WO2010130628A1 - Process for the purification of polyol pfpe derivatives - Google Patents
Process for the purification of polyol pfpe derivatives Download PDFInfo
- Publication number
- WO2010130628A1 WO2010130628A1 PCT/EP2010/056185 EP2010056185W WO2010130628A1 WO 2010130628 A1 WO2010130628 A1 WO 2010130628A1 EP 2010056185 W EP2010056185 W EP 2010056185W WO 2010130628 A1 WO2010130628 A1 WO 2010130628A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- per
- mixture
- polyol
- product
- formula
- Prior art date
Links
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
- C08G65/002—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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/34—Separation; Purification; Stabilisation; Use of additives
- C07C41/36—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
-
- 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
-
- 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
-
- 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
Definitions
- the invention pertains to a process for the purification of polyol fluoropolyether compounds useful as additives for lubricants for magnetic media.
- magnetic recording apparatus are 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 used as magnetic media lubricants are fluoropolyether derivatives comprising fluoropolyoxyalkylene chains and end-groups comprising multiple hydroxyl groups.
- Such materials can be notably manufactured by reaction of epihalohydrins with perfluoropolyether derivatives having two hydroxyl end-groups (see Scheme 1 here below), as taught in TURRI, Stefano, et al. End group chemistry of fluoro-oligomers: highly selective syntheses of diepoxy, diallyl, and tetraol derivatives.
- Scheme 1 J. polym. sci., A, Polym. chem.. 1996, vol.34, p.3263-3275.
- Scheme 1 HOChL ⁇ w ⁇ PFPE cha ⁇ n ⁇ vCH,OH
- 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, which require burdensome separation procedures.
- 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.
- PFPE hydroxyl (per)fluoropolyether derivative
- the (per)fluoropolyoxyalkylene chain (chain Rf) of the PFPE (OH) is typically a chain comprising recurring units R°, said recurring units having general formula -(CF 2 )J-CFK-O-, wherein j is an integer of from O to 3 and
- K is selected between a fluorine atom and a C1-C5 perfluoro(oxy)alkyl group.
- PFPE perfluoropolyether derivative
- Rf is a (per)fluoropolyoxyalkylene chain (chain Rf);
- T 2 - Ti and T 2 are independently selected from the end-groups having formulae (t-
- PFPE hydroxyl (per)fluoropolyether derivative
- M-A formula (M-A) here below: T 1 -O-(CFX 1 O) C i(CFX 2 CFX 3 O ⁇ (CF 2 CF 2 CF 2 O) C3 (CF 2 CF 2 CF 2 O) C4 -T 2 (H-A), wherein:
- - X 1 , X 2 and X 3 are independently selected between a fluorine atom and a -CF3 group;
- - c1 , c2 , c3 and c4, equal or different from each other are independently integers > O such that the sum c1 +c2+c3+c4 is in the range between 5 and 2000, preferably between 10 and 500; should at least two of c1 , c2, c3 and c4 be different from zero, the recurring units are generally statistically distributed along the (per)fluoropolyoxyalkylene chain.
- PFPE hydroxyl (per)fluoropolyether derivative
- Hl-A T 1 -O(CF 2 O) C i(CF 2 CF 2 O) C2 -T 2 (Ml-A), wherein:
- - c1 and c2 are independently integers > 0 such that the sum c1 + c2 is in the range between 5 and 2000, preferably between 10 and 500, the recurring units being generally statistically distributed along the (per)fluoropolyoxyalkylene chain.
- the polyol (per)fluoropolyether derivative [polyol (P)] preferably comprises a hydroxyl (per)fluoropolyether derivative [PFPE (OH)] complying with formula (I-A) as described above, wherein one of Ti and T2 is an end-group having formula (t.3) as defined above, the reminder being an end-group having formula (t.2) as defined above, that is to say that the polyol (P) preferably comprises a pentaol (per)fluoropolyether derivative [pentaol (P)].
- the polyol (P) more preferably comprises a hydroxyl (per)fluoropolyether derivative [PFPE (OH)] complying with formula (M-A) as described above, wherein Ti and T2 are defined as above.
- the polyol (P) even more preferably comprises a hydroxyl
- the mixture (M) preferably comprises a polyol (P) as defined above and at least one hydroxyl (per)fluoropolyether derivative [PFPE (OH)] which is different from said polyol (P) and complies with formula (I-A) as described above, wherein Ti and T2 independently represent end-groups having formulae (t-
- the mixture (M) more preferably comprises a polyol (P) as defined above and at least one hydroxyl (per)fluoropolyether derivative [PFPE (OH)] which is different from said polyol (P) and complies with formula (M-A) as described above, wherein Ti and T2 are defined as above.
- the mixture (M) even more preferably comprises a polyol (P) as defined above and at least one hydroxyl (per)fluoropolyether derivative [PFPE (OH)] which is different from said polyol (P) and complies with formula (Ml-A) as described above, wherein Ti and T2 are defined as above.
- the mixture (M) is typically manufactured reacting at least one diol (per)fluoropolyether derivative [PFPE (OH)2] comprising at least one (per)fluoropolyoxyalkylene chain (chain Rf) and two diol end-groups with epihalohydrins or with glycidol having formula:
- the diol (per)fluoropolyether derivative [PFPE (OH)2] typically complies with formula (I-A) as described above, wherein Ti and T2 both comply with end-groups having formula (t-
- the diol (per)fluoropolyether derivative [PFPE (OH)2] has preferably a polydispersity index (PDI) ranging from 1 to 1.4, more preferably from 1 to
- the polydispersity index (PDI) is hereby expressed as the ratio of weight average molecular weight (M w ) to number average molecular weight (M n ), as determined notably by GPC, wherein:
- Non-limitative examples of suitable PFPEs (OH)2 include, notably, diol
- FOMBLIN® Z-DOL 1000 polydispersity index of about 1.07
- FOMBLIN® Z-DOL 2000 polydispersity index of about 1.05
- FOMBLIN® Z-DOL 2000 polydispersity index of about 1.25
- FOMBLIN® Z-DOL 3000 polydispersity index of about 1.08
- the mixture (M) is preferably manufactured reacting at least one diol (per)fluoropolyether derivative [PFPEs (OH)2] as defined above with glycidol.
- the mixture (M) is more preferably manufactured reacting at least one diol (per)fluoropolyether derivative [PFPE (OH)2] as defined above with glycidol, wherein the glycidol/PFPE (OH)2 equivalent ratio is typically higher than 1.1 and typically lower than 1.4.
- T tetraol
- PFPE hydroxyl (per)fluoropolyether derivative
- hexaol (H) is hereby intended to denote a polyol (per)fluoropolyether derivative [polyol (P)] complying with formula (I-A) as described above, wherein Ti and T2 both comply with end-groups having formula (t.3) as defined above.
- the mixture (M) typically comprises a mixture of hydroxyl
- Step 1 of the process of the invention is advantageously carried out by reacting the mixture (M) with a ketone and/or an aldehyde so as to yield corresponding mixture of cyclic ketal/acetal (per)fluoropolyether derivatives [PFPEs (OH) p ] [protected mixture (P)].
- ketones and aldehydes include, notably, acetone, methylethylketone, cyclohexanone, phenylmethylketone, acetaldehyde.
- Step 1 is typically carried out in the presence of a protic acid.
- Non-limitative examples of suitable protic acids include, notably, p-toluensulphonic acid, acetic acid, sulphuric acid.
- Step 1 is optionally carried out in the presence of one or more organic solvents (S) able to at least partially dissolve the mixture (M) and the ketone and/or the aldehyde.
- suitable organic solvents (S) include, notably, petroleum ether, butyl acetate, dimethylformamide, toluene, hexane.
- step 1 is carried out in the absence of one or more organic solvents (S) as defined above, the ketone and/or the aldehyde also effecting at least partial solubilisation of mixture (M).
- Couples of hydroxyl groups on vicinal carbon atoms of the hydroxyl (per)fluoropolyether derivatives [PFPEs (OH)] of the mixture (M) are advantageously selectively protected in step 1 of the process of the invention due to the increased stability of the five-membered cyclic ketal/acetal structures so obtained with respect to reaction of distal hydroxyl groups of said PFPEs (OH) with a ketone and/or an aldehyde.
- step 1 of the process of the invention end-groups having formulae (t.2) and (t.3) as defined above typically react to advantageously yield corresponding protected or hemi-protected end-groups having formulae (t.2 P ) and (t,3 P ) respectively as sketched in the scheme here below, whereas end-groups having formula (t-
- RH and R'H are intended to independently represent a hydrogen atom or a C1-C-12 hydrocarbon group, with the proviso that at least one of RH and R'H is different from hydrogen.
- the cyclic ketal/acetal (per)fluoropolyether derivative [PFPE (OH) p ] typically comprises at least one (per)fluoropolyoxyalkylene chain (chain Rf) and at least one end-group selected from those having formulae (t-
- PFPE (OH) p cyclic ketal/acetal (per)fluoropolyether derivative
- Rf is a (per)fluoropolyoxyalkylene chain (chain Rf);
- T'i and T'2 are independently selected from the end-groups having formulae (t-
- the protected mixture (P) typically comprises a hemi-protected polyol (P) [polyol (Pp)], said polyol (P p ) comprising one or more cyclic ketal/acetal (per)fluoropolyether derivatives [PFPEs (OH) p ] comprising at least one (per)fluoropolyoxyalkylene chain (chain Rf) and at least one end-group having formula (f.3 P ) as defined above, and at least one cyclic ketal/acetal (per)fluoropolyether derivative [PFPE (OH) p ] which is different from said polyol (P p ) and comprises at least one (per)fluoropolyoxyalkylene chain (chain Rf) and at least one end-group selected from those having formulae (t-i) and (t2 P ) as defined above.
- PFPEs (OH) p ] comprising at least one (per)fluoropolyoxyalkylene chain (chain
- step 2 of the process of the invention the protected mixture (P) is submitted to adsorption on silica gel so as to yield an adsorbed protected product [adsorbed product (P p )] and a desorbed protected product [desorbed product (P p )] is then recovered by subsequent desorption from silica gel of said adsorbed product (P p ).
- the "adsorption on silica gel” is hereby intended to denote the reversible process of physical-chemical binding of a substance to an adsorbent silica gel substrate and the "desorption from silica gel” is hereby intended to denote the reverse process of adsorption on silica gel as defined hereinabove whereby the adsorbed substance is removed from the adsorbent silica gel substrate.
- silica gel is hereby intended to represent silica particles prepared by precipitation of colloidal silica followed by dehydration, said silica particles containing silicon dioxide in an amount of from about 96.5% by weight to about 99.6% by weight.
- colloidal silica is hereby intended to denote an aqueous dispersion containing amorphous silica particles in an amount of from about 15% by weight to about 50% by weight.
- amorphous silica particles is hereby intended to denote that silica particles do not have a crystalline structure as defined by X-ray diffraction measurements.
- the silica gel has a BET specific surface area ranging preferably from 200 m 2 /g to 800 m 2 /g, more preferably from 250 m 2 /g to 700 m 2 /g, even more preferably from 400 m 2 /g to 600 m 2 /g.
- the BET specific surface area is measured as per the Brunauer, Emmett and Teller method according to ISO 9277 using nitrogen.
- Non-limitative examples of suitable silica gels include, notably, silica gels having an average particle size in the range of 50-100 mesh, 70-230 mesh and 230-400 mesh as defined by the U.S. Standard Sieve Series according to ASTM E-11-61.
- step 2 of the process of the invention the protected mixture (P) is submitted to adsorption on silica gel typically in the presence of (per)fluoropolyethers having non functional end-groups which are able to dissolve said protected mixture (P).
- the protected mixture (P)/silica gel weight ratio generally ranges between 1 and 4, preferably ranges between 1 and 3.5, more preferably ranges between 1 and 3.
- the (per)fluoropolyethers having non functional end-groups preferably comply with formula here below:
- - X E1 , X E2 and X E3 are independently selected between a fluorine atom and a -CF3 group;
- - Ei and E2 are C-i-C ⁇ (per)fluoroalkyl groups, optionally comprising an atom selected between hydrogen and chlorine;
- - e1 , e2, e3 and e4 are independently integers > 0 such that the sum c1 +c2+c3+c4 is in the range between 1 and 100, preferably between 2 and 20; should at least two of e1 , e2, e3 and e4 be different from zero, the recurring units are generally statistically distributed along the (per)fluoropolyoxyalkylene chain.
- Non-limitative examples of suitable (per)fluoropolyethers having non-functional end-groups include, notably, GALDEN® ZV60 perfluoropolyether and hydrofluoropolyethers notably disclosed in US 2007051916 (3M INNOVATIVE PROPERTIES CO.) 08.03.2007 or in US 6953082 (3M INNOVATIVE PROPERTIES CO.) 11.10.2005 .
- step 2 of the process of the invention the desorption from silica gel of the adsorbed product (P p ) is typically carried out by extracting said adsorbed product (P p ) by one or more organic solvents (S') and then recovering by separation from the silica gel the corresponding desorbed product (Pp).
- the organic solvent (S') is typically a polar organic solvent (S' p ).
- the polar organic solvent (S' p ) is preferably selected among alcohols, ketones, carboxylic acids, nitriles, amides, esters, alkylsulphoxides, more preferably among alcohols.
- suitable polar organic solvents (S'p) include, notably, methanol, ethanol, propanol, acetic acid, methyl or ethyl acetate, acetonitrile, dimethylformamide, acetone, methylethylketone, dimethylsulphoxide.
- step 2 of the process of the invention the desorption from silica gel of the adsorbed product (P p ) is typically carried out at temperatures ranging between room temperature and the normal boiling point of the organic solvent (S') as defined above, preferably at temperatures ranging between room temperature and 100°C.
- the desorption from silica gel of the adsorbed product (P p ) is typically carried out at atmospheric pressure.
- the term "adsorbed protected product [adsorbed product (P p )]” is hereby intended to denote polyol (P p ) as defined above adsorbed on silica gel and the term “desorbed protected product [desorbed product (P p )]” is hereby intended to denote polyol (P p ) as defined above dissolved in one or more organic solvents (S') as defined above.
- step 3 of the process of the invention the desorbed product (P p ), as recovered from step 2, is submitted to distillation under reduced pressure so as to isolate a protected product residue [product (P,-)].
- step 4 of the process of the invention the product (P 1 -), as recovered from step 3, is submitted to hydrolysis so as to obtain polyol (P) as defined above.
- the hydrolysis is typically carried out under acid catalysis.
- the product (P r ), as recovered from step 3, is generally contacted with an acid aqueous or an acid aqueous alcoholic solution (e.g. an aqueous or an aqueous alcoholic solution of HCI, H2SO4, CH3COOH).
- an acid aqueous or an acid aqueous alcoholic solution e.g. an aqueous or an aqueous alcoholic solution of HCI, H2SO4, CH3COOH.
- the polyol (P) typically comprises an amount of pentaol (P) as defined above of at least 50% by moles, preferably of at least 55% by moles, more preferably of at least 60% by moles.
- the temperature was raised to 65°C and 4.89 moles of glycidol were fed into the reactor during 6 hours.
- the reaction was carried out during 4 hours.
- the reaction mixture was then cooled down to room temperature and a crude product was recovered by washing with a mixture of 690 g of demineralised water, 200 g of a 30 wt. % aqueous solution of HCI and 690 g of isobutylic alcohol and subsequent washing with 2 x 450 g of demineralised water.
- the reaction product (3.77 Kg, 3.47 eq.) was recovered by distillation under reduced pressure (yield: 95.9%) and characterized by 1 H-NMR analysis as such and after derivatization treatment with trifluoroacetic anhydride.
- Derivatized products were prepared by treating 5 g of the reaction product with 10 g of trifluoroacetic anhydride so as to convert hydroxyl groups into corresponding trifluoroacetate 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
- reaction mixture was refluxed under stirring and water was removed and collected in an external trap.
- water evolution stopped (about 20 hours)
- the mixture was cooled down to room temperature and 10 g of anhydrous sodium acetate were added.
- the mixture was filtered and petroleum ether and acetone were removed by distillation under reduced pressure.
- Step 1.4 Deorotection
- composition of the mixture as determined by 1 H-NMR analysis, was the following:
- the product had an average molecular weight of 2164 g/mol and a polydispersity index of 1.05.
- the product had an average molecular weight of 2196 g/mol and a polydispersity index of 1.28.
- Step 2. 1 Protection of vicinal hydroxy! groups
- step 1.1 Same procedure as detailed in Example 1 , step 1.1 , was followed but charging the reactor with 3.7 Kg (3.38 eq.) of the product obtained as in Example 2, synthesis of mixture (M2).
- Step 2.2 and 2.3 Adsorption/desorption on silica gel and distillation under reduced pressure
- step 1.2 and 1.3 Same procedure as detailed in Example 1 , step 1.2 and 1.3, was followed but charging the reactor with 3.74 Kg (3.3 eq.) of the product obtained as in Example 2, step 2.1 , and then treating silica gel recovered from filtration of the obtained suspension with 4.4 Kg of methanol.
- a clear low-viscous product (1.64 Kg, 1.44 eq.) was isolated by filtration and subsequent distillation under reduced pressure (yield: 94%) and characterized by 1 H-NMR.
- Step 2.4 De protection
- step 1.4 Same procedure as detailed in Example 1 , step 1.4, was followed but charging the reactor with 1.64 Kg of the product obtained as in Example 2, step 2.3.
- composition of the mixture as determined by 1 H-NMR analysis, was the following:
- the product had an average molecular weight of 2125 g/mol and a polydispersity index of 1.29.
- reaction product (1.11 Kg, 1.89 eq.) was recovered by distillation under reduced pressure (yield: 94.1 %) and characterized by 1 H-NMR analysis following same procedure as detailed in Example 1 , synthesis of mixture (M1).
- the product had an average molecular weight of 1207 g/mol and a polydispersity index of 1.06.
- Step 3. 1 Protection of vicinal hydroxy! groups
- step 1.1 Same procedure as detailed in Example 1 , step 1.1 , was followed but charging the reactor with 1.11 Kg (1.89 eq.) of the product obtained as in Example 3, synthesis of mixture (M3), 900 g of acetone, 425 g of petroleum ether and 0.5 ml of 96% sulphuric acid and, when water evolution stopped (about 15 hours), adding to the reaction mixture 5 g of anhydrous sodium acetate.
- Step 3.2 and 3.3 Adsorption/desorption on silica gel and distillation under reduced pressure
- step 1.2 and 1.3 Same procedure as detailed in Example 1 , step 1.2 and 1.3, was followed but charging a 10 It. reactor with 1.17 Kg (1.89 eq.) of the product obtained as in Example 3, step 3.1 , 6 Kg of GALDEN® ZV60 PFPE and 0.90 Kg of silica gel (60-90 mesh) dried at 200°C for 15 hours and then treating silica gel recovered from filtration of the so-obtained suspension with 2.2 Kg of methanol during 4 hours.
- step 1.4 Same procedure as detailed in Example 1 , step 1.4, was followed but reacting 0.51 Kg of the product obtained as in Example 3, step 3.3, 200 g of methanol, 85 g of demineralised water and 20 g of a 30 wt. % aqueous solution of HCI during 6 hours.
- composition of the mixture as determined by 1 H-NMR analysis, was the following:
- the product had an average molecular weight of 620 g/mol and a polydispersity index of 1.07.
- reaction product (5.55 Kg, 3.43 eq.) was recovered by distillation under reduced pressure (yield: 98%) and characterized by 1 H-NMR analysis following same procedure as detailed in Example 1 , synthesis of mixture (M1).
- the product had an average molecular weight of 3151 g/mol and a polydispersity index of 1.10.
- Step 4. 1 Protection of vicinal hydroxy! groups
- step 1.1 Same procedure as detailed in Example 1 , step 1.1 , was followed but charging the reactor with 5.55 Kg (3.43 eq.) of the product obtained as in Example 4, synthesis of mixture (M4), and refluxing under stirring the reaction mixture until water evolution stopped (about 25 hours). A clear low-viscous product (5.53 Kg, 3.36 eq.) was isolated (yield: 98%) and characterized by 1 H-NMR analysis.
- Step 4.2 and 4.3 Adsorption/desorption on silica gel and distillation under reduced pressure
- step 1.2 and 1.3 Same procedure as detailed in Example 1 , step 1.2 and 1.3, was followed but charging the reactor with 5.53 Kg (3.36 eq.) of the product obtained as in Example 4, step 4.1 , and then treating silica gel recovered from filtration of the obtained suspension with 4.5 Kg of methanol during 5 hours.
- a clear low-viscous product (2.1 Kg, 1.27 eq.) was isolated by filtration and subsequent distillation under reduced pressure (yield: 95%) and characterized by 1 H-NMR.
- Step 4.4 Deorotection
- step 1.4 Same procedure as detailed in Example 1 , step 1.4, was followed but reacting 2.05 Kg of the product obtained as in Example 4, step 4.3, 370 g of methanol, 160 g of demineralised water and 50 g of a 30 wt. % aqueous solution of HCI during 8 hours.
- composition of the mixture is the following:
- the product had an average molecular weight of 3032 g/mol and a polydispersity index of 1.09.
Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2012510218A JP5707393B2 (en) | 2009-05-15 | 2010-05-06 | Method for purifying polyol PFPE derivatives |
EP10716364.4A EP2430067B1 (en) | 2009-05-15 | 2010-05-06 | Process for the purification of polyol pfpe derivatives |
KR1020117029035A KR101694567B1 (en) | 2009-05-15 | 2010-05-06 | Process for the purification of polyol pfpe derivatives |
US13/319,680 US8664353B2 (en) | 2009-05-15 | 2010-05-06 | Process for the purification of polyol PFPE derivatives |
CN201080032226.XA CN102482410B (en) | 2009-05-15 | 2010-05-06 | Process for the purification of polyol pfpe derivatives |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP09160387 | 2009-05-15 | ||
EP09160387.8 | 2009-05-15 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2010130628A1 true WO2010130628A1 (en) | 2010-11-18 |
Family
ID=40829631
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2010/056185 WO2010130628A1 (en) | 2009-05-15 | 2010-05-06 | Process for the purification of polyol pfpe derivatives |
Country Status (7)
Country | Link |
---|---|
US (1) | US8664353B2 (en) |
EP (1) | EP2430067B1 (en) |
JP (1) | JP5707393B2 (en) |
KR (1) | KR101694567B1 (en) |
CN (1) | CN102482410B (en) |
TW (1) | TWI510516B (en) |
WO (1) | WO2010130628A1 (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2013060658A1 (en) | 2011-10-28 | 2013-05-02 | Solvay Specialty Polymers Italy S.P.A. | Process for enriching the difunctional content of (per)fluopolyether mixtures |
WO2013115380A1 (en) * | 2012-02-01 | 2013-08-08 | ダイキン工業株式会社 | Fluorine-containing copolymer, and oil- and/or water-repellent coating agent |
CN104768623A (en) * | 2012-11-05 | 2015-07-08 | 索尔维特殊聚合物意大利有限公司 | Process for the purification of (per)fluoropolyethers with carboxylate end groups |
WO2017198545A1 (en) * | 2016-05-16 | 2017-11-23 | Solvay Specialty Polymers Italy S.P.A. | (per)fluoropolyether derivatives |
EP3505553A4 (en) * | 2016-08-25 | 2020-05-06 | Daikin Industries, Ltd. | Method for separating perfluoro(poly)ether-group-containing alcohol compounds |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2010130625A1 (en) * | 2009-05-15 | 2010-11-18 | Solvay Solexis S.P.A. | Process for the purification of polyol pfpe derivatives |
EP2812738B1 (en) | 2012-02-09 | 2016-10-12 | Dow Corning Corporation | Gradient polymer structures and methods |
JP6894313B2 (en) | 2017-07-18 | 2021-06-30 | 住友化学株式会社 | Aromatic polysulfone composition |
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 |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
IT1269202B (en) * | 1994-01-31 | 1997-03-21 | Ausimont Spa | FLUOROPOLYETER-BASED COATINGS |
KR20030041279A (en) | 2001-11-19 | 2003-05-27 | 엘지전자 주식회사 | Redundancy network system and method |
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 |
US6953082B2 (en) | 2003-12-16 | 2005-10-11 | 3M Innovative Properties Company | Hydrofluoroether as a heat-transfer fluid |
ITMI20041370A1 (en) * | 2004-07-09 | 2004-10-09 | Solvay Solexis Spa | SEPARATION OF PERFLUOROPOLYTERI -PEPE-BIFUNCTIONAL AT TERMNINATION -CH20H FROM THEIR MIXTURES WITH SINGLE-FUNCTION PEPPER-CH2OH |
WO2006009057A1 (en) * | 2004-07-23 | 2006-01-26 | Matsumura Oil Research Corp. | Lubricant for recording medium and magnetic disk |
US7691282B2 (en) | 2005-09-08 | 2010-04-06 | 3M Innovative Properties Company | Hydrofluoroether compounds and processes for their preparation and use |
ITMI20062306A1 (en) * | 2006-11-30 | 2008-06-01 | Solvay Solexis Spa | FLUORINE LUBRICANTS |
JP5515224B2 (en) * | 2007-02-28 | 2014-06-11 | 日油株式会社 | Multi-branched polyoxyalkylene derivatives |
CN101878249B (en) * | 2007-10-05 | 2013-01-23 | 索维索莱克西斯公开有限公司 | Process for the manufacture of polyol perfluoropolyether derivative |
WO2010130625A1 (en) | 2009-05-15 | 2010-11-18 | Solvay Solexis S.P.A. | Process for the purification of polyol pfpe derivatives |
-
2010
- 2010-05-06 EP EP10716364.4A patent/EP2430067B1/en active Active
- 2010-05-06 WO PCT/EP2010/056185 patent/WO2010130628A1/en active Application Filing
- 2010-05-06 JP JP2012510218A patent/JP5707393B2/en active Active
- 2010-05-06 US US13/319,680 patent/US8664353B2/en active Active
- 2010-05-06 TW TW099114525A patent/TWI510516B/en active
- 2010-05-06 CN CN201080032226.XA patent/CN102482410B/en active Active
- 2010-05-06 KR KR1020117029035A patent/KR101694567B1/en active IP Right Grant
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 |
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2013060658A1 (en) | 2011-10-28 | 2013-05-02 | Solvay Specialty Polymers Italy S.P.A. | Process for enriching the difunctional content of (per)fluopolyether mixtures |
US9145471B2 (en) | 2011-10-28 | 2015-09-29 | Solvay Specialty Polymers Italy S.P.A. | Process for enriching the difunctional content of (per) fluopolyether mixtures |
WO2013115380A1 (en) * | 2012-02-01 | 2013-08-08 | ダイキン工業株式会社 | Fluorine-containing copolymer, and oil- and/or water-repellent coating agent |
CN104203998A (en) * | 2012-02-01 | 2014-12-10 | 大金工业株式会社 | Fluorine-containing copolymer, and oil- and/or water-repellent coating agent |
JPWO2013115380A1 (en) * | 2012-02-01 | 2015-05-11 | ダイキン工業株式会社 | Fluorine-containing copolymer and oil-repellent and / or water-repellent coating agent |
CN104203998B (en) * | 2012-02-01 | 2017-07-04 | 大金工业株式会社 | Fluorinated copolymer and group oiliness and/or water-repellancy coating agent |
CN104768623A (en) * | 2012-11-05 | 2015-07-08 | 索尔维特殊聚合物意大利有限公司 | Process for the purification of (per)fluoropolyethers with carboxylate end groups |
CN104768623B (en) * | 2012-11-05 | 2017-02-08 | 索尔维特殊聚合物意大利有限公司 | Process for the purification of (per)fluoropolyethers with carboxylate end groups |
WO2017198545A1 (en) * | 2016-05-16 | 2017-11-23 | Solvay Specialty Polymers Italy S.P.A. | (per)fluoropolyether derivatives |
US10941316B2 (en) | 2016-05-16 | 2021-03-09 | Solvay Specialty Polymers Italy S.P.A. | (Per)fluoropolyether derivatives |
US11702568B2 (en) | 2016-05-16 | 2023-07-18 | Solvay Specialty Polymers Italy S.P.A. | (Per)fluoropolyether derivatives |
EP3505553A4 (en) * | 2016-08-25 | 2020-05-06 | Daikin Industries, Ltd. | Method for separating perfluoro(poly)ether-group-containing alcohol compounds |
Also Published As
Publication number | Publication date |
---|---|
TWI510516B (en) | 2015-12-01 |
KR20120023747A (en) | 2012-03-13 |
US8664353B2 (en) | 2014-03-04 |
EP2430067A1 (en) | 2012-03-21 |
CN102482410A (en) | 2012-05-30 |
EP2430067B1 (en) | 2013-07-17 |
KR101694567B1 (en) | 2017-01-09 |
TW201043648A (en) | 2010-12-16 |
US20120059144A1 (en) | 2012-03-08 |
JP2012526875A (en) | 2012-11-01 |
CN102482410B (en) | 2014-06-25 |
JP5707393B2 (en) | 2015-04-30 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP2430067B1 (en) | Process for the purification of polyol pfpe derivatives | |
JP6239642B2 (en) | (Per) Fluoropolyether alcohol alkoxylation method | |
EP1705203B1 (en) | Fluoropolyether compound | |
EP2197939B1 (en) | Process for the manufacture of polyol perfluoropolyether derivative | |
EP2646491B1 (en) | Triazine derivative | |
EP2430066B1 (en) | Process for the purification of polyol pfpe derivatives | |
EP2254931B1 (en) | Process for the purification of polyol pfpe derivative |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 201080032226.X Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 10716364 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2010716364 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 13319680 Country of ref document: US |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2012510218 Country of ref document: JP |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 20117029035 Country of ref document: KR Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 9230/CHENP/2011 Country of ref document: IN |