WO2002088218A1 - Procede de production de composes de polyoxyalkylene fluore - Google Patents

Procede de production de composes de polyoxyalkylene fluore Download PDF

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Publication number
WO2002088218A1
WO2002088218A1 PCT/JP2002/004264 JP0204264W WO02088218A1 WO 2002088218 A1 WO2002088218 A1 WO 2002088218A1 JP 0204264 W JP0204264 W JP 0204264W WO 02088218 A1 WO02088218 A1 WO 02088218A1
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Prior art keywords
compound
group
polyoxyalkylene compound
fluorinated
esterified
Prior art date
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PCT/JP2002/004264
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English (en)
Japanese (ja)
Inventor
Daisuke Shirakawa
Takashi Okazoe
Norihide Sugiyama
Genichirou Enna
Shin Tatematsu
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Asahi Glass Company, Limited
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Application filed by Asahi Glass Company, Limited filed Critical Asahi Glass Company, Limited
Priority to JP2002585515A priority Critical patent/JP4088773B2/ja
Publication of WO2002088218A1 publication Critical patent/WO2002088218A1/fr

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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
    • 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
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/337—Polymers modified by chemical after-treatment with organic compounds containing other elements
    • 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
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/321—Polymers modified by chemical after-treatment with inorganic compounds
    • C08G65/323—Polymers modified by chemical after-treatment with inorganic compounds containing halogens
    • C08G65/3233—Molecular halogen
    • C08G65/3236—Fluorine

Definitions

  • the present invention is industrially useful compounds, port 1 which is fluorinated
  • the present invention relates to a method for producing a compound. Rice field
  • a fluorinated polymer compound obtained by fluorinating a polymer compound having a chemical structure (C-H) in which a hydrogen atom is bonded to a carbon atom, or a derivative of the fluorinated polymer compound is an industrially useful compound.
  • fluorinated polyoxyalkylene compounds are industrially useful compounds as surfactants, surface modifiers, water / oil repellents, coating agents, lubricants, and the like.
  • the fluorination method includes (1) a method of fluorination by contact with fluorine gas (La Mar method), and (2) a method of dissolving, suspending, or dispersing a polymer compound in a solvent, There is known a liquid phase fluorine method in which fluorine gas is introduced into the solvent to fluorinate the solvent.
  • Examples of the method of (1) examples of fluorination of fluorine-free polyether was initiator Pentaerisuri Torr (Kohyo three to 5 0 0 1 7 3 JP), as essential Okishimechi Ren units Example of fluorinating non-fluorinated polyethers (Japanese Patent Publication No. Sho 63-501 667), Example of fluorinating hydrocarbon ethers (Japanese Patent Publication No. 63-501 297) ) It has been known. Examples of the method (2) include non-fluorinated poly An example of fluorinating ether (Japanese Patent Application Laid-Open No.
  • 510/520 is to fluorinate a non-fluorinated polyether having a terminal hydroxyl group as an alkoxy group to have a molecular weight of about 250 to 200.
  • Examples of producing perfluorinated polyethers in the range of (JP-A-1-225628) and examples of fluorinating partially fluorinated polyethers having terminal fluorinated alkyloxy groups Japanese Patent Application Laid-Open No.
  • An example of fluorinating a perfluorinable substance such as polyethylene glycol bis (trifluoroacetate) (Japanese Patent Application Laid-Open No. 50423019) has been published. Are known.
  • a perfluorinated organic solvent is used as a solvent during the fluorination reaction.
  • Non-fluorinated polymer compound-low fluorine content, polymer compound has low solubility in perfluorinated organic solvent and is insoluble in fluorination reaction solvent or suspended in the solvent Will exist in a state. Therefore, the problem of performing the fluorination reaction in a heterogeneous reaction system and the problem of breaking the molecular chain were remarkably recognized, and it was difficult to obtain the desired polymer compound.
  • An object of the present invention is to solve the above problems and to provide a method for producing a fluorinated polyoxyalkylene compound having various structures by an industrially advantageous method.
  • the present inventors synthesized a specific esterified polyoxyalkylene compound by subjecting a specific polyoxyalkylene compound and a specific fluorine-containing compound to an esterification reaction, and converted the esterified polyoxyalkylene compound into liquid phase fluorine.
  • the present inventors have found that the above-mentioned problems can be solved, and have led to the present invention. That is, the present invention provides the following method.
  • a method for producing a fluorinated polyalkylene compound which comprises:
  • R F1 —COX 1 By subjecting a compound represented by R F1 —COX 1 to an esterification reaction with a hydroxyl group of a polyoxyalkylene compound having at least one hydroxyl group, an esterified polyoxyalkylene compound having an R F1 —CO— group is obtained.
  • the esterified polyalkylene compound By subjecting the esterified polyalkylene compound to liquid phase fluorination, one or more of the hydrogen atoms present in the esterified polyalkylene compound are fluorinated to obtain a fluorinated polyoxyalkylene having a R F1 —CO— group.
  • R F1 represents a perfluoromonovalent organic group having 2 or more carbon atoms
  • X 1 represents a halogen atom or a hydroxyl group.
  • the perfluoro monovalent organic group is a group in which an alkyl group containing an etheric oxygen atom is perfluorinated, or a partially fluorinated alkyl group containing an etheric oxygen atom is a perfluorinated group. Manufacturing method.
  • the polyoxyalkylene compound having at least one hydroxyl group is — O (CH 2 ) (Where a represents an integer of 2 or more.)
  • the polyoxyalkylene compound having at least one hydroxyl group has a molecular weight of 300 to 10,000. 5. The method according to any one of items 1 to 4.
  • the polyoxyalkylene compound having at least one hydroxyl group is a compound containing no fluorine atom, and 95% or more of the total number of hydroxyl groups of the polyoxyalkylene compound is esterified by an esterification reaction. 7. The method according to any one of 7.
  • polyoxyalkylene compound having one or more hydroxyl groups is referred to as “polyoxyalkylene compound”.
  • a compound having a group that reacts with a hydroxyl group of the polyoxyalkylene compound to form an ester bond and a fluorinated organic group having 2 or more carbon atoms is referred to as “compound (F)”.
  • compound (F) The “polyoxyalkylene compound in which the fluorine-containing organic group is ester-bonded” is referred to as “esterified polyoxyalkylene compound”.
  • organic group refers to a group that essentially requires a carbon atom, and is a saturated group. Or an unsaturated group, and is preferably a saturated group (ie, a saturated organic group).
  • halogen atom a fluorine atom or a chlorine atom is preferable
  • Examples of the monovalent saturated organic group include an alkyl group and an alkyl group containing an etheric oxygen atom.
  • a cycloalkyl group a cycloalkyl group containing an etheric oxygen atom, or a group in which one or more of the hydrogen atoms present in these groups is substituted with a halogen atom.
  • Examples of the alkyl group include a group having a linear structure, a branched structure, and a structure partially forming a ring, and include a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, a sec-butyl group, Examples thereof include a tert-butyl group and a cycloalkyl group.
  • Examples of the alkyl group containing an etheric oxygen atom include groups in which one or more etheric oxygen atoms are interposed between carbon-carbon bonds of the alkyl group (for example, alkoxyalkyl groups and the like).
  • Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and the like.
  • Examples of the cycloalkyl group containing an etheric oxygen atom include groups in which an etheric oxygen atom is inserted between carbon-carbon bonds of the cycloalkyl group.
  • the polyoxyalkylene compound in the present invention is a compound having two or more oxyalkylene units and a hydroxyl group.
  • the polyoxyalkylene compound is a compound obtained by ring-opening addition polymerization of an alkylene oxide using a compound having a hydroxyl group as an initiator, or a large amount of an alkylene oxide such as polyoxyethylene daricol or polyoxypropylene glycol.
  • the body is preferred.
  • the oxyalkylene unit is preferably an oxyalkylene unit having 1 to 6 carbon atoms, particularly preferably an oxyalkylene unit having 2 to 6 carbon atoms, and is preferably an oxyethylene unit, an oxypropylene unit, an oxytrimethylene unit, Or, examples of oxytetramethylene unit and the like are given.
  • fluorinated oxyalkylene units are From the viewpoint that the product is stable in the oxidation reaction and the product can be obtained in a high yield, it is preferably an oxyalkylene unit having a linear structure, and one O (CH 2 ) a — (where a is 2 It is preferably an oxyalkylene unit represented by the formula: and particularly preferably the unit wherein a is 2 to 6. Further, it is preferable that two or more oxyalkylene units are present in a row.
  • the oxyalkylene unit may be one type or two or more types. When two or more kinds of oxyalkylene units are present, their connection is not particularly limited, and examples thereof include a random shape, a block shape, and a graft shape.
  • the unit derived from the initiator is preferably a divalent or higher valent alcohol residue (an alcohol residue is a residue obtained by removing a hydrogen atom from a hydroxyl group of an alcohol compound).
  • Alcohol residues having 2 to 10 valences are preferred, and alcohol residues having 2 to 6 valences are particularly preferred.
  • the molecular weight of the polyoxyalkylene compound is preferably from 300 to 10,000, particularly preferably from 300 to 400, particularly preferably from 300 to 300.
  • the fluorination reaction can be performed more smoothly and with higher yield, and the fluorinated polyoxyalkylene compound having a desired molecular weight can be obtained. Can be produced in good yield.
  • the polyoxyalkylene compound may or may not contain a fluorine atom, but is preferably a compound that does not contain a fluorine atom because of its advantage that various structures can be obtained at low cost.
  • the polyoxyalkylene compound in the present invention includes an oxyalkylene represented by the formula: (a structure other than a unit derived from the initiator) is represented by 1 O (CH 2 ) a — (where a represents an integer of 2 or more.) Compounds consisting only of units are preferred.
  • the polyoxyalkylene compound according to the present invention can be obtained by adding a polyalkylene moiety to a compound having two or more hydroxyl groups by a known method. In the production method of the present invention, first, a compound (F) having a group that forms an ester bond by reacting with a hydroxyl group and a fluorine-containing organic group having 2 or more carbon atoms is reacted with a polyoxyalkylene compound.
  • the compound (F) has one or more hydrogen atoms and one of the hydrogen atoms in a monovalent saturated organic group having two or more carbon atoms as the fluorine-containing organic group in the compound (F).
  • the fluorine-containing monovalent saturated organic group (hereinafter, referred to fluorinated monovalent saturated organic group with R F group.) are preferred, in particular fluorinated all hydrogen atoms was Perufuruoro of monovalent saturated organic group (hereinafter, referred to Perufuruoro monovalent saturated organic group as R F1 group.) is rather preferred, especially pel full O b alkyl group, Perufuruoro of an alkyl group containing an etheric oxygen atom And a group in which a partially fluorinated alkyl group containing an etheric oxygen atom is perfluorinated, and the latter two groups containing an etheric oxygen atom are more preferable.
  • the number of aethenoyloxygen atoms in the group in which the ether oxygen atom is inserted is not particularly limited, and is preferably 1 or more, and particularly preferably 1 to 5
  • the number of carbon atoms of the fluorinated organic group is 2 or more. Yes, 5 or more is preferable, and 5 to 10 is particularly preferable.
  • the number of carbon atoms of the RF group is 2 or more, particularly 5 or more, the yield of the product in the fluorination reaction tends to be remarkably increased.
  • the fluorine-containing organic group is a group containing an etheric oxygen atom, the yield of the fluorination reaction increases due to the improvement in solubility in the liquid phase during the fluorination reaction, and the like. There is an advantage that decomposition of the substrate is suppressed.
  • X 1 represents a halogen atom or a hydroxyl group.
  • a compound represented by the general formula RW—COX 1 is preferable, and a compound represented by R F1 —C ⁇ F is particularly preferable.
  • R F1 and X 1 have the same meaning as above Show.
  • the method of obtaining an esterified polyoxyalkylene compound by the reaction of a compound represented by R F1 —COX 1 is a method that is economical and can easily produce an esterified polyoxyalkylene compound having various structures.
  • R m examples include CF 3 (CF 2 ) 2 ⁇ CF (CF 3 ), CF 3 (CF 2 ) 2 OCF (CF 3 ) CF 2 OCF (CF 3 ), CF 2 C 1 (CF 2 ) 2 OCF (CF 3 ) ⁇ , CF 2 C 1 (CF 2 ) 20 [CF (CF 3 ) CF 20 ] u CF (CF 3 ) one, CF 2 C 1 (CF 2 ) 2 ⁇ CF ( CF 2 C 1) 1, CF 2 C 1 (CF 2 ) 2 ⁇ [CF (CF 2 C 1) CF z O] u CF (CF 2 C 1) 1, CF 2 C 1 CFC 1 CF 2- , CF 2 C 1 C FC 1 (CF 2 ) 2 OCF (CF 3 ) ⁇ , CF 2 C 1 CFC 1 (CF 2 ) 2 ⁇ [CF (CF 3 ) CF 20 ] u CF (CF 3 ), CF 2 C 1 CFC 1 (CF 2 ) 2 OCF (CF 2
  • the compound (F) a compound produced by the method described in WO00 / 56694 by the present applicant may be used, or a commercially available product may be used.
  • the esterification reaction between the polyoxyalkylene compound and the compound (F) is appropriately changed depending on the type of the group that reacts with the hydroxyl group present in the compound (F), and known reaction conditions can be employed.
  • the compound (F) is a compound represented by R F1 —COX 1 (R F1 and X 1 each have the same meaning as described above)
  • a known esterification reaction method and conditions May be applied.
  • the esterification reaction is preferably carried out by dissolving the polyoxyalkylene compound in a solvent (hereinafter, referred to as an esterification solvent) and reacting with the compound (F) in the solvent.
  • a solvent that dissolves the polyoxyalkylene compound and is inert to the compound (F) is preferable.
  • the reaction S is preferably carried out while dropping a solvent capable of dissolving the product, thereby suppressing the precipitation of the product.
  • the amount of the esterification solvent used is preferably 50 to 500% by mass based on the total amount of the polyoxyalkylene compound and the compound (F).
  • an acid eg, HC 1, HF, etc.
  • an alkali metal fluoride preferably NaF or KF
  • a trialkylamine is used. Is preferably present in the reaction system.
  • the base is not used, it is preferable to discharge the acid out of the reaction system by accompanying the acid with a nitrogen stream.
  • the amount of the base is preferably 1 to 10 moles per mole of the compound (F).
  • the reaction temperature of the esterification reaction is preferably ⁇ 50 ° C. or higher, more preferably +10 o t: or lower, or lower than the boiling point of the esterification solvent.
  • the reaction pressure (the pressure is indicated by a gauge pressure; the same applies hereinafter) is preferably from 0 to 2 MPa.
  • the proportion of the hydroxyl groups that react with the compound (F) can be appropriately changed according to the structure of the target fluorinated polyoxyalkylene compound. It is preferred that 95% or more of the number react with the compound (F).
  • the product has a sufficient molecular weight, so that it is difficult for the product to be entrained in a gas phase in which fluorine gas is present, and carbon-carbon which easily occurs in the gas phase Cleavage of bonds can be prevented.
  • esterifying the hydroxyl group a structural change of the hydroxyl group in the fluorination reaction can be avoided.
  • the ester bond present in the product can be converted to a 1 COF group or a 1OH group by performing thermal decomposition or hydrolysis.
  • a compound containing no fluorine atom in the hydroxyl group may be reacted.
  • the compound include a compound represented by R H —COX 2 (R H represents a monovalent organic group containing no fluorine atom, and X 2 represents a halogen atom).
  • R H is preferably an alkyl group or an alkyl group containing an etheric oxygen atom, and X 2 is preferably a chlorine atom or a fluorine atom.
  • the amount of each compound in the esterification reaction between the polyoxyalkylene compound and the compound (F) is such that the amount of the compound (F) is 1 to 5 moles per mole of the hydroxyl groups present in the polyoxyalkylene compound. It is particularly preferable that the molar amount is 1 to 2 times.
  • the crude product obtained by the esterification reaction may be purified according to the purpose or used as it is in the next reaction, etc., but is purified from the viewpoint of stably performing the next liquid phase fluorination reaction.
  • the compound (F) and the esterification solvent in the crude product are separated by a method such as drying under reduced pressure.
  • both the compound (F) and the esterification solvent were dissolved, and the crude reaction product was added dropwise to the solvent for precipitating the product to reprecipitate the esterified polyoxyalkylene compound. Thereafter, a method is preferred in which the solvent is removed by drying under reduced pressure to recover the precipitate.
  • esterified polyoxyalkylene compound a polyoxyalkylene compound having an R F1 —CO— group obtained by using a compound represented by R F1 —COX 1 as the compound (F) (R F1 and X 1 are And each has the same meaning as described above.
  • the fluorine content in the esterified polyoxyalkylene compound is preferably at least 25% by mass, more preferably at least 30% by mass, based on the molecular weight.
  • the upper limit of the fluorine content is preferably 76% by mass, and particularly preferably 65% by mass.
  • the esterified polyoxyalkylene compound is usually soluble in the liquid phase during the liquid phase fluorination reaction described below.
  • soluble means that the compound is dissolved in the liquid phase in an amount of 0.1% by mass or more under the conditions of the fluorination reaction, and the dissolving power is preferably 0.5% by mass or more.
  • the molecular weight of the esterified polyoxyalkylene compound is preferably from 130 to 160, particularly preferably from 160 to 1100.
  • the minute An esterified polyoxyalkylene compound having a molecular weight in the range of the molecular weight has the advantage that it is not entrained in the gas phase and the breakage of carbon-carbon bonds is significantly prevented. If the molecular weight of the esterified polyoxyalkylene compound is too large, the solubility in the liquid phase tends to decrease, and the type of solvent that can be used as the liquid phase decreases.
  • the esterified polyoxyalkylene compound is then subjected to a liquid-phase fluorination reaction to convert one or more of the hydrogen atoms present in the esterified polyoxyalkylene compound to fluorine.
  • a fluorinated boroxyalkylene compound is then subjected to a liquid-phase fluorination reaction to convert one or more of the hydrogen atoms present in the esterified polyoxyalkylene compound to fluorine.
  • fluorination is performed by a liquid phase fluorination reaction method.
  • a fluorination method a cobalt fluorination method and an ECF method are known.
  • a liquid phase fluorination method in which a target product is obtained with remarkable yield is used.
  • the liquid phase fluorination is carried out by reacting an esterified polyoxyalkylene compound, preferably a polyoxyalkylene compound having an R Fi- CO— group, with fluorine in a solution in a fluorinated solvent.
  • an esterified polyoxyalkylene compound preferably a polyoxyalkylene compound having an R Fi- CO— group
  • fluorine gas may be used as it is, or fluorine gas diluted with an inert gas may be used.
  • an inert gas nitrogen gas and helium gas are preferable, and nitrogen gas is particularly preferable for economic reasons.
  • the amount of fluorine gas in the nitrogen gas is not particularly limited, and is preferably 5 to 50% from the viewpoint of efficiency, and particularly preferably 5 to 20%.
  • the liquid phase fluorination is preferably carried out under the condition that the amount of fluorine is always excessively equivalent to the hydrogen atom in the esterified polyoxyalkylene compound, and particularly, the amount of fluorine becomes 1.5 times or more. This is preferable from the viewpoint of selectivity.
  • the upper limit of the amount of fluorine is preferably 3 times or less from the viewpoint of economy.
  • Fluorine may be dissolved in a fluorinated solvent in advance, and fluorine gas may be continuously introduced into the fluorinated solvent.
  • This liquid phase fluorination reaction In other words, one or more of the hydrogen atoms bonded to the carbon atoms in the esterified boroxyalkylene compound are replaced with fluorine atoms, thereby producing a fluorinated polyoxyalkylene compound.
  • C-H present in the esterified polyoxyalkylene compound is partially or completely fluorinated to produce a fluorinated polyoxyalkylene compound.
  • a reaction in which a fluorine atom is added to the bond may occur.
  • the fluorination reaction in the present invention may be a reaction for fluorinating all of the hydrogen atoms in the C—H portion (ie, complete fluorination) or a partial fluorination.
  • 40 mol% or more of the hydrogen atoms are preferably fluorinated, and particularly preferably 90 mol% or more are fluorinated.
  • the fluorinated solvent in the liquid-phase fluorination among the solvents capable of dissolving the esterified polyoxyalkylene compound, the solvent capable of dissolving the fluorine gas and preferably containing no CH bond is preferable.
  • Perfluoroalkanes FC-72, etc.
  • perfluoroethers FC-75, FC-77, etc.
  • perfluoropolyethers trade names: Crytox, Fmpulin, Galden, Demnum, etc.
  • black mouth fluorocarbons trade name: CFC
  • black mouth fluoropolyethers perfluoroalkylamines (eg, perfluorotrialkylamine, etc.), inert fluids ( (Product name: Florinert) and the like.
  • a fluorinated polyoxyalkylene compound generated by a fluorination reaction may be used. In this case, there is an advantage that the step of separating the product from the fluorinated solvent can be used.
  • chlorinated solvent chlorinated fluorinated hydrocarbons are preferable, and dichloropen fluorinated propane, and chlorinated tetrafluoroethylene oligomer are exemplified.
  • the fluorinated solvent is based on the esterified polyoxyalkylene compound. It is preferable to use a 5-fold mass or more, particularly preferably 10- to 100-fold mass.
  • L P a * s can be smoothly carried out liquid phase fluorination reaction preferably reasons, particularly preferably less particularly 5 X 1 0- 4 ⁇ 5 X 10- 3 P a ⁇ s.
  • the reaction temperature of the fluorination reaction is preferably not lower than 160 ° C and not higher than the boiling point of the fluorinated solvent.
  • the reaction temperature is preferably from 150 ° C to Is particularly preferred, and a temperature of from 20 ° C to 10100 ° C is particularly preferred.
  • reaction pressure of the fluorination reaction is preferably set to a pressurized condition, more preferably 0.01 to 5 MPa (gauge pressure, the same applies hereinafter).
  • pressure is preferably reduced to atmospheric pressure.
  • the reaction system of the fluorination reaction is preferably a batch system or a continuous system, and includes the following method 1 or method 2. Among them, the following method 2 is preferable in terms of the reaction yield and the selectivity.
  • the fluorine gas used in the following method may be diluted with an inert gas such as nitrogen gas.
  • Method 1 An esterified polyoxyalkylene compound and a fluorinated solvent are charged into a reactor, and stirring is started. Next, the reaction is performed while continuously supplying fluorine gas to the liquid phase in the reactor at a predetermined reaction temperature and reaction pressure.
  • Method 2 A fluorinated solvent is charged into a reactor, and stirring is started. Next, at a predetermined reaction temperature and reaction pressure, the esterified polyoxyalkylene compound dissolved in the fluorinated solvent and fluorine gas are continuously and simultaneously added to the liquid phase in the reactor at a predetermined molar ratio. How to supply.
  • HF is by-produced because a hydrogen atom is replaced with a fluorine atom.
  • no HF scavenger is present in the reaction system, there is an advantage that the decomposition reaction of the ester bond can be prevented, the reaction can be carried out in good yield, and the post-treatment becomes easy.
  • HF scavenger those similar to those described above can be used, and NaF is preferred.
  • the amount of the HF scavenger coexisting in the reaction system is preferably 1 to 20 times, and more preferably 1 to 5 times the mole of the total hydrogen atoms present in the esterified polyoxyalkylene compound.
  • a cooler preferably maintained at 10 ° C. to room temperature, particularly preferably maintained at about 20 ° C.
  • a cooler preferably maintained at 78 ° C to 10 ° C, preferably maintained at 30 ° C to 0 ° C.
  • a liquid return line for returning the flocculated fluorinated solvent or the like to the reactor from the cooler (j) may be provided.
  • the use of a liquid return line is particularly preferable in that the increase in the viscosity of the reaction solution due to the scattering of the fluorinated solvent can be suppressed.
  • the fluorinated solvent is continued inside the reactor.
  • Add compounds or irradiate UV And are preferred.
  • the ultraviolet irradiation time is preferably from 0.1 to 3 hours.
  • the C—H bond-containing compound is selected from organic compounds other than the esterified polyoxyalkylene compound, particularly preferably an aromatic hydrocarbon, particularly preferably benzene, toluene and the like.
  • the amount of the C—H bond-containing compound to be added is preferably from 0.1 to 10 mol%, more preferably from 0.1 to 5 mol%, based on the total number of hydrogen atoms in the esterified polyoxyalkylene compound. It is preferred that
  • the C—H bond-containing compound is preferably added in a state where fluorine gas is present in the reaction system. Further, when a C—H bond-containing compound is added, it is preferable to pressurize the reaction system.
  • the pressure at the time of pressurization is preferably from 0.01 to 5 MPa.
  • the fluorinated solvent it is preferable to remove the fluorinated solvent from the crude product of the fluorination reaction to obtain the product.
  • the crude product may be used as it is for the intended use.
  • the liquid-phase fluorination reaction in the present invention is a method that can be carried out while preventing a carbon-carbon bond breaking reaction and an ester bond decomposition reaction, so that a product having a target molecular weight can be obtained.
  • the fluorinated polyoxyalkylene compound has an oxy (perfluoroalkylene) unit represented by — ⁇ (CF 2 ) a — (where, a represents an integer of 2 or more).
  • the unit has a portion in which two or more units are connected), and is a compound having an R Fi —CO— group.
  • R Fi —CO— group.
  • all of the C—H structures be C—F structures.
  • the molecular weight of the fluorinated polyoxyalkylene compound is preferably from 330 to 370,000, particularly preferably from 410 to 300.000.
  • the fluorinated polyoxyalkylene compound in the present invention is a compound that can be usefully used as it is or by derivatization to another compound.
  • Examples of derivatization include hydrolyzing an ester bond of a fluorinated polyoxyalkylene compound into one COOH group, or decomposing the ester bond into one COF group, and further derivatizing these groups. And the like.
  • the fluorinated polyoxyalkylene compound or a derivative obtained by chemically converting the compound is useful as a surfactant, a surface modifier, a water / oil repellent, a coating agent, and a lubricant.
  • Example 11-1 Production Example of Polyoxypropylene Compound Introducing Fluorine-Containing Organic Group
  • (CF 3 ) OCF 2 CF (CF 3 ) OCF 2 CF 2 CF 3 (41 g) was added dropwise over 1.0 hour while maintaining the internal temperature at 25 ° C or higher.
  • R-113 (312 g) was added to a 50 OmL Hastelloy autoclave, and the mixture was stirred and kept at 25 ° C.
  • a cooler kept at 20 ° C, a packed bed of NaF pellets, and a cooler kept at 120 ° C were installed in series.
  • a liquid return line was installed to return the condensed liquid from the cooler kept at 20 ° C to the autoclave.
  • fluorine gas diluted to 20% with nitrogen gas hereinafter referred to as 20% fluorine gas was blown at a flow rate of 5.63 L / h for 1 hour.
  • Example 11 a solution prepared by dissolving the product obtained in Example 11 (1.20 g) in R-113 (59.5 g) was injected for 3.25 hours while blowing 20% fluorine gas at the same flow rate. And injected.
  • a Penyu erythritol-to-6EO adduct (manufactured by Asahi Glass Co., Ltd.) was prepared by adding Pentan Erythritol as an initiator and adding ethylene oxide on average 6 times.
  • a 20-OmL round-bottomed flask sufficiently purged with nitrogen was prepared, and a solution prepared by dissolving pentaerythritol-16 EO adduct (10. Og) in R-225 (100.0 g) was charged. Nitrogen gas was flowed at a flow rate of 100 ml min, the temperature was raised to 25 ° C with vigorous stirring, and CF 3 CF 2 CF 2 ⁇ CF (CF 3 ) CF 2 OCF was passed through a dropping funnel installed at the top of the device. (CF 3) was added COF (1 00. O g). After completion of the dropwise addition, the mixture was kept for 15 hours, and then cooled to room temperature to recover a crude liquid.
  • the recovered crude liquid was dried under reduced pressure, and R- 2 25, excess 3 2 2 ⁇ CF (CF 3) CF 2 OCF (CF 3) After evaporation of the COF, the residual liquid R - 22 5 (100 g) and the operation of dropping in hexane (500 g) was performed twice. Next, the product was dried under reduced pressure (100 ° (:, 24 hours) to obtain a liquid product (56.32 g) at room temperature. It was confirmed that the component was the title compound. The number average molecular weight measured by gel permeation chromatography was 2620.
  • Example 2-2 Example of fluorination of the product of Example 2-1
  • Example 2-1 Prepare the same reactor as in Example 2-1 except that the 20% fluorine gas in Example 2-1 is changed to fluorine gas diluted to 10% with nitrogen gas (hereinafter referred to as 10% fluorine gas). Prepared for the same conditions.
  • Example 2-1 While injecting 10% fluorine gas into the autoclave at the same flow rate, a solution of the product of Example 2-1 (10.3 g) dissolved in R-113 (206 g) was taken for 5.0 hours. Injected. Further, while blowing 10% fluorine gas at the same flow rate, 6 mL of the R-113 solution was injected. In addition, nitrogen gas was blown for 1.0 hour.
  • fluorinated polyoxyalkylene compounds having various structures can be produced using polyoxyalkylene compounds having various structures as starting materials. According to the production method of the present invention, by using a specific esterified polyoxyalkylene compound, a molecular chain scission reaction during a liquid phase fluorination reaction is prevented, and a desired fluorinated polyoxyalkylene compound is obtained. Compounds can be produced. Further, the fluorinated polyxylene compound produced by the reaction can be obtained without gelling.
  • the fluorinated polyoxylen compound can be used as various functional materials as it is or after derivatization to another compound by chemical conversion of an ester bond.

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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Polyethers (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé de production de composés de polyoxyalkylène fluoré de différentes structures et à un coût avantageux. Le procédé est caractérisé en ce qu'on fait réagir un composé de polyoxyalkylène ayant au moins un groupe hydroxyle, avec un composé ayant un groupe organique fluoré en C2 ou plus, et un groupe réagissant avec un groupe hydroxyle pour former un enchaînement ester, réalisant ainsi la synthèse d'un composé polyoxyalkylène ayant le groupe fluoré lié par un enchaînement ester, et en ce qu'on effectue ensuite la fluoration en phase liquide, en vue de remplacer par le fluor, un ou plusieurs des atomes d'hydrogène présents dans le composé polyoxyalkylène ayant le groupe organique fluoré lié par un enchaînement ester.
PCT/JP2002/004264 2001-04-27 2002-04-26 Procede de production de composes de polyoxyalkylene fluore WO2002088218A1 (fr)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005068534A1 (fr) * 2004-01-13 2005-07-28 Asahi Glass Company, Limited Compose de fluoropolyether
WO2007013412A1 (fr) * 2005-07-27 2007-02-01 Asahi Glass Company, Limited Composition d'ether et composition de solution
US7230140B2 (en) 2002-10-18 2007-06-12 Asahi Glass Company, Limited Perfluoropolyether derivative
JP2007204586A (ja) * 2006-02-01 2007-08-16 Yunimatekku Kk パーフルオロポリエーテルカルボン酸フロライドの製造法
WO2014126107A1 (fr) * 2013-02-13 2014-08-21 旭硝子株式会社 Composition d'éthers fluorés, modificateur de surface, tensioactif, composition liquide et article

Families Citing this family (2)

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Publication number Priority date Publication date Assignee Title
JPH0714270U (ja) * 1993-08-12 1995-03-10 株式会社荒井製作所 密封装置
CN108778014B (zh) * 2016-04-19 2021-01-15 Dic株式会社 手套

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EP0148482A2 (fr) * 1983-12-26 1985-07-17 Daikin Industries, Limited Procédé de préparationdes polyéthers contenant un halogène
WO1990003409A1 (fr) * 1988-09-28 1990-04-05 Exfluor Research Corporation Fluorination d'epoxydes
WO1990006296A1 (fr) * 1988-12-02 1990-06-14 Minnesota Mining And Manufacturing Company Procede direct de fluoration permettant de produire des substances organiques perfluorees
US5274180A (en) * 1991-10-22 1993-12-28 British Petroleum Company Plc Esters

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Publication number Priority date Publication date Assignee Title
EP0148482A2 (fr) * 1983-12-26 1985-07-17 Daikin Industries, Limited Procédé de préparationdes polyéthers contenant un halogène
WO1990003409A1 (fr) * 1988-09-28 1990-04-05 Exfluor Research Corporation Fluorination d'epoxydes
WO1990006296A1 (fr) * 1988-12-02 1990-06-14 Minnesota Mining And Manufacturing Company Procede direct de fluoration permettant de produire des substances organiques perfluorees
US5274180A (en) * 1991-10-22 1993-12-28 British Petroleum Company Plc Esters

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7230140B2 (en) 2002-10-18 2007-06-12 Asahi Glass Company, Limited Perfluoropolyether derivative
US7388114B2 (en) 2002-10-18 2008-06-17 Asahi Glass Company, Limited Perfluoropolyether derivative
WO2005068534A1 (fr) * 2004-01-13 2005-07-28 Asahi Glass Company, Limited Compose de fluoropolyether
CN100392000C (zh) * 2004-01-13 2008-06-04 旭硝子株式会社 含氟聚醚化合物
US7795375B2 (en) 2004-01-13 2010-09-14 Asahi Glass Company, Limited Fluoropolyether compound
KR101089078B1 (ko) 2004-01-13 2011-12-05 아사히 가라스 가부시키가이샤 함불소 폴리에테르 화합물
JP5028801B2 (ja) * 2004-01-13 2012-09-19 旭硝子株式会社 含フッ素ポリエーテル化合物
WO2007013412A1 (fr) * 2005-07-27 2007-02-01 Asahi Glass Company, Limited Composition d'ether et composition de solution
EP1914273A4 (fr) * 2005-07-27 2010-04-21 Asahi Glass Co Ltd Composition d'ether et composition de solution
US8053538B2 (en) 2005-07-27 2011-11-08 Asahi Glass Company, Limited Ether composition and solution composition
JP2007204586A (ja) * 2006-02-01 2007-08-16 Yunimatekku Kk パーフルオロポリエーテルカルボン酸フロライドの製造法
WO2014126107A1 (fr) * 2013-02-13 2014-08-21 旭硝子株式会社 Composition d'éthers fluorés, modificateur de surface, tensioactif, composition liquide et article

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