WO1994010222A1 - Polyethers perfluoroalkyles hydroxyles, procede de preparation et application a la synthese de materiaux polyurethanes - Google Patents
Polyethers perfluoroalkyles hydroxyles, procede de preparation et application a la synthese de materiaux polyurethanes Download PDFInfo
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- WO1994010222A1 WO1994010222A1 PCT/FR1993/001037 FR9301037W WO9410222A1 WO 1994010222 A1 WO1994010222 A1 WO 1994010222A1 FR 9301037 W FR9301037 W FR 9301037W WO 9410222 A1 WO9410222 A1 WO 9410222A1
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- perfluoroalkylated
- hydroxylated
- preparation
- fluorinated
- oxirane
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- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5003—Polyethers having heteroatoms other than oxygen having halogens
- C08G18/5015—Polyethers having heteroatoms other than oxygen having halogens having fluorine atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
- C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
- C08G65/16—Cyclic ethers having four or more ring atoms
- C08G65/18—Oxetanes
-
- 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
- C08G65/223—Cyclic ethers having at least one atom other than carbon and hydrogen outside the ring containing halogens
- C08G65/226—Cyclic ethers having at least one atom other than carbon and hydrogen outside the ring 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
- C08G65/26—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 and other compounds
- C08G65/2639—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 and other compounds the other compounds containing elements other than oxygen, nitrogen or sulfur
Definitions
- the present invention relates to new hydroxylated polyethers having perfluorinated side groups, to their preparation and to their use for the synthesis of materials such as fluorinated polyurethanes.
- fluorine to a polymer material leads to better surface properties, improves chemical inertness and resistance to solvents and in some cases biocompatibility.
- Fluoropolymers used as coating materials have experienced significant growth in recent years. They provide exceptional properties in this area with regard to resistance to UV radiation, the lubricating power linked to a low coefficient of friction, and in relation to the decrease in surface tension: non-wettability (hydrophobia, oleophobia), 1 anti-adhesion, anti fouling ...
- fluorinated polyurethanes which have better abrasion resistance, are of particular interest; however, the synthesis of fluorinated polyurethanes has been limited by the availability of difunctional fluorinated molecules.
- the fluorinated diols sold are very limited in number: hexafluoropentane diol, tetrafluoro hydroquinone or 4.4 ′ (hexafluoro isopropylidene) diphenol.
- the surface tension and the non-wettability of fluorinated materials are not directly linked to the level of fluorine contained in the material but to the chemical structure, to the positioning of the perfluorinated groups with respect to the macromolecular chain, and to the length of the perfluorinated chain. With equivalent fluorine levels, a polymer with perfluorinated side groups will have a much lower surface tension than a polymer comprising a polyfluorinated backbone.
- the diols having perfluorinated lateral Rp links are often obtained by acid hydrolysis of fluorinated epoxides: JP patents n ° 01.305.045 and DE n ° 3.525.494.
- the alcohol functions (primary and secondary) carried by vicinal carbons exhibit differences in reactivity.
- the diols of this type described in patents JP n ° 02.258.821 and JP n ° 02.258.822 or DE n ° 3.319.368 lead to rigid urethane segments not very favorable to favor the organization of perfluorinated groups .
- macrodiols such as polyethers, comprising pendant fluorinated groups
- polyethers comprising pendant fluorinated groups
- the ⁇ ⁇ hydroxytelechelic oligomers with pendant fluorinated groups can be obtained by grafting polyfluorinated olefins onto methylenic groups of hydroxylated polyesters: EP patent No. 0.260.842; this radical grafting necessarily leads to a random distribution of the lateral fluorinated groups, and to polyfluorinated and non-perfluorinated grafts; we know that the presence of atoms of hydrogen reduces the contribution of fluorine to surface properties.
- perfluoroalkylated ⁇ ⁇ hydroxytelechelic oligomers can be obtained by polymerization of cyclic ethers such as perfluoro or polyfluoro alkyl glycidyl ethers: US Pat. No. 3,591,547; but the polymerization conditions described in this patent are such that the chemical structure of the oligomers formed cannot be controlled. Indeed, during the cationic polymerization of cyclic ethers in the presence of acid catalysts, the initiation reaction involves a nucleophilic attack of the ether monomer (a) on the monomer activated by protonation (b). The opening of the cycle leads to the formation of a tertiary oxonium (c).
- cyclic ethers such as perfluoro or polyfluoro alkyl glycidyl ethers: US Pat. No. 3,591,547; but the polymerization conditions described in this patent are such that the chemical structure of the oligomers formed cannot be controlled. Indeed, during
- the propagation reaction is carried out by successive additions of monomer molecules to the growing chain formed by the oxonium ion (see reaction scheme 1 below). This last approach is very attractive because of its evolving nature. However, the polymerization reaction is disturbed by intramolecular transfer reactions in particular, which lead to cyclic compounds with low molecular weights. The consequences of these parasitic reactions are an increase in polymolecularity and the formation of non-functional molecules.
- the inventors observed that the coupled use of a hydroxylated initiator and of particular conditions of implementation, made it possible by cationic polymerization of perfluoroalkyl oxiranes, the obtaining of linear hydroxylated polyethers with pendant Rp chains having, unlike the prior art, a perfectly known functionality and predetermined by that of the initiator.
- This process makes it possible in particular to obtain macrodiols ⁇ ⁇ with lateral perfluoroalkylated groups, the advantage of which has been shown for the production of polyurethane materials of low surface tension.
- This synthetic route also leads to other families of fluorinated polyethers, including polyfluorinated macromonomers.
- the invention relates in particular to the following four sub-families:
- R F where Rp is a perfluorinated group comprising from 1 to 12 carbon atoms.
- These difunctional oligomers can lead to fluorinated materials by polycondensation reactions and in particular to perfluoroalkylated polyurethanes.
- Rp where R-] comprises an acrylic, ethacrylic or allylic polymerizable group.
- These macromonomers can lead to fluorinated materials by radical or photochemical polymerization.
- difunctional oligomers which incorporate a non-fluorinated co onomer can have polymerizable groups capable of subsequently inducing crosslinking.
- hydroxylated perfluoroalkylated polyethers in accordance with the invention having perfluorinated side groups, are obtained by polymerization of a monomer based on perfluoroalkylated oxiranes (homopolymerization of oxiranes and, where appropriate, copolymerization with cyclic non-fluorinated ethers substituted or not ) in an inert organic solvent.
- the polymerization is carried out in the presence of a monomeric or polymeric alcohol, and of an acid catalyst in amounts such that the ratio of the acid functions of said catalyst to the hydroxylated functions of said alcohol is substantially between 1 O -4 and 10 -1 ,
- - oxirane-based monomer is added to the reaction medium continuously or semi-continuously, so that the rate of addition of said monomer is less than or equal to the rate of consumption of perfluoroalkyl oxirane.
- oxiranes By “monomer based on oxiranes” is meant both a perfluoroalkyl oxirane used alone and in admixture with other cyclic ethers.
- the alcohol used can be a mono alcohol or a polyol, monomer or polymer; the acid catalyst is used in low concentration in a ratio with the hydroxylated functions preferably ranging between 2.10 -4 and 10.
- the monomer can be constituted by one or more polyfluorinated oxiranes or by a mixture of polyfluorinated oxirane / non-fluorinated cyclic ether (in particular rings with 3, 4 or 5 atoms) with a view to carrying out a ho opolyerization of Oxiranes, with if necessary copolymerization with said cyclic ethers.
- the non-fluorinated cyclic ether can be tetrahydrofuran, an oxetane such as dimethyl 3,3 oxetane or an allyl oxirane such as glycidyl allyl ether.
- the reaction medium is produced by mixing, in the solvent, the alcohol, the oxirane-based monomer in an amount at most equal to the stoichiometry relative to the hydroxylated functions of said alcohol, and the acid catalyst.
- the addition of said monomer takes place slowly and the duration of addition is in particular between 1 and 60 hours depending on the nature of the alcohol used as initiator and the degree of polymerization of the polyfluorinated polyether desired.
- the speed of addition of the monomer is advantageously chosen to be close to half the speed of consumption of perfluoroalkyl oxirane (by "close to” is meant an speed of addition deviating at most from 20% of the speed of consumption).
- the concentration of hydroxy functions present in the reaction medium remains throughout the duration of the reaction greater than the concentration of polyfluorinated oxirane, and preferably twice the latter.
- the polymerization reaction is preferably carried out in the inert organic solvent at a temperature between 20 ° C and 80 ° C.
- chlorinated hydrocarbon solvents such as CH 2 C1 2 , CHCI3, CCI4, CCI3CH3 or CH 2 C1CH 2 C1 are suitable for the reaction; they can be used as a pure product or as a mixture.
- the cationic polymerization of fluorinated oxiranes according to this process is carried out with a conversion rate greater than 95%.
- the acid catalyst used in the process of the invention is preferably a superacid catalyst having a Hammet acidity function of less than -6 (by "acid catalyst” is meant a simple compound or a mixture of compounds); it can be chosen from those known in the art, including Lewis acids and Bronsted acids, and more particularly from the following group: BF 3 [(C 2 H 5 ) 2 0], HBF4 (C 2 H 5 ) 2 0], CF3SO3H.
- Monoalcohols and polymer polyols can also be used: polyethylene glycol methyl ether, polyethylene glycol, polypropylene glycol, polytetrametylene glycol, bisphenol A ethoxylated, polybutadiene hydroxytelechelic, polyester hydroxytelechelic, polysiloxane ⁇ hydroxylated, in particular polydimethylsiloxyl hydroxyl in particular polydimethylsiloxane ⁇ ⁇ dihydroxylated, polyphenylmethylsiloxane hydroxytelechelic, ethoxylated glycerol.
- These polymers are in particular chosen from molar masses of between 250 and 3,500 g.mole -1 .
- hydroxylated bisblock copolymers in the presence of a polymer monoalcohol.
- hydroxylated polyfluorinated polyethers it is possible to incorporate into the polymer chain non-fluorinated cyclic ethers in particular with 3, 4 or 5 atoms, which include but are not limited to epichlorohydrin, to 3, 3 di ethyl oxetane, tetrahydrofuran, glycidyl allyl ether, so as to obtain hydroxylated perfluoroalkylated copolymers with random sequences.
- the fluorinated polyethers according to the present invention are essentially linear and have one or more reactive hydroxyl functions at the chain ends.
- the functionality of these fluorinated polyethers is determined by the number of OH functions contained in the alcohol molecule introduced at the start of the reaction.
- the alcohol which plays the role of initiator is consumed at the very beginning of the reaction and completely integrated in the polyether chain.
- the hydroxylated functions formed at the chain end during the homopolymerization of fluorinated oxiranes are almost exclusively secondary. The degree of _
- perfluoroalkylated polyethers determined by 1 H NMR, is controlled by the ratio of the concentrations of monomer based on oxiranes and of alcohol used as initiator.
- the average molar mass of perfluoroalkylated polyethers limited by their solubility in the reaction medium, does not exceed 20,000.
- the level of fluorine, incorporated in the form of perfluoroalkylated side groups, is between 10 and 70% and in particular between 25 and 67%.
- the hydroxy index of said perfluoroalkylated polyethers is between 20 and 200.
- Their glass transition or melting temperature can vary between -80 ° C. and + 100 ° C.
- the perfluorinated groups R F may have a crystalline structure.
- perfluoroalkylated hydroxylated polyethers which are the subject of the present invention are capable of reacting with organic compounds comprising isocyanate groups to lead to polyurethanes. These fluorinated polyethers can be introduced into the polyurethane matrix:
- the hydroxylated ⁇ ⁇ polyethers having perfluoroalkylated pendant groups obtained by the process described above, by reaction with diisocyanates lead to linear prepolymers terminated by isocyanate functions.
- organic diisocyanates which can be used for the synthesis of these prepolymers, mention may be made of:
- the perfluoroalkylated ⁇ ⁇ diisocyanate prepolymers obtained are brought to polymerize in the presence of a crosslinking agent and / or of a chain extender, with or without the addition of catalyst to lead to fluorinated polyurethanes.
- Polyols and polyamines are suitable as chain extenders or crosslinking agents, in particular aliphatic diols or triols (2,2 dimethyl propane 1,3 diol; 2,2 diethyl propane 1, 3 diol; 2 ethyl 2 hydroxymethyl propane 1, 3 diol ) or polyesters glycols; or polyether glycols (polyethylene, polypropylene, polytetramethylene), or aliphatic or aromatic diamines.
- the perfluoroalkylated polyurethanes obtained from the polyethers which are the subject of the present invention have remarkable surface properties.
- reaction solvents free of stabilizers, are dried in the presence of calcium hydride, calcium chloride or sodium sulphate.
- the alcohols used as initiators are dried over a molecular sieve.
- the fluorinated oxiranes are purified on a silica column.
- the polymerization is carried out under a nitrogen atmosphere.
- the nitrogen used to purge the reaction medium is dried on molecular sieve columns and silica gel before use.
- the alcohol (polymerization initiator), the solvent or the mixture of solvents and a volume (V) of fluorinated oxirane solution or of the fluorinated oxirane mixture are introduced.
- comonomer representing an amount of stoichiometric monomer (s) relative to the hydroxylated functions.
- the amount of acid catalyst injected and the reaction temperature depend on the nature of the initiator.
- the solution containing the monomer (s) is then introduced into the reaction medium continuously using a syringe pump with an equal flow rate V / 2.t.
- hydroxylated perfluoroalkylated polyethers are analyzed by 1 H and 19 F NMR, by steric exclusion chromatography and by differential scanning calorimetry (DSC).
- the molar masses and the functionality (F n ) of the fluorinated polyethers are determined by 1 H NMR, based on the resonance of the protons of the ends of hydroxyl chains (- CH - OH) after modification to trifluoroacetic ester or to phenyl carbamate.
- the theoretical molar masses are calculated from the ratio [monomer (s)] / [hydroxylated initiator].
- the molar masses M w and M n as well as the polymolecularite (I) are evaluated by steric exclusion chromatography, in polyethylene glycol equivalents, when the fluorinated polyethers are soluble in tetrahydrofuran, eluent from chromatography.
- General experimental conditions for the preparation of perfluoroalkylated polyurethanes from the aforementioned polyethers The preparation of perfluoroalkylated polyurethanes comprises two stages.
- an ⁇ ⁇ diisocyanate prepolymer is prepared by reacting an ⁇ ⁇ perfluoroalkylated macrodiol described in the present patent with a diisocyanate in the presence of a catalyst.
- the reaction is carried out under a nitrogen atmosphere under conditions analogous to those described above.
- the perfluoroalkylated macrodiol in solution and the catalyst are introduced in a ratio [catalyst] / [diol] between 10 -2 and 5.10.
- a quantity of diisocyanate is then injected into the reaction medium, such that the ratio [isocyanate functions] / [hydroxylated functions] is equal to 2.
- the prepolymer ⁇ ⁇ diisocyanate in solution is reacted with a chain extender diol and / or a crosslinking agent, in a proportion such that the stoichiometry between the isocyanate and hydroxylated functions is respected.
- the polymerization is carried out at room temperature.
- the reaction medium is deactivated with a solution of ammonia in tetrahydrofuran when the fluorinated oxirane is no longer detected by steric exclusion chromatography.
- the reaction solvent is evaporated under reduced pressure.
- Example 1 The diol used in Example 1 is substituted. " with diethylene glycol (0.48 g, 4.5 mmol.). The ratio [HBF 4 etherate] / [diol] is equal to 2.10" 3 .
- the fluorinated Oxirane solution is added in an amount of 0.34 mole of fluorinated monomer per hour and per mole of diol. For a theoretical degree of polymerization equal to 8, the addition time is 18 hours. All the experimental conditions are also analogous to those described in Example 1.
- the polymerization initiator is 3 allyl oxy 1,2 propanediol, the polymerization conditions have been modified on the following points:
- Example 4 The experimental conditions comparable to those described in Example 1 differ on the following points:
- the fluorinated monomer solution is injected with a flow rate of 1.5 moles per hour and per mole of diol,
- the duration of addition of the fluorinated oxirane is between 4 hours and 10 hours for DP th of 8 and 16.
- the diol (1.4 g, 3.32 mmol.), an ethoxylated bispnenol A of average mass 420 g per mole, is in solution in a dichloromethane - 1.1.1 trichloroethane mixture in a volume ratio 1/3,
- the duration of addition of the fluorinated monomer is 12 hours for a theoretical degree of polymerization of 8.
- Example 6 Under experimental conditions comparable to those described in Example 5, the HBF4 etherate catalyst is substituted by BF3 etherate, in a ratio [BF3 etherate] / [diol] equal to 10.
- the fluorinated oxirane (26.6 mmol.) Is added with a flow rate of 0.6 mole per hour and per mole of diol.
- the duration of addition of the fluorinated oxirane is 10 hours for a DP ⁇ equal to 8.
- the diol used is ethylene glycol (0.35 g, 3.32 mmol.) in solution in a dichloromethane / 1.1.1 trichloroethane mixture in a volume ratio 1/4,
- perfluorobutyl methyl oxirane is substituted by perfluorohexyl methyl oxirane (10 g, 26.6 mmol.) in solution in 1,1,1 trichloroethane,
- the HBF4 etherate catalyst is substituted with CF3SO3H in a [CF3SO3H] / [diol] ratio equal to 2.10 "2 .
- the fluorinated oxirane is added with a flow rate of 1.1 moles per hour and per mole of diol.
- the duration of addition of the oxirane is 5.5 hours for a DP ⁇ equal to 8.
- Example 4 Compared with Example 4, the bisphenol A ethoxylated is replaced by 1.6 hexanediol (Example 8) and 1.4 dimethanol cyclohexane (Example 9) (3.32 mmol.), solution in 1,2 dichloroethane.
- the solution of perfluorohexyl methyl oxirane is added with a flow rate of 1 mole per hour and per mole of 1.6 hexanediol and 3 moles per hour and per mole of 1.4 dimethanol cyclohexane.
- the addition times are 6 hours and 2 hours respectively.
- the temperature of the reaction medium is maintained at 55 ° C.
- reaction solvent is 1.1.1 trichloroethane
- ratio [HBF 4 etherate] / [diol] is equal to 1.5 ⁇ 10 -2 ,
- Example 1 The conditions described in Example 1 are replaced by the following data concerning:
- perfluorooctyl methyl oxirane (10 g, 21 mmol.) is in solution (1 mole.l -1 ) in 1,1,1 trichloroethane,
- the flow rate is 1 mole per hour and per mole of diol
- the duration of the polymerization it varies from 6 hours for a DP ⁇ equal to 8, to 14 hours for a DP ⁇ h equal to 16.
- the perfluorooctyl methyl oxirane is added at the rate of 1.4 mole per hour and per mole of 3 allyloxy 1,2 propanediol,
- the temperature of the reaction medium is maintained at 55 ° C.
- perfluorohexyl methyl oxirane (10 g, 26.6 mmol.) Is used as the monomer in place of the perfluorobutyl methyl oxirane and as initiator 1 hydroxy ethyl methacrylate (0.43 g, 3.32 mmol.).
- a DP ⁇ 8
- the addition time of the monomer in solution in 1,1,1 triochloroethane (reaction solvent) is 4.5 hours with a flow rate of 1.5 moles of fluorinated oxirane per hour and per mole of hydroxyethyl methacrylate.
- the polymerization is carried out under the same conditions as those described in Example 14, 1 hydroxy ethyl methacrylate being substituted by allyl alcohol.
- the ratio [HBF etherate] / [diol] is equal to 8.5 10 -3 , - the duration of addition of the monomer is 30 hours for a DP ⁇ of 8, with a flow rate of 0.2 mole of fluorinated oxirane per hour and per mole of diol.
- the duration of addition of the monomer is 25 hours for a DPth of 7 with a flow rate of 0.3 moles of fluorinated oxirane per hour and per mole of diol,
- the temperature of the reaction medium is maintained at 40 ° C.
- perfluorohexyl methyl oxirane 5 g, 13.3 mmol.
- a non-fluorinated cyclic ether in this case allyl glycidyl ether (0.76 g, 6.6 mmol.).
- the [HBF4 etherate] / [diol] ratio is equal to 10-.
- the duration of addition of the monomers is 8.5 hours with a flow rate of 1 mole per hour and per mole of diol.
- a prepolymer ⁇ ⁇ diisocyanate is prepared.
- a mixture of perfluoroalkylated macrodiol (10 g) having a DP ⁇ equal to 16, prepared according to the conditions described in Example 1, in solution in 1,1,1 trichloroethane (0.1 Ml "1 ) and dibutyl dilaurate tin (23 mg) is introduced into the reaction flask maintained under a nitrogen atmosphere
- the isophorone diisocyanate (1.03 g) is then injected by the septum into the reaction medium, maintained under magnetic stirring.
- the reaction is carried out at 45 ° C.
- the reaction time is 12 hours and the reaction solvent is evaporated under reduced pressure.
- the prepolymer ⁇ ⁇ diisocyanate obtained previously in solution in THF is reacted with 2 ethyl 2 hydroxy methyl 1,3 propanediol in an amount such that the stoichiometry between the hydroxy and isocyanate functions is generally respected.
- the isophorone diisocyanate (1.3 g) is added to a mixture of perfluoroalkylated macrodiol (10 g) with DP ⁇ equal to 8, prepared according to the conditions described in Example 7 and tin dibutyl dilaurate (31 mg).
- the critical surface tension of the polyurethane thus obtained is 9.4 mN.m.
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- Organic Chemistry (AREA)
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Abstract
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Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
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JP6510760A JPH08502541A (ja) | 1992-10-23 | 1993-10-21 | 水酸化パーフルオロアルキルポリエーテル、その調製方法、及びポリウレサン材料合成への応用 |
EP93924103A EP0665857A1 (fr) | 1992-10-23 | 1993-10-21 | Polyethers perfluoroalkyles hydroxyles, procede de preparation et application a la synthese de materiaux polyurethanes |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR9212835A FR2697256B1 (fr) | 1992-10-23 | 1992-10-23 | Polyéthers perfluoroalkylés hydroxylés, procédé de préparation et application à la synthèse de matériaux polyuréthanes. |
FR92/12835 | 1992-10-23 |
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WO1994010222A1 true WO1994010222A1 (fr) | 1994-05-11 |
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PCT/FR1993/001037 WO1994010222A1 (fr) | 1992-10-23 | 1993-10-21 | Polyethers perfluoroalkyles hydroxyles, procede de preparation et application a la synthese de materiaux polyurethanes |
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EP (1) | EP0665857A1 (fr) |
JP (1) | JPH08502541A (fr) |
FR (1) | FR2697256B1 (fr) |
WO (1) | WO1994010222A1 (fr) |
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WO1998051726A1 (fr) * | 1997-05-14 | 1998-11-19 | Minnesota Mining And Manufacturing Company | Composition fluoree contenant un produit de condensation d'un polyether fluore et d'un poly-isocyanate pour doter un substrat d'une aptitude au detachage |
US6162369A (en) * | 1997-05-14 | 2000-12-19 | 3M Innovative Properties Company | Fluorochemical composition comprising a polyurethane having a fluorochemical oligomer and a hydrophilic segment to impart stain release properties to a substrate |
US6224782B1 (en) | 1997-05-14 | 2001-05-01 | 3M Innovative Properties Company | Fluorochemical composition comprising a polyurethane having a fluorochemical oligomer and a hydrophilic segment to impart stain release properties to a substrate |
US6239247B1 (en) | 1997-05-14 | 2001-05-29 | 3M Innovative Properties Company | Fluorochemical composition comprising a urethane having a fluorochemical oligomer and a hydrophilic segment to impart stain release properties to a substrate |
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US9643130B2 (en) | 2015-03-31 | 2017-05-09 | Pall Corporation | Hydrophilically modified fluorinated membrane (IV) |
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JP4031831B2 (ja) * | 1996-01-30 | 2008-01-09 | 株式会社Adeka | 化合物及び界面活性剤 |
CN106750236B (zh) * | 2016-12-18 | 2019-01-11 | 苏州大学 | 一种含氟烷基共聚醚及其制备方法 |
WO2020109460A1 (fr) * | 2018-11-29 | 2020-06-04 | Fundacion Tecnalia Research & Innovation | Polyols à base de lignine |
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EP0152065A2 (fr) * | 1984-02-08 | 1985-08-21 | Daikin Industries, Limited | Copolymère de 1,2-époxyalcane oméga-perfluroalkylé et son utilisation |
EP0331307A2 (fr) * | 1988-03-02 | 1989-09-06 | E.I. Du Pont De Nemours And Company | Polyétherglycol perfluoroalcoylé et sa préparation |
EP0335664A2 (fr) * | 1988-03-28 | 1989-10-04 | Becton, Dickinson and Company | Polyétheréthanes fluorés et les dispositifs médicaux à partir de ceux-ci |
WO1990015092A1 (fr) * | 1989-05-31 | 1990-12-13 | The Secretary Of State For Defence In Her Britannic Majesty's Government Of The United Kingdom Of Great Britain And Northern Ireland | Polymerisation d'ethers cycliques |
-
1992
- 1992-10-23 FR FR9212835A patent/FR2697256B1/fr not_active Expired - Fee Related
-
1993
- 1993-10-21 JP JP6510760A patent/JPH08502541A/ja active Pending
- 1993-10-21 WO PCT/FR1993/001037 patent/WO1994010222A1/fr not_active Application Discontinuation
- 1993-10-21 EP EP93924103A patent/EP0665857A1/fr not_active Withdrawn
Patent Citations (5)
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FR2453871A1 (fr) * | 1979-04-11 | 1980-11-07 | Minnesota Mining & Mfg | Polyetherurethane-acrylates fluorocarbyl-substitues durcissables par des radiations et melanges polymerisables en renfermant |
EP0152065A2 (fr) * | 1984-02-08 | 1985-08-21 | Daikin Industries, Limited | Copolymère de 1,2-époxyalcane oméga-perfluroalkylé et son utilisation |
EP0331307A2 (fr) * | 1988-03-02 | 1989-09-06 | E.I. Du Pont De Nemours And Company | Polyétherglycol perfluoroalcoylé et sa préparation |
EP0335664A2 (fr) * | 1988-03-28 | 1989-10-04 | Becton, Dickinson and Company | Polyétheréthanes fluorés et les dispositifs médicaux à partir de ceux-ci |
WO1990015092A1 (fr) * | 1989-05-31 | 1990-12-13 | The Secretary Of State For Defence In Her Britannic Majesty's Government Of The United Kingdom Of Great Britain And Northern Ireland | Polymerisation d'ethers cycliques |
Non-Patent Citations (1)
Title |
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X-H. YU ET AL.: "Synthesis and Physical Properties of Poly(fluoroalkylether)urethanes", JOURNAL OF APPLIED POLYMER SCIENCE, vol. 41, no. 7/8, 1990, NEW YORK, pages 1777 - 1795 * |
Cited By (14)
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US6485789B1 (en) | 1997-04-14 | 2002-11-26 | 3M Innovative Properties Company | Fluorochemical composition containing a condensation product of a fluorochemical polyether and a poly-isocyanate to impart stain release properties to a substrate |
WO1998051726A1 (fr) * | 1997-05-14 | 1998-11-19 | Minnesota Mining And Manufacturing Company | Composition fluoree contenant un produit de condensation d'un polyether fluore et d'un poly-isocyanate pour doter un substrat d'une aptitude au detachage |
US6162369A (en) * | 1997-05-14 | 2000-12-19 | 3M Innovative Properties Company | Fluorochemical composition comprising a polyurethane having a fluorochemical oligomer and a hydrophilic segment to impart stain release properties to a substrate |
US6224782B1 (en) | 1997-05-14 | 2001-05-01 | 3M Innovative Properties Company | Fluorochemical composition comprising a polyurethane having a fluorochemical oligomer and a hydrophilic segment to impart stain release properties to a substrate |
US6239247B1 (en) | 1997-05-14 | 2001-05-29 | 3M Innovative Properties Company | Fluorochemical composition comprising a urethane having a fluorochemical oligomer and a hydrophilic segment to impart stain release properties to a substrate |
US6383633B1 (en) | 1997-05-14 | 2002-05-07 | 3M Innovative Properties Company | Fluorochemical composition comprising a polymer derived from a fluorochemical urethane (meth)acrylate monomer for imparting stain release properties to a substrate |
WO2004067499A1 (fr) * | 2003-01-31 | 2004-08-12 | Daikin Industries, Ltd. | Composé uréthane fluoré et son utilisation |
US20140259753A1 (en) * | 2013-03-15 | 2014-09-18 | Nike, Inc. | Modified thermoplastic elastomers for increased compatibility with supercritical fluids |
KR101760591B1 (ko) * | 2013-03-15 | 2017-07-21 | 나이키 이노베이트 씨.브이. | 초임계 유체와의 상용성 증가를 위한 개질된 열가소성 탄성중합체 |
US9643130B2 (en) | 2015-03-31 | 2017-05-09 | Pall Corporation | Hydrophilically modified fluorinated membrane (IV) |
US9849428B2 (en) | 2015-04-30 | 2017-12-26 | Pall Corporation | Hydrophilically modified fluorinated membrane (VI) |
CN106390782A (zh) * | 2015-07-31 | 2017-02-15 | 帕尔公司 | 亲水性多孔聚四氟乙烯膜(ii) |
CN106390782B (zh) * | 2015-07-31 | 2019-03-22 | 帕尔公司 | 亲水性多孔聚四氟乙烯膜(ii) |
US10315168B2 (en) * | 2015-07-31 | 2019-06-11 | Pall Corporation | Hydrophilic porous polytetrafluoroethylene membrane (II) |
Also Published As
Publication number | Publication date |
---|---|
FR2697256A1 (fr) | 1994-04-29 |
EP0665857A1 (fr) | 1995-08-09 |
FR2697256B1 (fr) | 1994-12-09 |
JPH08502541A (ja) | 1996-03-19 |
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