.
Disclosure of Invention
[0019] It is thus an object of the present invention a process for the purification of a tetraol PFPE derivative [tetraol (T)] of formula (I): HO-CH2-CH(OH)-CH2-O-CH2-CF2-O-Rf-CF2-CH2O-CH2-CH(OH)-CH2OH
(I), wherein Rf represents a fluoropolyoxyalkene chain (chain Rf), i.e. a fluorocarbon segment comprising ether linkages in main chain, from a mixture of hydroxyl (per)fluoropolyether derivatives [mixture (M)], said mixture comprising said tetraol (T) and at least one hydroxyl
(per)fluoropolyether [PFPE (OH)] comprising a chain Rf terminated with at least one end group of formula:
-CF2CH2OHJ -CF2CH2O-CH(OH)-CH2-O-CH2-CH(OH)-CH2OH; said process comprising: step 1 : reacting the mixture (M) with ketones and/or aldehydes so as to selectively protect couples of hydroxyl groups on vicinal carbon atoms by forming corresponding cyclic ketal/acetal derivatives, so as to yield a
protected mixture [mixture (P)]; step 2: reacting residual hydroxyl groups of the mixture (P) with suitable functionalizing agents enabling substantial volatility modification, so as to obtain a functionalized protected mixture [mixture (Pf)]; step 3: fractional distillation of the mixture (Pf) so as to isolate the cyclic acetal/ketal derivatives of tetraol (T); step 4: hydrolyzing the acetal/ketal derivatives of tetraol (T) so as to recover pure tetraol (T). [0020] The applicant has found that by means of the process of the invention it is advantageously possible to successfully isolate in high yields (exceeding
85 %) tetraol (T) with high level of purity (exceeding 99 %). [0021] Mixture (M) generally comprises a mixture of hydroxyl (per)fluoropolyether derivative(s) and tetraol (T) complying with formula:
T1-O-Rf-T2 wherein:
- Rf is a fluoropolyoxyalkene chain; and
- T1 and T2 are selected among the following groups: (t1) -CF2-CH2O-CH2-CH(OH)-CH2OH;
(t2) -CF2CH2OH;
(t3) -CF2CH2O-CH(OH)-CH2-O-CH2-CH(OH)-CH2OH, with the provisio that the mixture (M) comprise at least one compound wherein T1=T2 = t1 (i.e. a tetraol (T)) and at least one hydroxyl (per)fluoropolyether with at least one Of T1 and T2 different from t1 (i.e. a PFPE (OH)).
[0022] Typically, composition of mixture (M), as determined notably by 1H-NMR on corresponding derivative obtained from derivatization with trifluoroacetic anhydride, is such that the mixture (M) comprises:
- from 60 to 90 % moles of groups (t1) as above detailed;
- from 5 to 20 % moles of groups (t2) as above detailed;
- from 5 to 20 % moles of groups (t3) as above detailed.
[0023] The fluoropolyoxyalkene chain (Rf) of the PFPE (OH) and of the tetraol (T), equal or different from each other and at each occurrence, is preferably a chain comprising repeating units R°, said repeating units being chosen among the group consisting of :
(i) -CFXO-, wherein X is F or CF3,
(ii) -CFXCFXO-, wherein X, equal or different at each occurrence, is F or CF3, with the provision that at least one of X is -F, (iii) -CF2CF2CF2O-, (iv) -CF2CF2CF2CF2O-,
(v) -(CF2)J-CFZ-O- wherein j is an integer from O to 3 and Z is a group of general formula -ORfT3, wherein Rf' is a fluoropolyoxyalkene chain comprising a number of repeating units from O to 10, said recurring units being chosen among the followings : -CFXO- , -CF2CFXO-, -CF2CF2CF2 O-, -CF2CF2CF2CF2O-, with each of each of X being independently F or CF3. and T3 being a C1-C3 perfluoroalkyl group.
[0024] Thus, the mixture (M) preferably comprises hydroxyl (per)fluoropolyether derivatives and tetraols (T) complying with formula here below: T2-O-(CFX1O)C1(CFX2CFX3O)C2(CF2CF2CF2O)C3(CF2CF2CF2CF2O)C4-T1 wherein
- X1, X2, X3 equal or different from each other and at each occurrence are independently -F, -CF3;
- T1 and T2 are as above defined;
- c1 , c2 , c3, and c4, equal or different from each other, are independently integers >0, such that and c1+c2+c3+c4 is in the range 5 to 2000, preferably between 10 and 500; should at least two of c1 , c2, c3 and c4 be different from zero, the different recurring units are generally statistically distributed along the chain.
[0025] Mixture (M) can be notably manufactured by reaction of perfluoropolyether derivatives having two hydroxyl end-group with epihalohydrins, as taught in TURRI, Stefano, et al. End Group Chemistry of Fluoro-Oligomers: Highly Selective Synthese of Diepoxy, Diallyl, and Tetraol Derivatives. (A) J. polym. sci., A, Polym. chem.. 1996, vol.34, p.3263-3275. or with glycidol of formula:
, as described in SCHICCHITANO, Massimo, et al. Synthesis and characterization of low-viscosity fluoropolyether-based segmented
oligomers. Die Angewandte Makromoleculare Chemie. 1995, vol.231 , no.4000, p.47-60. [0026] Step 1 is advantageously carried out by contacting the mixture (M) with an aldehyde or a ketone in the presence of a protic acid. [0027] The choice of the aldehyde or ketone is not critical, provided that it selectively reacts with vicinal hydroxyl groups for providing corresponding cyclic acetal/ketal. [0028] Among suitable aldehydes and ketones, mention can be made of acetone, methyl ethyl ketone cyclohexanone, phenylmethylketone, acetaldehyde. [0029] As protic acid, mention can be notably made of p-toluensulfonic acid, of acetic acid, or sulphuric acid. [0030] The reaction is advantageously carried out in the presence of a suitable solvent able to at least partially solubilise both the mixture (M), the aldehyde or ketone and the protic acid. [0031] Among suitable solvents mention can be made of ketones, esters, aprotic polar solvents, hydrocarbons, aromatics or their mixtures. Examples of these are acetone, methyl ethyl ketone, butyl acetate, dimethylformamide
(DMF), toluene, petroleum ether, hexane [0032] The increased stability of 5-membered cyclic acetal/ketal structure formed by reaction of vicinal hydroxyl groups (i.e. from hydroxyl groups in 1 ,2 relative position) with aldehydes/ketones advantageously provides for high selectivity of protection of said hydroxyl groups, with respect to isolated or distal hydroxyl groups. [0033] Thus, among above mentioned end groups of hydroxyl
(per)fluoropolyether derivatives and tetraols (T), it has been found that reactivity of groups t1 and t3 as above detailed advantageously yields in step 1 protected or hemi-protected end-groups, whereas t2 remains unreacted in same conditions, as detailed in following scheme:
(t3) wherein RH and R'H, equal or different from each other, are independently selected among H and C1-C12 hydrocarbon group, with the provisio that at least one of RH and R'H is different from H.
[0034] Thus the protected mixture or mixture (P) generally comprises a mixture of at least partially protected hydroxyl (per)fluoropolyether derivatives and protected tetraols (T) complying with formula: TVO-Rf-T2 wherein:
- Rf is a fluoropolyoxyalkene chain, as above detailed; and
- T1 and T2 are selected among the following groups: (Pt1 )
(ptl)
(t2) -CF2CH2OH;
(pt3)
[0035] In step 2, residual hydroxyl groups of the mixture (P) are made to react with suitable functionalizing agents enabling substantial volatility modification, so as to obtain a functionalized protected mixture [mixture (Pf
)] ■
[0036] Generally, in step 2, reactivity of end groups t2 and pt3 of mixture (P) as above detailed yields functionalized or hemi-functionalized end-groups for compounds different from tetraol (T), while group pt1 remains unreacted in same conditions, as detailed in following scheme:
(pti) (pti)
(pt3) (fPt3> wherein RH and R'H have the same meaning as above defined and Gf is a functional group enabling substantial volatility modification, optionally bond at its distal end to another (ft2) or (fpt3) group.
[0037] The functionalized protected mixture or mixture (Pf) generally comprises a mixture of functionalized, optionally partially protected, hydroxyl (per)fluoropolyether derivatives and protected tetraols (T) complying with formula: T1-O-Rf-T2 wherein:
- Rf is a fluoropolyoxyalkene chain, as above detailed; and
- T1 and T2 are selected among the following groups: (pt1 )
(ft2) -CF2CH2Gf; (pt3)
(fpt3) wherein RH , R'H and Gf have the same meaning as above defined, with the provisio that the mixture (Pf) comprises at least one compound wherein T"-ι=T"2 = pt1 (i.e. a protected tetraol (T)) and at least one (per)fluoropolyether with at least one of T1 and T2 different from pt1.
[0038] Among suitable methods for functionalizing residual hydroxyl group mention can be made of esterification reactions, reactions with carbonate monomers (like for example, biphenyl carbonate or dimethyl carbonate) to yield corresponding mono-, bis- or poly-carbonates, or reactions with substrates able to act as electrophiles in Williamson-like reactions (ether linkage formation), e.g. with α-ω-dihaloalkanes, to yield corresponding di- or poly-ether compounds.
[0039] It is nevertheless generally preferred to functionalize said residual hydroxyl groups by conversion in corresponding esters moieties, via reaction with suitable carbonyl derivatives (acyl halides, anhydrides, acids).
[0040] The choice if carbonyl derivative is not particularly limited. Preferred will be those carbonyl derivatives able to provide esters having high thermal stability, in particular able to withstand temperatures as high as 200-250°C, such as those applied during fractional distillation in step 3.
[0041] Among mono-carbonyl derivatives, mention can be notably made of:
- organic fatty acids of formula R3-COOH, with R3 being an aliphatic C8-36 group;
- (per)fluoropolyether monoacyl derivatives of formula:
T-O- CF7CF-O- CF O CRR' -Y
CF, X
wherein X' is F or CF3; R and R', equal or different from each other are chosen independently among F, Cl, Br; Y is a -C(O)X group, with X = Cl, F, OH; T is a C1-C3 perfluorocarbon group, optionally comprising one halogen atom different from fluorine; n ranges from 1 to 25, with m/n being from 0.01 to 0.5, units being statistically distributed along the chain;
- (per)fluoropolyether monoacyl derivatives of formula: CF3CF2CF2O-(CF(CF3)-CF2O)n-CF(CF3)-C(O)-X with X = Cl, F, OH and n selected so as the average molecular weight is comprised between 100 and 10 000, preferably from 1 000 and 3 000;
- (per)fluoropolyether monoacyl derivatives of formula: CF3O-(CF2CF2O)p-(CF2O)q-C(O)-X with X = Cl, F, OH and p and q are selected so as the average molecular weight is comprised between 100 and 10 000, preferably from 1 000 and 3 000 with p/q being > 0.5, units being statistically distributed along the chain.
[0042] While monocarbonyl derivatives can be successfully used, it is generally preferred to use dicarbonyl derivatives, in particular those having remote (alpha, omega) carbonyl groups.
[0043] Among di-carbonyl derivatives, mention can be notably made of:
- organic fatty diacids of formula HOOC-Rb-COOH, with Rb being a divalent aliphatic C6-24 group;
- (per)fluoropolyether diacyl derivatives of formula: Y-CRR'-O-(CF2CF(CF3)O)n(CF(X')O)m-CRRΥ wherein X' is F or CF3; R and R', equal or different from each other are chosen independently among F, Cl, Br; Y is a -C(O)X group, with X = Cl, F, OH; n ranges from 1 to 25, with m/n being from 0.01 to 0.5, recurring units being statistically distributed along the chain;
- (per)fluoropolyether diacyl derivatives of formula: X-C(O)CF2O-(CF2CF2O)p-(CF2O)q-CF2C(O)-X wherein X = Cl, F, OH; p and q are selected so that the average molecular
weight is comprised between 100 and 10000, preferably from 1000 and 3000 with p/q being > 0.5, recurring units being statistically distributed along the chain.
[0044] By reaction with said dicarbonyl derivatives, diesters are formed having bound thereto two residues derived from a partially protected hydroxyl (per)fluoropolyether or an unprotected hydroxyl (per)fluoropolyether.
[0045] In step 3, the functionalized protected mixture [mixture (Pf)] is submitted to a fractional distillation.
[0046] As previously mentioned, the functionalization step 2 advantageously substantially modifies the relative volatility of different components of protected mixture (P), so that those components of formula TVO-RrT2 as above detailed, having at least one Of T1 and T2 different from pt1 , thus bearing a functionalized group Gf, have a substantially modified, generally strongly depressed, volatility with respect to protected tetraols (T) having both end groups of formula pt1 , as above detailed.
[0047] Thus, standard fractional distillation procedure can easily enable separation of the cyclic ketal/acetal derivatives of the tetraol (T).
[0048] Among said procedures, mention can be notably made of thin film distillation, generally carried out at reduced pressure.
[0049] Light fraction generally consists essentially of cyclic ketal/acetal derivatives of the tetraol (T), while heavy residue generally consists essentially of a mixtures of derivatives of formula T1-O-Rf-T2 as above detailed, having at least one Of T1 and T2 different from pt1 , i.e. comprising at least one group Gf.
[0050] In step 4, the cyclic ketal/acetal derivatives of the tetraol (T), as recovered in high purity from step 3, are submitted to hydrolysis so as to yield pure tetraol (T).
[0051] Hydrolysis conditions are not particularly limited and are generally chosen as a function of ketal/acetal derivative. Typically, hydrolysis is carried out under acid catalysis. Typically an aqueous or aqueous alcoholic solution of a strong acid (e.g. HCI, H2SO4, CH3COOH...) is contacted with cyclic ketal/acetal derivatives of the tetraol (T).
[0052] Tetraol (T) is finally recovered with high purity from this latter step.
[0053] The Applicant has surprisingly found that, despite the multistep procedure, each of above mentioned step proceeds with quantitative conversion and high selectivity, even when the mixture (M) comprises a tetraol (T) having broad molecular weight distribution, so as to obtain in high yields highly pure tetraol (T), which can be used as such in highly demanding lubricating applications, e.g. in magnetic media lubrication.
[0054] The present invention will be now described in more detail with reference to the following examples, whose purpose is merely illustrative and not intended to limit the scope of the invention.
[0055] EXAMPLE 1 (Tetraol 2000 narrow MWD+ Diac 2000)
[0056] Analysis of raw mixture (M1)
[0057] A mixture (M1) comprising a tetraol PFPE derivative and other hydroxyl derivatives and having an average molecular weight of 2000 was submitted to NMR analysis as such and after derivatization with trifluoroacetic anhydride. For obtaining derivatized products, 5 g of mixture were treated with 10 g of trifluoroacetic anhydride so as to convert hydroxyl groups into trifluoacetate groups. The excess trifluoroacetic anhydride was removed by distillation under reduced pressure. Results are summarized here below:
- 1H NMR (neat sample): a complex pattern of signals around 3.3-4.0 ppm (due to -CH2- and -CH(-)- groups, intensity: about 7 H) and a signal at 4.9 ppm (due to the OH groups, intensity: about 2 H) were detected.
- 1H-NMR (freon 113-acetone solution of derivatized sample):
• 5.7 ppm -CH- group of RfCF2CH2OCH2CH(OCOCF3)CH2OCOCF3
• 5.4 ppm -CH- group of RfCF2CH2OCH2CH(OCOCF3)CH2OCH2CH (OCOCF3)CH2OCOCF3
• 5.0 ppm -CH2- group of RfCFoCH2OCOCFc,
• 3.7-4.8 signals of other -CH2- group.
[0058] The analysis yielded the following composition for mixture (M1):
• 10% end groups of formula -CF2CH2OH
• 14% end groups of formula -CF2CH2O-CH2CH(OH)-CH2O-CH2 -CH(OH)-CH2OH (bis-adduct);
• 76% end groups of formula -CF2CH2O-CH2CH(OH)-CH2OH.
[0059] Its other relevant molecular parameters, as determined by GPC analysis are: average molecular weight = 2000, Polydispersity 1.05.
[0060] Step 1. 1 : Protection of vicinal hydroxy! groups
In a 500 ml two necked flask, equipped with a magnetic stirrer, and a total reflux phase-separating head, 300 g of the mixture as above detailed, 110 g (140 ml, 1.9 moles) of acetone, 140 ml of low boiling petroleum ether and 0.12 g sulphuric acid 96% were introduced.
[0061] The reaction mixture was refluxed under stirring and the water was removed and collected in an external trap, until formation of water ended (about 10 hours).
The mixture was cooled down to room temperature and 0.6 g of anhydrous sodium acetate were added. After 30 minutes under stirring, the mixture was filtered and the excess of petroleum ether and acetone removed by distillation at reduced pressure. After a further filtration, a clear low viscosity protected mixture comprising tetraol-ketal was isolated (297 g) and analyzed by NMR.
1H NMR (A113/CD3OD) CH3 1.32 and 1.37 ppm (6H); a complex pattern of signal at 3.5-4.3 ppm (about 7 H) due to other protons (the complexity is originated by the presence of the cyclic ketal witch contains a stereogenic center).
[0062] Step 1.2: Esterification with a PFPE diacid
[0063] Step 1.2a): Preparation ofacyl chloride derivative of a PFPE diacid
[0064] In a four-necked 500 ml flask, equipped with a mechanical stirrer and a dropping funnel, 152 g (1.28 moles) of thionyl chloride and 5 ml of pyridine were heated at 60°C under stirring. Then 420 g (0.21 moles) of a
(per)fluoropolyether diacid having linear structure and carboxylic acid end group of Mn =2000 (Z-DIAC), complying with formula:
HO-C(O)CF2O-(CF2CF2O)P-(CF2OVCF2C(O)-OH with p/q being 1.0, units being statistically distributed along the chain, were added drop-wise. Evolution of HCI and SO2 was observed.
The reaction mixture was stirred at 60°C for 4 hours, then cooled at room temperature. The heavy fluorinated phase was separated and dried at reduced pressure at 60°C. A low viscous clear liquid (404 g) was obtained.
The 19F-NMR analysis confirmed quantitative acylation of the diacid Z-DIAC, as monitored by the pre-terminal shift. IR analysis further confirmed the fully conversion of the fluorinated reagent so as to yield the corresponding PFPE-diacyl chloride.
[0065] 19F NMR spectrum (neat simple), diagnostic signals: of Z DIAC Mn=2000: -CF2COOH -80.2 and -78.4 ppm of PFPE acyl chloride: -CF2COCI -79 and -77.4 ppm Typical IR band of Z DIAC Mn=2000: 1780 cm"1 (carbonyl stretching); of PFPE acyl chloride: 1801 cm"1 (carbonyl stretching).
[0066] Step 1.2b): PFPE-esterification
[0067] In a three-necked 500 ml flask, equipped with a mechanical stirrer and a dropping funnel, 250 g of the product obtained in the step 1 (containing 0.06 moles of free OH groups) and 16 g (0.123 moles) of N-ethyldiisopropylamine were introduced under nitrogen. The PFPE-diacyl chloride (60 g, 0.03 mol) from step 2a) was then added over a period of 1 hour at 400C, and allowed to react for 1 hour at 800C. The reaction product, recovered after distillation under reduced pressure of the excess of amine and filtration of ammonium salts, was a viscous light yellow liquid, which was characterized by IR and 19F NMR analysis. Both techniques confirmed the formation of the expected fully esterified derivatives.
[0068] IR band at 1810 cm"1 (carbonyl stretching).
[0069] 19F NMR spectrum (neat simple), diagnostic signals: -CF2CH2OC(O)- -79.5 and -77.5 ppm -CF2COOCHn- (n=1 or 2) -79 and -77 ppm
[0070] This corresponds to the following average composition:
- tetraol protected as ketal having <Mn>= 2000: 47%w/w
- esters between acyl chloride and PFPE macromolecules containing a -CF2CH2OH and/or -CF2CH2O-CH2CH(OH)-CH2O-CH2-CH(OH)-CH2OH end group with ketal protected vicinal hydroxyls, having <Mn>= 6000; 53% w/w
[0071] Step 1.3: Thin film distillation of the product obtained in the step 2
214 g of the product obtained in the step 2 were purified in a thin film
distiller at 250°C at 8x10~3mBar. Two fractions were collected, a heavy residue (56% wt) and a light fraction (44% wt). The IR and NMR analysis of the distilled light fraction confirmed that the isolated product is the protected tetraol derivate that didn't undergo esterification (< 1 %). IR analysis showed absence of the ester peak at 1810 cm"1. 19F NMR spectrum (neat simple) diagnostic signals:
-CF2CH2OCH2- -79.5 and -77.7 ppm
1H NMR (AI 13/CD3OD), diagnostic signals:
CH3 1.32 and 1.37 ppm (6H); a complex pattern of signal at 3.5-4.3 ppm
(about 7 H).
Complementary analysis of the residue was fully consistent with the analysis of the distilled fraction, the residue containing the ester between acyl chloride and PFPE macromolecules containing -CF2CH2OH and/or bis adduct hemi-protected end groups, and showing IR band at 1810 cm"1.
19F NMR spectrum (neat simple), diagnostic signals:
-CF2CH2OC(O)- -79.5 and -77.5 ppm
-CF2COOCHn- (n=1 or 2) -79 and -77 ppm
[0072] Step 1.4: Deorotection of Tetraol-ketal
[0073] The light fraction consisting of tetraol ketal (107 g) was treated at 60°C for 4 hours with methanol (50 ml) and 20 g of 7 %wt HCI aqueous solution. Final product analysis (significant signals):
1H-NMR on derivatized compound with trifluoroacetic anhydride (see above):
• 5.7 ppm -CH- group of RfCF2CH2OCH2CH(OCOCF3)CH2OCOCF3;
• No signal at 5.0 and 5.4 ppm (peaks due to the bis-adduct and/or -CF2 CH2OH);
• 3.7-4.8 signals of other -CH2- groups
The overall recovery yield of the pure tetraol was found to be 94%, while purity of said tetraol was 99%. [0074] EXAMPLE 2 (Tetraol 2000 broad MWD+ Diac 2000) [0075] Analysis of raw mixture (M2) [0076] A mixture (M2) was submitted to NMR analysis as such and after derivatization with trifluoroacetic anhydride, as detailed in example 1.
The analysis yielded the following composition for mixture (M2):
• 12% end groups of formula -CF2CH2OH
• 12% end groups of formula -CF2CH2O-CH2CH(OH)-CH2O-CH2 -CH(OH)-CH2OH (bis-adduct);
• 76% end groups of formula -CF2CH2O-CH2CH(OH)-CH2OH.
[0077] Its other relevant molecular parameters, as determined by GPC analysis are: average molecular weight = 2000, Polydispersity 1.45.
[0078] Step 2. 1: Protection of vicinal hydroxy! groups
Same procedure as detailed in step 1.1 (ex. 1) was followed, but using 600 g (0.30 moles) of mixture (M2), 220 g (280 ml, 3.8 moles) of acetone, 280 ml of petroleum ether and 0.24 g of sulphuric acid, as well as 1.2 g of sodium acetate. 590 g of protected ketal mixture were isolated and characterized.
[0079] Step 2.2: Esterification with a PFPE diacid
[0080] Step 2.2a): Preparation ofacyl chloride derivative of a PFPE diacid
[0081] Same procedure as detailed in step 1.2a) were followed, but using 840 g of same Z-DIAC perfluoropolyether diacid derivative, 300 g (2.55 moles) of thionyl chloride and 10 ml of pyridine. 808 g of Z-DIAC acyl chloride derivative were obtained and characterized by NMR and IR spectroscopy.
[0082] Step 2.2b): PFPE -esterification
[0083] Same procedure as detailed in step 1.2b) (Ex. 1) was followed, but using 500 g of the product from step 2.1 (containing 0.12 moles of free OH groups), 32 g (0.245 moles) of N-Ethyldiisopropylamine and 120 g (0.06 mol) of Z-DIAC acyl chloride from step 2.2a).
A viscous light yellow liquid (588 g) was isolated and found to have the following composition by IR and 19F-NMR analysis:
- tetraol protected as ketal having <Mn>= 2000: 47%w/w
- esters between acyl chloride and PFPE macromolecules containing a -CF2CH2OH and/or -CF2CH2O-CH2CH(OH)-CH2O-CH2-CH(OH)-CH2OH end group with ketal protected vicinal hydroxyls, having <Mn>= 6000; 53% w/w.
[0084] Step 2.3: Thin film distillation of the product obtained in the step 2.2 [0085] 428 g of the product obtained in the step 2.2 were purified in a thin film
distiller at 250°C at 7x10~3mBar. Two fractions were collected, a heavy residue (58% weight) and a light fraction (42%). The IR and NMR analysis of the distilled light fraction confirmed that the isolated product is the protected tetraol derivative that didn't undergo esterification (< 1 %) via same characteristic absorption bands/peaks as detailed in step 1.3.
[0086] Step 2.4: Deorotection of Tetraol-ketal
[0087] Same procedure as detailed in step 1.4 was applied to 108 g of light fraction from step 2.3, obtaining 100 g of pure tetraol, whose structure was confirmed by 19F-NMR analysis, as detailed in 1.4 here above. The overall recovery yield of the pure tetraol was found to be 89%, while purity of said tetraol was 99%.
[0088] EXAMPLE 3 (Tetraol 1000 narrow MWD+ Diac 2000)
[0089] Analysis of raw mixture (M1)
[0090] A mixture (M3) was submitted to NMR analysis as such and after derivatization with trifluoroacetic anhydride, as detailed in example 1. The analysis yielded the following composition for mixture (M3):
• 10% end groups of formula -CF2CH2OH
• 14% end groups of formula -CF2CH2O-CH2CH(OH)-CH2O-CH2 -CH(OH)-CH2OH (bis-adduct);
• 76% end groups of formula -CF2CH2O-CH2CH(OH)-CH2OH.
[0091] Its other relevant molecular parameters, as determined by GPC analysis are: average molecular weight = 1000, Polydispersity 1.08.
[0092] Step 3. 1: Protection of vicinal hydroxy! groups
Same procedure as detailed in step 1.1 (ex. 1) was followed, but using 300 g (0.30 moles) of mixture (M3), 220 g (280 ml, 3.8 moles) of acetone, 280 ml of petroleum ether and 0.24 g of sulphuric acid, as well as 1.2 g of sodium acetate. 320 g of protected ketal mixture were isolated and characterized.
[0093] Step 3.2: Esterification with a PFPE diacid
[0094] Step 3.2a): Preparation ofacyl chloride derivative of a PFPE diacid An aliquot of the Z-DIAC acyl chloride from step 2.2a) was used.
[0095] Step 3.2b): PFPE -esterification
[0096] Same procedure as detailed in step 1.2b) (Ex. 1) was followed, but using
250 g of the product from step 3.1 (containing 0.12 moles of free OH groups), 32 g (0.245 moles) of N-Ethyldiisopropylamine and 120 g (0.06 mol) of Z-DIAC acyl chloride from step 2.2a).
A viscous light yellow liquid (351 g) was isolated and found to have the following composition by IR and 19F-NMR analysis
- tetraol protected as ketal having <Mn>= 1000: 37%w/w
- esters between acyl chloride and PFPE macromolecules containing a -CF2CH2OH and/or -CF2CH2O-CH2CH(OH)-CH2O-CH2-CH(OH)-CH2OH end group with ketal protected vicinal hydroxyls, having <Mn>= 4000; 63% w/w.
[0097] Step 3.3: Thin film distillation of the product obtained in the step 3.2
[0098] 319 g of the product obtained in the step 3.2 were purified in a thin film distiller at 200°C at 7x10~3mBar. Two fractions were collected, a heavy residue (67% weight) and a light fraction (33%). The IR and NMR analysis of the distilled light fraction confirmed that the isolated product is the protected tetraol derivative that didn't undergo esterification (< 1 %) via same characteristic absorption bands/peaks as detailed in step 1.3.
[0099] Steo 3.4: Deorotection of Tetraol-ketal
[0100] Same procedure as detailed in step 1.4 was applied to 58 g of light fraction from step 3.3, obtaining 50 g of pure tetraol, whose structure was confirmed by 19F-NMR analysis, as detailed in 1.4 here above. The overall recovery yield of the pure tetraol was found to be 88.7%, while purity of said tetraol was 99%.
[0101] EXAMPLE 4 (Tetraol 2000 narrow MWD+ dodecandioic acid acyl chloride)
[0102] Analysis of raw mixture (M1)
[0103] Same mixture (M1) of example 1 was used.
[0104] Step 4. 1: Protection of vicinal hydroxy! groups
Vicinal groups in mixture (M 1) were protected following procedure detailed in step 1.1 (Ex. 1).
[0105] Step 4.2: Esterification with a fatty diacid
[0106] Step 4.2a): Preparation of acyl chloride derivative of dodecandioic acid
[0107] Same procedure as detailed in step 1.2a) were followed, but using 51.6 g (0.43 moles) of thionyl chloride, 1 ml of pyridine, and 28 g (0.12 moles) of
dodecandioic acid of formula: HO-C(O)-(CH2)10-C(O)-OH.
A low viscous dark liquid (32 g) was obtained, which was found to be by IR analysis corresponding diacyl chloride derivative. IR band of: acid moieties: 1710 cm"1 (carbonyl stretching); acyl chloride moieties: 1800 cm"1 (carbonyl stretching). [0108] Step 4.2b): PFPE -esterification [0109] Same procedure as detailed in step 1.2b) (Ex. 1) was followed, but using
400 g of the product from step 4.1 (containing 0.1 moles of free OH groups), 16 g (0.123 moles) of N-Ethyldiisopropylamine and 100 g (0.05 mol) of the diacyl chloride from step 4.2a). [0110] A viscous light yellow liquid was isolated and found to have the following composition by IR (band at 1810 cm"1) and 1H-NMR analysis:
- tetraol protected as ketal having <Mn>= 2000: 61 %w/w;
- esters between acyl chloride and PFPE macromolecules containing a -CF2CH2OH and/or -CF2CH2O-CH2CH(OH)-CH2O-CH2-CH(OH)-CH2OH end group with ketal protected vicinal hydroxyls, having <Mn>= 4300; 39% w/w .
[0111] Step 4.3: Thin film distillation of the product obtained in the step 4.2
[0112] 360 g of the product obtained in the step 4.2 were purified in a thin film distiller at 250°C at 8x10"3mBar. Two fractions were collected, a heavy residue (44% weight) and a light fraction (56%). The IR and NMR analysis of the distilled light fraction confirmed that the isolated product is the protected tetraol derivative that didn't undergo esterification (< 1 %) via same characteristic absorption bands/peaks as detailed in step 1.3.
[0113] Step 4.4: Deorotection of Tetraol-ketal
[0114] Same procedure as detailed in step 1.4 was applied to 107 g of light fraction from step 4.3, obtaining 100 g of pure tetraol, whose structure was confirmed by 19F-NMR analysis, as detailed in 1.4 here above. The overall recovery yield of the pure tetraol was found to be 90%, while purity of said tetraol was 99%.
[0115] EXAMPLE 5 (Tetraol 1000 narrow MWD+ Diac 1000)
[0116] Analysis of raw mixture (M^)
[0117] A mixture (M5) was submitted to NMR analysis as such and after
derivatization with trifluoroacetic anhydride, as detailed in example 1. The analysis yielded the following composition for mixture (M5):
• 14% end groups of formula -CF2CH2OH
• 10% end groups of formula -CF2CH2O-CH2CH(OH)-CH2O-CH2 CH(OH)-CH2OH (bis-adduct);
• 76% end groups of formula -CF2CH2O-CH2CH(OH)-CH2OH.
[0118] Its other relevant molecular parameters, as determined by GPC analysis are: average molecular weight = 1000, Polydispersity 1.10.
[0119] Step 5. 1: Protection of vicinal hydroxy! groups
Same procedure as detailed in step 1.1 (ex. 1) was followed, but using 150 g (0.30 moles) of mixture (M5), 110 g (140 ml, 1.9 moles) of acetone, 140 ml of petroleum ether and 0.12 g of sulphuric acid, as well as 0.6 g of sodium acetate. 160 g of protected ketal mixture were isolated and characterized.
[0120] Step 5.2a): Preparation ofacyl chloride derivative of a PFPE diacid
[0121] Same procedure as detailed in step 1.2a) were followed, but using 21O g of Z-DIAC perfluoropolyether diacid having linear structure and carboxylic acid end group of Mn =1000 (Z-DIAC), complying with formula: HO-C(O)CF2O-(CF2CF2O)p-(CF2O)q-CF2C(O)-OH with p/q being 1.0, 125 g (1.28 moles) of thionyl chloride and 5 ml of pyridine. 201 g of Z-DIAC acyl chloride derivative were obtained and characterized by NMR and IR spectroscopy.
[0122] Step 5.2b): PFPE-esterification
[0123] Same procedure as detailed in step 1.2b) was followed, but using 125 g of the product from step 5.1 (containing 0.06 moles of free OH groups), 16 g (0.123 moles) of N-Ethyldiisopropylamine and 30 g (0.03 mol) of Z-DIAC acyl chloride from step 5.2a).
A viscous light yellow liquid (142 g) was isolated and found to have the following composition by IR and 19F-NMR analysis:
- tetraol protected as ketal having <Mn>= 1000: 47%w/w
- esters between acyl chloride and PFPE macromolecules containing a -CF2CH2OH and/or -CF2CH2O-CH2CH(OH)-CH2O-CH2-CH(OH)-CH2OH end group with ketal protected vicinal hydroxyls, having <Mn>= 3000; 53%
w/w.
[0124] Step 5.3: Thin film distillation of the product obtained in the step 5.2
[0125] 100 g of the product obtained in the step 5.2 were purified in a thin film distiller at 190°C at 8x10~3mBar. Two fractions were collected, a heavy residue (56% weight) and a light fraction (44%). The IR and NMR analysis of the distilled light fraction confirmed that the isolated product is the protected tetraol derivative that didn't undergo esterification (< 1 %) via same characteristic absorption bands/peaks as detailed in step 1.3.
[0126] Step 5.4: Deorotection of Tetraol-ketal
[0127] Same procedure as detailed in step 1.4 was applied to 47 g of light fraction from step 5.3, obtaining 43 g of pure tetraol, whose structure was confirmed by 19F-NMR analysis, as detailed in 1.4 here above. The overall recovery yield of the pure tetraol was found to be 93.6%, while purity of said tetraol was 99%.
[0128] EXAMPLE 6 (Tetraol 1000 narrow MWD+ isostearic acid acyl chloride)
[0129] Analysis of raw mixture (Ms)
[0130] A mixture (M6) was submitted to NMR analysis as such and after derivatization with trifluoroacetic anhydride, as detailed in example 1. The analysis yielded the following composition for mixture (M6):
• 8% end groups of formula -CF2CH2OH
• 16% end groups of formula -CF2CH2O-CH2CH(OH)-CH2O-CH2 CH(OH)-CH2OH (bis-adduct);
• 76% end groups of formula -CF2CH2O-CH2CH(OH)-CH2OH.
[0131] Its other relevant molecular parameters, as determined by GPC analysis are: average molecular weight = 1000, Polydispersity 1.07.
[0132] Step 6. 1: Protection of vicinal hydroxy! groups
Vicinal groups in mixture (M6) were protected following procedure detailed in step 1.1 (Ex. 1), using 150 g of mixture (M6), 110 g (140 ml, 1.9 moles) of acetone, 140 ml of low boiling petroleum ether and 0.12 g sulphuric acid.
147 g of clear viscous ketal derivative were obtained whose structure was confirmed by NMR analysis.
[0133] Step 6.2: Esterification with a fattv acid
[0134] Step 6.2a): Preparation ofacyl chloride derivative of isostearic acid
[0135] Same procedure as detailed in step 1.2a) were followed, but using 152 g (1.28 moles) of thionyl chloride, 5 ml of pyridine, and 59.7 g (0.21 moles) of isostearic acid of formula: (H3C)2CH(CH2)I4-C(O)-OH. A low viscous dark liquid (63.1 g) was obtained, which was found to be by IR analysis corresponding acyl chloride derivative. IR showed following absorption bands: acid moieties: 1720 cm"1 (carbonyl stretching); acyl chloride moieties: 1800 cm"1 (carbonyl stretching).
[0136] Step 6.2b): PFPE -esterification
[0137] Same procedure as detailed in step 1.2b) was followed, but using 125 g of the product from step 6.1 (containing 0.06 moles of free OH groups), 16 g (0.123 moles) of N-Ethyldiisopropylamine and 18 g (0.05 mol) of the acyl chloride from step 6.2a).
A slightly viscous light yellow liquid was isolated and found to have the following composition by IR (band at 1810 cm"1) and 1H-NMR analysis:
- tetraol protected as ketal having <Mn>= 1000: 52%w/w;
- esters between isostearic acyl chloride and PFPE macromolecules containing a -CF2CH2OH and/or -CF2CH2O-CH2CH(OH)-CH2O-CH2 -CH(OH)-CH2OH end group with ketal protected vicinal hydroxyls, having <Mn>= 1300; 48% w/w .
[0138] Step 6.3: Thin film distillation of the product obtained in the step 6.2
[0139] 107 g of the product obtained in the step 6.2 were purified in a thin film distiller at 180°C at 6x10"3mBar. Two fractions were collected, a heavy residue (53% weight) and a light fraction (47%). The IR and NMR analysis of the distilled light fraction confirmed that the isolated product is the protected tetraol derivative that didn't undergo esterification (< 1 %) via same characteristic absorption bands/peaks as detailed in step 1.3.
[0140] Step 6.4: Deprotection of Tetraol-ketal
[0141] Same procedure as detailed in step 1.4 was applied to 37 g of light fraction from step 6.3, obtaining 33 g of pure tetraol, whose structure was confirmed by 19F-NMR analysis, as detailed in 1.4 here above. The overall recovery yield of the pure tetraol was found to be 90%, while
purity of said tetraol was 99%. [0142] EXAMPLE 7 (Tetraol 1000 narrow MWD+ Krytox® 3000)
[0143] Raw mixture (M5)
[0144] Same mixture (M6) whose properties are detailed herein above in Ex. 6 was employed.
[0145] Step 7. 1: Protection of vicinal hydroxy! groups
Protected ketal mixture obtained from mixture (M6) as detailed in section 6.1 was used.
[0146] Step 7.2: Esterification with a PFPE diacid
[0147] Step 7.2b): PFPE -esterification
[0148] Same procedure as detailed in step 1.2b) (Ex. 1) was followed, but using 125 g of the product from step 6.1 (containing 0.06 moles of free OH groups), 16 g (0.123 moles) of N-Ethyldiisopropylamine and 180 g (0.06 moles) of KRYTOX® perfluoropolyether acyl fluoride (commercially available from DuPont) of formula CF3CF2CF2O-(CF(CFs)-CF2O)n-CF(CF3 )-C(O)F, with n being an integer such that the average molecular weight is 3000.
A viscous light yellow liquid (274 g) was isolated and found to have the following composition by IR and 19F-NMR analysis:
- tetraol protected as ketal having <Mn>= 1000: 25.5%w/w
- esters between KRYTOX® acyl fluoride and PFPE macromolecules containing a -CF2CH2OH and/or -CF2CH2O-CH2CH(OH)-CH2O-CH2 -CH(OH)-CH2OH end group with ketal protected vicinal hydroxyls, having <Mn>= 4000: 74.5% w/w.
[0149] Step 7.3: Thin film distillation of the product obtained in the step 7.2
[0150] 214 g of the product obtained in the step 7.2 were purified in a thin film distiller at 180°C at 6x10~3mBar. Two fractions were collected, a heavy residue (25% weight) and a light fraction (75%). The IR and NMR analysis of the distilled light fraction confirmed that the isolated product is the protected tetraol derivative that didn't undergo esterification (< 1 %) via same characteristic absorption bands/peaks as detailed in step 1.3.
[0151] Step 7.4: Deprotection of Tetraol-ketal
[0152] Same procedure as detailed in step 1.4 was applied to 50 g of light fraction
from step 7.3, obtaining 44.5 g of pure tetraol, whose structure was confirmed by 19F-NMR analysis, as detailed in 1.4 here above. The overall recovery yield of the pure tetraol was found to be 98%, while purity of said tetraol was 99%.
Claims
1. A process for the purification of a tetraol PFPE derivative [tetraol (T)] of formula (I):
HO-CH2-CH(OH)-CH2-O-CH2-CF2-O-Rf-CF2-CH2O-CH2-CH(OH)-CH2OH (I), wherein Rf represents a fluoropolyoxyalkene chain (chain Rf), i.e. a fluorocarbon segment comprising ether linkages in main chain, from a mixture of hydroxyl (per)fluoropolyether derivatives [mixture (M)], said mixture comprising said tetraol (T) and at least one hydroxyl (per)fluoropolyether [PFPE (OH)] comprising a chain Rf terminated with at least one end group of formula: -CF2CH2OHJ -CF2CH2O-CH(OH)-CH2-O-CH2-CH(OH)-CH2OH; said process comprising: step 1 : reacting the mixture (M) with ketones and/or aldehydes so as to selectively protect couples of hydroxyl groups on vicinal carbon atoms by forming corresponding cyclic ketal/acetal derivatives, so as to yield a protected mixture [mixture (P)]; step 2: reacting residual hydroxyl groups of the mixture (P) with suitable functionalizing agents enabling substantial volatility modification, so as to obtain a functionalized protected mixture [mixture (Pf)]; step 3: fractional distillation of the mixture (Pf) so as to isolate the cyclic acetal/ketal derivatives of tetraol (T); step 4. hydrolyzing the acetal/ketal derivatives of tetraol (T) so as to recover pure tetraol (T).
2. The process according to claim 1 , wherein mixture (M) comprises a mixture of hydroxyl (per)fluoropolyether derivative(s) and tetraol (T) complying with formula:
T1-O-Rf-T2 wherein:
- Rf is a fluoropolyoxyalkene chain; and
- T1 and T2 are selected among the following groups: (t1) -CF2-CH2O-CH2-CH(OH)-CH2OH;
(t2) -CF2CH2OH;
(t3) -CF2CH2O-CH(OH)-CH2-O-CH2-CH(OH)-CH2OH, with the provisio that the mixture (M) comprise at least one compound wherein T1=T2 = t1 (i.e. a tetraol (T)) and at least one hydroxyl (per)fluoropolyether with at least one Of T1 and T 2 different from t1 (i.e. a PFPE (OH))
3. The process of claim 2, wherein step 1 is carried out by contacting the mixture (M) with an aldehyde or a ketone in the presence of a protic acid.
4. The process of claim 3, wherein groups t1 , t2 and t3 yield in step 1 protected or hemi-protected end-groups as detailed in following scheme:
5. The process of claim 4, wherein the protected mixture or mixture (P) comprises a mixture of at least partially protected hydroxyl (per)fluoropolyether derivatives and protected tetraols (T) complying with formula: TVO-Rf-T2 wherein:
- Rf is a fluoropolyoxyalkene chain, as above detailed; and
- T1 and T2 are selected among the following groups: (pt1)
(ptl) (t2) -CF2CH2OH; (pt3)
6. The process of claim 5, wherein the functionalized protected mixture from step 2 [mixture (Pf)] comprises a mixture of functionalized, optionally partially protected, hydroxyl (per)fluoropolyether derivatives and protected tetraols (T) complying with formula: T1VO-Rf-T2 wherein:
- Rf is a fluoropolyoxyalkene chain, as above detailed; and
- T1 and T2 are selected among the following groups: (Pt1)
(ptl)
(ft2) -CF2CH2Gf; (pt3)
(fpt3) wherein wherein RH and R'H, equal or different from each other, are independently selected among H and C1-C12 hydrocarbon group, at least one of RH and R'H being different from H, and Gf is a functional group enabling substantial volatility modification, optionally bond at its distal end to another (ft2) or (fpt3) group, with the provisio that the mixture (Pf) comprises at least one compound wherein T\=T'2 = pt1 (i.e. a protected tetraol (T)) and at least one (per)fluoropolyether with at least one of T1 and T2 different from pt1.
7. The process of claim 6, wherein residual hydroxyl groups are functionalized in step 2 by conversion in corresponding esters moieties, via reaction with suitable carbonyl derivative(s) (acyl halides, anhydrides, acids).
8. The process of claim 7, wherein the carbonyl derivative(s) are selected among mono-carbonyl derivatives, selected from:
- organic fatty acids of formula R3-COOH, with Ra being an aliphatic C8-36 group;
- (per)fluoropolyether monoacyl derivatives of formula:
T-O- CF7CF-O- CF O CRR' -Y
CF, X
wherein X' is F or CF3; R and R', equal or different from each other are chosen independently among F, Cl, Br; Y is a -C(O)X group, with X = Cl, F, OH; T is a C1-C3 perfluorocarbon group, optionally comprising one halogen atom different from fluorine; n ranges from 1 to 25, with m/n being from 0.01 to 0.5, units being statistically distributed along the chain;
- (per)fluoropolyether monoacyl derivatives of formula: CF3CF2CF2O-(CF(CF3)-CF2O)n-CF(CF3)-C(O)-X with X = Cl, F, OH and n selected so as the average molecular weight is comprised between 100 and 10 000, preferably from 1 000 and 3 000;
- (per)fluoropolyether monoacyl derivatives of formula: CF3O-(CF2CF2O)p-(CF2O)q-C(O)-X with X = Cl, F, OH and p and q are selected so as the average molecular weight is comprised between 100 and 10 000, preferably from 1 000 and 3 000 with p/q being > 0.5, units being statistically distributed along the chain.
9. The process of claim 7, wherein the carbonyl derivative(s) are selected among di-carbonyl derivatives, selected from:
- organic fatty diacids of formula HOOC-Rb-COOH, with Rb being a divalent aliphatic C6-24 group;
- (per)fluoropolyether diacyl derivatives of formula: Y-CRR'-O-(CF2CF(CF3)O)n(CF(X')O)m-CRRΥ wherein X' is F or CF3; R and R', equal or different from each other are chosen independently among F, Cl, Br; Y is a -C(O)X group, with X = Cl, F, OH; n ranges from 1 to 25, with m/n being from 0.01 to 0.5, recurring units being statistically distributed along the chain;
- (per)fluoropolyether diacyl derivatives of formula: X-C(O)CF2O-(CF2CF2O)p-(CF2O)q-CF2C(O)-X wherein X = Cl, F, OH; p and q are selected so that the average molecular weight is comprised between 100 and 10000, preferably from 1000 and 3000 with p/q being > 0.5, recurring units being statistically distributed along the chain.
10. The process of claim 8 or 9, wherein the mixture (Pf) is fractional distilled by thin film distillation.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010550212A JP5710278B2 (en) | 2008-03-14 | 2009-03-13 | Method for purifying a polyol PFPE derivative |
| AT09721134T ATE522562T1 (en) | 2008-03-14 | 2009-03-13 | METHOD FOR PURIFYING PFPE POLYOL DERIVATIVES |
| US12/921,844 US8304515B2 (en) | 2008-03-14 | 2009-03-13 | Process for the purification of polyol PFPE derivative |
| EP09721134A EP2254931B1 (en) | 2008-03-14 | 2009-03-13 | Process for the purification of polyol pfpe derivative |
| CN200980116503.2A CN102015829B (en) | 2008-03-14 | 2009-03-13 | Process for the purification of polyol PFPE derivative |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP08152770A EP2100910A1 (en) | 2008-03-14 | 2008-03-14 | Process for the purification of polyol PFPE derivative |
| EP08152770.7 | 2008-03-14 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2009112578A1 true WO2009112578A1 (en) | 2009-09-17 |
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| PCT/EP2009/052999 WO2009112578A1 (en) | 2008-03-14 | 2009-03-13 | Process for the purification of polyol pfpe derivative |
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|---|---|
| US (1) | US8304515B2 (en) |
| EP (2) | EP2100910A1 (en) |
| JP (1) | JP5710278B2 (en) |
| KR (1) | KR101626995B1 (en) |
| CN (1) | CN102015829B (en) |
| AT (1) | ATE522562T1 (en) |
| WO (1) | WO2009112578A1 (en) |
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| GB201001345D0 (en) | 2010-01-27 | 2010-03-17 | Equateq Ltd | Process for preparing and purifying fatty acids |
| GB2533778B (en) * | 2014-12-24 | 2019-07-31 | Cambridge Display Tech Ltd | Method of treating a polymer |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0822216A2 (en) * | 1996-08-02 | 1998-02-04 | Ausimont S.p.A. | Process for preparing perfluoropolyethers |
| JP2003041279A (en) * | 2001-07-26 | 2003-02-13 | Hitachi Ltd | Method for purifying lubricant and magnetic disk having membrane of lubricant obtained from the purification method |
| US20030100454A1 (en) * | 2001-10-24 | 2003-05-29 | Fuji Electric Co., Ltd. | Method of refining a lubricant for use on a magnetic recording medium |
| US20040092406A1 (en) * | 2002-07-17 | 2004-05-13 | Fuji Electric Co., Ltd. | Method to refine lubricant for a magnetic recording medium |
| US20070298982A1 (en) * | 2004-01-14 | 2007-12-27 | Koichi Shimokawa | Lubricant for Magnetic Disks, Method for Producing the Lubricant Used in the Magnetic Disks, and Method for Manufacturing the Same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US298982A (en) * | 1884-05-20 | Breech-loading fire-arm | ||
| US92406A (en) * | 1869-07-06 | Improvement in the manufacture of granulated sugar | ||
| US100454A (en) * | 1870-03-01 | Hugh sangbtek | ||
| JP4041353B2 (en) | 2002-06-13 | 2008-01-30 | 株式会社日立グローバルストレージテクノロジーズ | Method for manufacturing magnetic recording medium |
| JP4535251B2 (en) | 2004-08-23 | 2010-09-01 | Ｈｏｙａ株式会社 | Manufacturing method of lubricant for magnetic disk |
| JP2007095234A (en) | 2005-09-30 | 2007-04-12 | Hoya Corp | Magnetic recording disk and its manufacturing method |
-
2008
- 2008-03-14 EP EP08152770A patent/EP2100910A1/en not_active Withdrawn
-
2009
- 2009-03-13 EP EP09721134A patent/EP2254931B1/en active Active
- 2009-03-13 US US12/921,844 patent/US8304515B2/en active Active
- 2009-03-13 JP JP2010550212A patent/JP5710278B2/en active Active
- 2009-03-13 WO PCT/EP2009/052999 patent/WO2009112578A1/en active Application Filing
- 2009-03-13 AT AT09721134T patent/ATE522562T1/en not_active IP Right Cessation
- 2009-03-13 CN CN200980116503.2A patent/CN102015829B/en active Active
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0822216A2 (en) * | 1996-08-02 | 1998-02-04 | Ausimont S.p.A. | Process for preparing perfluoropolyethers |
| JP2003041279A (en) * | 2001-07-26 | 2003-02-13 | Hitachi Ltd | Method for purifying lubricant and magnetic disk having membrane of lubricant obtained from the purification method |
| US20030100454A1 (en) * | 2001-10-24 | 2003-05-29 | Fuji Electric Co., Ltd. | Method of refining a lubricant for use on a magnetic recording medium |
| US20040092406A1 (en) * | 2002-07-17 | 2004-05-13 | Fuji Electric Co., Ltd. | Method to refine lubricant for a magnetic recording medium |
| US20070298982A1 (en) * | 2004-01-14 | 2007-12-27 | Koichi Shimokawa | Lubricant for Magnetic Disks, Method for Producing the Lubricant Used in the Magnetic Disks, and Method for Manufacturing the Same |
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| Publication number | Publication date |
|---|---|
| ATE522562T1 (en) | 2011-09-15 |
| CN102015829B (en) | 2014-01-22 |
| US20110003968A1 (en) | 2011-01-06 |
| JP2011513570A (en) | 2011-04-28 |
| KR20100134019A (en) | 2010-12-22 |
| US8304515B2 (en) | 2012-11-06 |
| EP2100910A1 (en) | 2009-09-16 |
| JP5710278B2 (en) | 2015-04-30 |
| CN102015829A (en) | 2011-04-13 |
| EP2254931B1 (en) | 2011-08-31 |
| KR101626995B1 (en) | 2016-06-03 |
| EP2254931A1 (en) | 2010-12-01 |
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