WO2011072418A1 - 高交换容量全氟离子交换树脂及其制备方法和用途 - Google Patents

高交换容量全氟离子交换树脂及其制备方法和用途 Download PDF

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WO2011072418A1
WO2011072418A1 PCT/CN2009/001457 CN2009001457W WO2011072418A1 WO 2011072418 A1 WO2011072418 A1 WO 2011072418A1 CN 2009001457 W CN2009001457 W CN 2009001457W WO 2011072418 A1 WO2011072418 A1 WO 2011072418A1
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Prior art keywords
ion exchange
fuel cell
exchange capacity
monomer
ether
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PCT/CN2009/001457
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English (en)
French (fr)
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张永明
张恒
秦胜
高自宏
王丽
李勇
宋学章
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山东东岳神舟新材料有限公司
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Priority to PCT/CN2009/001457 priority Critical patent/WO2011072418A1/zh
Priority to JP2012543434A priority patent/JP5486693B2/ja
Priority to EP09852156.0A priority patent/EP2514773B1/en
Priority to CA2784539A priority patent/CA2784539C/en
Priority to US13/516,691 priority patent/US9090723B2/en
Publication of WO2011072418A1 publication Critical patent/WO2011072418A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F214/18—Monomers containing fluorine
    • C08F214/26—Tetrafluoroethene
    • C08F214/265—Tetrafluoroethene with non-fluorinated comonomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F214/18—Monomers containing fluorine
    • C08F214/26—Tetrafluoroethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F214/18—Monomers containing fluorine
    • C08F214/26—Tetrafluoroethene
    • C08F214/262—Tetrafluoroethene with fluorinated vinyl ethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F214/18—Monomers containing fluorine
    • C08F214/26—Tetrafluoroethene
    • C08F214/265—Tetrafluoroethene with non-fluorinated comonomers
    • C08F214/267—Tetrafluoroethene with non-fluorinated comonomers with non-fluorinated vinyl ethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/20—Manufacture of shaped structures of ion-exchange resins
    • C08J5/22—Films, membranes or diaphragms
    • C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
    • C08J5/2218—Synthetic macromolecular compounds
    • C08J5/2231—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds
    • C08J5/2243—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds obtained by introduction of active groups capable of ion-exchange into compounds of the type C08J5/2231
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
    • H01M8/1023—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having only carbon, e.g. polyarylenes, polystyrenes or polybutadiene-styrenes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1039—Polymeric electrolyte materials halogenated, e.g. sulfonated polyvinylidene fluorides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M2008/1095—Fuel cells with polymeric electrolytes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the invention belongs to the field of fluorine-containing polymer materials, relates to a perfluoro ion exchange resin with high exchange capacity, a preparation method and application thereof, and particularly relates to a multicomponent copolymerized high exchange capacity perfluoro ion exchange resin, a preparation method thereof and use thereof. Background technique
  • Fluoride ion exchange membranes containing ion exchange groups are more suitable for use as ion exchange membranes for fuel cells and chloralkali cells due to their chemical resistance.
  • a sulfonic acid resin prepared from a novel structure of a perfluoroacyl fluoride monomer is described in US Pat. No. 3,884,885 and US Pat. No. 3,013,317.
  • 4,940,525 discloses a process for preparing a sulfonyl fluoride monomer copolymer resin using a vinylidene fluoride monomer and a short side group which does not have a perfluoro structure and is inferior in corrosion resistance.
  • the preparation of low EW sulfonic acid resins is disclosed in EP 0 289 869.
  • the sulfonyl fluoride monomers used are currently commonly used monomer structures with EW values between 575 and 800.
  • EP1451233 reports a process for preparing low EW resins by miniemulsion.
  • Patent US7022428, US7041409, US6S614894 smashed the preparation of low EW sulfonic acid resin, using miniemulsion polymerization, and adding a monomer containing diene ether during the polymerization.
  • GB 1034197 discloses perfluoroacid polymers containing a cross-acid group
  • EP 1091435 discloses a structure of a block sulfonic acid resin.
  • Other monomeric components which do not have an ion exchange function contain a double bond monomer component such as U.S. Patent 4,940,525.
  • the polymerization process may employ techniques well known in the art, such as solution polymerization.
  • perfluorosulfonic acid resins are their use as a membrane material in fuel cells.
  • a very important requirement for such ion exchange membranes is their ionic conductivity.
  • the practice is to increase the ion exchange capacity of the sulfonic acid resin, but as the ion exchange capacity increases, its mechanical properties are degraded. In extreme cases, the high exchange capacity ion exchange resin can even be dissolved in water.
  • the patent EP0031724 mentions that the total ion exchange capacity for the membrane used in the cell is between 0.5 and 1.6 mmol/g (dry resin), preferably between 0.8 and 1.2 mmol/g.
  • the total ion exchange capacity is less than 0.5 mmol/g, the resistivity of the membrane is too high, and the voltage and energy consumption of the electrolytic cell are relatively high, which cannot meet the industrial application. If the total ion exchange capacity is greater than 1.6 mmol/g, the membrane material The mechanical properties are not good, and the life and use are limited. In order to increase the exchange capacity and minimize the loss of mechanical properties, other methods are to use composite membranes. For example, US 5654109 and US5246792 are combined with double or triple membrane materials. The inner membrane has a high EW value and bears mechanical strength.
  • the outer membrane has a low EW value, which acts as an ion transport; US5981097 uses a plurality of layers of different ion exchange capacity membranes for recombination; and US5082472 uses a biaxially stretched polytetrafluoroethylene porous membrane to recombine with a low EW resin. The film is used. Although these practices maintain the mechanical strength of the membrane to a certain extent, there is still a certain lack of uniformity in ion conduction and improvement in electrical conductivity.
  • the other existing method is to shorten the side groups of the comonomer sulfonyl fluoride, and increase the mechanical strength of the membrane material while increasing the ion exchange capacity.
  • short side sulfonyl fluoride polymer by polymerization of monomer synthesis conditions will produce different cyclization reaction leading to chain transfer polymerization, thereby reducing molecular weight, the mechanical strength of the material Decreasing, and increasing the molar ratio of the short-side sulfonyl monomer to the tetrafluoroethylene monomer further promotes the occurrence of such side reactions, limiting the improvement of ion exchange capacity and material stability.
  • perfluorosulfonic acid resins are their use as a membrane material in fuel cells.
  • An important requirement for such membrane electrodes formed by ion exchange membranes and catalyst layers is their chemical stability and Enhance the toxic ability of the electrode catalyst against carbon monoxide (CO).
  • CO carbon monoxide
  • the operating temperature of the fuel cell membrane electrode widely studied and demonstrated is between 25-80 ° C. In the environment where the CO content reaches 10 ppm, the catalyst layer of the membrane electrode will be poisoned, and it is difficult to overcome the current low-temperature fuel cell membrane electrode.
  • the present invention provides a high exchange capacity perfluorinated ion exchange resin which is a multicomponent copolymerization of tetrafluoroethylene, two different structural short-side decanoyl fluoroether monomers, and a bromine-based olefin ether monomer.
  • the resin mainly contains the repeating unit represented by the following formula (I):
  • the structural formulas of the two different short side group structure sulfonyl fluoroether ether monomers are:
  • the molar percentage of each polymerized unit in the resin is: the total mole fraction of the tetrafluoroethylene polymerized unit is 50-85%, and the total mole fraction of the short-side sulfonyl fluoroalkenyl ether polymer unit of two different structures
  • the total mole fraction of the bromo olefinic ether polymerized unit is from 5 to 49%, and the total mole fraction is from 1 to 10%.
  • the molar content percentage of each polymerized unit in the resin is preferably: the total mole fraction of the tetrafluoroethylene polymerized unit is 70 to 80%, and the total mole fraction of the short-side sulfonyl fluoride ether polymerization unit of two different structures For 15 ⁇ 29%, the total mole fraction of the bromo olefinic ether polymerization unit is from 1 to 5%.
  • the molar ratio of the polymer units of the short-side decanoyl fluoroalkenyl ether monomers (1) and (2) of the two different structures in the resin is 0.2-0.8: 0.8-0.2; preferably 0.4-0.6: 0.6-0.4.
  • the present invention provides a process for the preparation of the above high exchange capacity perfluororesin, which comprises tetrafluoroethylene, two different structures of short-side sulfonyl fluoroalkenyl ether monomers, and a bromo-based pendant olefin.
  • the ether monomer is subjected to polymerization under the action of an initiator.
  • the polymerization reaction has a reaction time of 1 to 8 hours, a reaction temperature of 10 to 80 ° C, and a reaction pressure of 2 to 10 MPa.
  • the initiator is selected from one or more of N 2 F 2 , perfluoroalkyl peroxide and persulphate.
  • the perfluoroalkyl peroxide is selected from the group consisting of a perfluoroalkyl acyl peroxide compound, a perfluoroalkoxy acyl compound, a peroxide partial fluoroalkyl acyl compound, and a peroxylated partial fluoroalkane.
  • a perfluoroalkyl acyl peroxide compound a perfluoroalkoxy acyl compound
  • a peroxide partial fluoroalkyl acyl compound a peroxylated partial fluoroalkane.
  • the persulfate is one or more selected from the group consisting of ammonium persulfate, alkali metal persulfide and alkaline earth metal persulfide.
  • the perfluoroalkyl peroxide is selected from the group consisting of perfluoropropionyl peroxide, 3-chlorofluoropropionyl peroxide, perfluorodecyl acetyl peroxide, ⁇ - ⁇ -perfluoro Butyryl peroxide, c-S0 2 F-perfluoro-2,5,8-trimethyl-3,6,9-trioxa-undecyl peroxide, CF 3 CF 2 CF 2 CO -00-COCF 2 CF 2 CF 3 ,
  • the persulfate salt is one or more selected from the group consisting of ammonium persulfate and potassium peroxide.
  • the emulsifier is selected from the group consisting of a female emulsifier such as sodium fatty acid, sodium lauryl sulfate, sodium alkyl sulfonate and sodium alkylaryl sulfonate; and a nonionic emulsifier.
  • alkylphenol polyether alcohols such as nonylphenol ethoxylates, polyoxyethylene fatty acids, and polyoxyethylene fatty acid ethers.
  • the mass percentage concentration of the emulsifier in water is
  • the concentration of the short-side sulfonyl fluoroether ether monomer in two different structures is 5-30% in water, and the mass concentration of the bromo-based olefin ether monomer in water is 1 ⁇ 12 %.
  • the present invention provides an ion exchange membrane prepared from the above-described high exchange capacity perfluororesin.
  • the present invention provides a fuel cell or electrolytic cell device comprising the above ion exchange membrane; the fuel cell is preferably a proton membrane fuel cell or a high temperature fuel cell, more preferably a high temperature proton membrane fuel cell; It is preferably a chloralkali electrolytic cell.
  • the present invention provides the use of the above high exchange capacity perfluororesin for the manufacture of an ion exchange membrane in a fuel cell or cell device;
  • the fuel cell is preferably a proton membrane fuel cell or a high temperature fuel cell, more preferably a high temperature proton Membrane fuel cell;
  • the electrolytic cell is preferably a chloralkali electrolytic cell; preferably, the bromo-based side groups are chemically cross-linked by chemical methods prior to use.
  • the present invention has at least the following advantages:
  • the perfluoro resin of the present invention has two different structures of short-side sulfonyl fluoride and bromo-based side groups, which solves the contradiction between the ion exchange capacity and the mechanical strength in the prior art, and provides A high-fluorine resin with high ion exchange capacity and good mechanical properties.
  • the perfluoro resin of the present invention has two different structures of short-side sulfonyl fluoride and cyano side groups, which solves the chain transfer reaction of the short-side oleoyl fluoroolefin monomer during polymerization.
  • the problem of the molecular weight of the resin is not high enough.
  • the specific reaction mechanism can be as follows: First, two kinds of short-side sulfonyl fluoroether ether monomers with different structures are used in the polymerization process, and the two monomers cooperate with each other; The presence of bromoalkenyl ether, the presence of these different kinds of enols allows the polymerization to proceed in a direction of high molecular weight, eliminating the chain transfer cyclization reaction.
  • the invention adopts tetrafluoroethylene (TFE) and two kinds of short-side decanoyl fluoroether ether monomers and bromine-side olefin ether monomers to carry out multi-component copolymerization to obtain a high molecular weight high exchange capacity perfluororesin.
  • TFE tetrafluoroethylene
  • This multicomponent copolymer has high chemical stability, high ion exchange capacity and good high temperature mechanical stability.
  • the high exchange capacity perfluororesin of the present invention can be used for the preparation of ion exchange membranes in devices such as fuel cells (e.g., high temperature fuel cells) and chloralkali cells.
  • the film material prepared by using this resin has high current efficiency, low film resistance, high dimensional stability, and high mechanical strength. The following is a detailed description of the invention:
  • the present invention provides a high-exchange capacity perfluororesin having two different structures of short-side sulfonyl fluoride and bromo-based side groups.
  • the perfluoro resin is composed of tetrafluoroethylene and two different structures of short-side base.
  • the acyl fluoride ether is a single bromine pendant olefin ether monomer, and the molecular formula of the polymer chain is:
  • tetrafluoroethylene aggregate unit total The molar fraction is 50 to 8 5 %, the total molar fraction of the short-side decanoyl fluoride ether polymerization unit is 5 to 49%, and the total mole fraction of the brominated side olefin ether polymerization unit is 1 to 10%;
  • the percentage of moles of various polymerized units in the polymer is 70 to 80%, and the total mole fraction of the polymerized units of the sulfonyl fluoride side olefin ether is 15-29%, bromine
  • the pendant alkylene ether polymerized unit has a total molar fraction of from 1 to 5%.
  • the ratio of the tetrafluoroethylene, the short-side structure sulfonyl fluoroether ether monomer and the bromine-side olefin ether monomer in the resin is: 50 to 85: 5-49: 1-10; molar ratio.
  • the ratio of the polymerized units of the two different short-side structure sulfonyl fluoroether ether monomers (1) and (2) in the resin is 0.2-0.8: 0.8-0.2, molar ratio; preferably, two different short-side structure
  • the ratio of the sulfonyl fluoroether ether monomers (1) and (2) polymerized units in the resin is from 0.4 to 0.6: 0.6 to 0.4, molar ratio.
  • the number average molecular weight of the above high exchange capacity perfluororesin is from 10 to 600,000, preferably from 15 to 300,000, and most preferably from 18 to 250,000.
  • the molecular weight distribution value (referred to as the weight average molecular weight ratio number average molecular weight) of the above high exchange capacity perfluororesin is 1.5 to 2.0.
  • the invention provides a preparation method of the above-mentioned perfluoro ion exchange resin with two different structures of short-side sulfonyl fluoride and bromine side groups, which is prepared by tetrafluoroethylene, two different structures of short-side sulfonyl fluoride
  • the olefin monomer and a bromine-side olefin ether monomer are prepared by copolymerization (polymerization) at 10 to 80 ° C under the action of an initiator, and the reaction time of the copolymerization reaction is 1 to 8 hours.
  • the reaction pressure is 2 to 10 MPa.
  • an initiator known in the art may be used as the initiator, or a self-made initiator may be used.
  • the initiator is selected from the group consisting of: N 2 F 2 , perfluoroalkyl peroxide or persulphate.
  • the perfluoroalkyl peroxide comprises: a perfluoroalkyl acyl peroxide compound, a perfluoroalkoxy acyl compound, a fluorinated partial fluoroalkyl acyl compound, a peroxylated partial fluorinated alkoxylate Alkyl compound.
  • perfluoropropionyl peroxide 3-chlorofluoropropionyl peroxyl Compound, perfluorodecyl acetyl peroxide, ⁇ - ⁇ -perfluorobutyryl peroxide, d)-S0 2 F-perfluoro-2,5,8-trimethyl-3,6,9- Trioxa-undecyl peroxide, CF 3 CF 2 CF 2 CO-00-COCF 2 CF 2 CF 3 , CF 3 CF 2 CF 2 OCFCF 3 CO-00-COCFCF 3 OCF 2 CF 2 CF 3 ,
  • the persulfate salt comprises an ammonium persulfate salt, an alkali metal persulfide or an alkaline earth metal persulfide; further preferably ammonium persulfate or potassium persulfate.
  • the molar ratio of the tetrafluoroethylene polymerization unit in the resin, the short-side sulfonyl fluoroalkenyl ether polymerization unit and the bromo-based olefin ether polymerization unit of the two different structures is: 50 to 85: 5-49: 1 ⁇ 10.
  • the molar ratio of the short-side acyl fluoride ether polymer units (1) and (2) of the two different structures in the resin is 0.2-0.8: 0.8-0.2; more preferably, the short side of the two different structures
  • the molar ratio of the polymer units (1) and (2) of the sulfonyl fluoride ether in the resin is from 0.4 to 0.6: 0.6 to 0.4.
  • the above copolymerization reaction is carried out in an aqueous phase for emulsion polymerization.
  • the specific emulsion polymerization method is as follows:
  • the emulsifier comprises one or more anionic emulsifiers and/or nonionic emulsifiers.
  • Anionic emulsifiers include sodium fatty acid, sodium lauryl sulfate, sodium alkyl citrate, sodium alkylaryl sulfonate, etc.; nonionic emulsifiers include alkylphenol polyether alcohols, such as nonylphenol polyoxyl Vinyl ether, polyoxyethyl hydride fatty acid, polyoxyethylene fatty acid ether.
  • the above emulsifiers may be used singly or in combination of plural kinds.
  • the reactor is heated to 10 ⁇ 80 ° C, the reaction is initiated by adding an initiator to the reaction system through a metering pump, and continuously adding tetrafluoroethylene monomer and initiator to the reaction vessel to maintain the reaction pressure of the reaction vessel 2 - 10MPa, reaction time is 1 ⁇ 8 hours;
  • the initiator and the tetrafluoroethylene monomer are stopped from being added to the reaction vessel, and the unreacted tetrafluoroethylene monomer is recovered by venting the reactor vent line and the recovery tank; and the milky white polymer slurry is obtained.
  • the liquid slurry is passed through a discharge system into a post-treatment apparatus, sheared at a high speed, and separated by filtration to obtain a white polymer powder at 100.
  • the C oven was allowed to dry to obtain a high ion exchange capacity perfluoro ion exchange resin having a short side group of a lateral acyl fluoride and a bromine side group having two different structures.
  • the sulfonyl fluoroether ether monomer and the bromine side olefin ether monomer in the filtrate are recycled through a recovery system.
  • the ratio of the short-side sulfonyl fluoroether ether monomers (1) and (2) polymerized units of the two different structures in step 1) is 0.2-0.8: 0.8-0.2, molar ratio; preferably, two different structures Short side sulfonyl
  • the ratio of the fluoroether ether monomers (1) and (2) polymerized units is from 0.4 to 0.6: 0.6 to 0.4, molar ratio.
  • the initiator is selected from the group consisting of: N 2 F 2 , perfluoroalkyl peroxide or persulphate; those skilled in the art can select the concentration of the initiator according to common knowledge in the art.
  • the perfluoroalkyl peroxide comprises: a perfluoroalkyl acyl compound, a perfluoroalkoxy acyl compound, a fluorinated partial fluoroalkyl compound or a peroxidized partial fluoroalkoxy acyl compound. ;
  • the persulphate salt comprises ammonium persulfate, an alkali metal persulfate or an alkaline earth metal persulfate; preferably ammonium citrate or potassium peroxylate.
  • the use of the high ion exchange capacity perfluorinated ion exchange resin of the present invention having a short side sulfonyl fluoride and a bromo pendant group having two different structures can be used to produce an ion exchange membrane for a fuel cell or a high temperature fuel cell.
  • the invention relates to the application of the high ion exchange capacity perfluoro ion exchange resin with two different structures of short side radicals of acyl fluoride and bromo groups, in particular for proton membrane fuel cells, high temperature proton membranes
  • An ion exchange membrane is used in a device such as a fuel cell or a chlor-alkali electrolysis cell.
  • Such ion exchange membranes have high chemical stability, high current efficiency, low membrane resistance, high dimensional stability, and high mechanical strength.
  • the invention relates to a high ion exchange capacity perfluoro ion exchange resin with two different structures of short-side sulfonium fluoride and bromo pendant groups, and the resin can be prepared by a solution casting process to obtain a suitable thickness of perfluorocarbon.
  • the sulfonic acid ion exchange membrane or a melt extrusion apparatus is used to prepare a film material of a suitable thickness by high temperature melt extrusion.
  • the membrane material is then debrominated and crosslinked by known methods such as radiation crosslinking, heat treatment crosslinking, addition of a photoinitiator to initiate crosslinking or crosslinking by a free radical initiator to initiate crosslinking, followed by debromination of the bromo group;
  • the side group is transformed into a side group of sulfonic acid, and the perfluoro ion exchange membrane is not only resistant to various chemical media, but also has high conductivity, high mechanical strength and high dimensional stability, and low membrane resistance, which is very suitable. Used in fuel cells, high temperature fuel cells or chlor-alkali cells.
  • the use of the high ion exchange capacity perfluorinated ion exchange resin with two different structures of short-side acyl fluoride and bromo pendant groups in the fuel cell of the present invention can be further based on debromination of bromine side groups. Improve the water retention capacity, dimensional stability and mechanical strength of the ion exchange membrane, effectively improve the usability of the membrane material, and further increase the service life of the membrane material.
  • the beneficial effects of the invention are:
  • the perfluorinated ion exchange resin synthesized by the invention has an ion exchange capacity of 0.5-2.6 mmol/g (dry resin), and the smaller the ion exchange capacity, the greater the mechanical strength, wherein the ion exchange capacity is between 1.28 and 1.95 mmol/
  • the mechanical strength of the uncrosslinked resin of g exceeds 20 MPa, and the prepared film material has Very good thermal stability, the mechanical strength of the membrane material after cross-linking treatment exceeds 30MPa.
  • the conductivity of the membrane material is more than 0.2S/cm at room temperature, and the conductivity measured at 100 °C and 45% humidity is still higher than 0.0 5 S/cm, which can fully meet the requirements of fuel cell proton membrane and chlor-alkali electrolyte membrane material. .
  • Fig. 1 shows a F 19 NMR spectrum of a perfluoro resin of one embodiment of the present invention.
  • Fig. 2 is a view showing an infrared spectrum of a perfluoro resin according to an embodiment of the present invention.
  • Fig. 3 is a view showing an infrared spectrum of a perfluoro resin of one embodiment of the present invention.
  • Fig. 4 is a view showing the F 19 NMR spectrum of the perfluoro resin of one embodiment of the present invention. The best way to implement the invention
  • the reactors used in the examples are 10L stainless steel high pressure reactors, equipped with temperature sensors, pressure sensors, heating circulation systems, cooling circulation systems, mixing motors, internal cooling water pipes, liquid metering pumps, gases. Feed valve, liquid feed valve, material discharge valve in the reaction kettle.
  • perfluoroalkyl initiators employed in the synthesis of the present invention can be prepared according to techniques well known in the art. For the preferred preparation methods of the present invention, see J. Org. Chem., 1982, 47(1 1):
  • the potassium persulfate, ammonium persulfate, and N 2 F 2 gases used in the synthesis of the present invention are all commercially available.
  • the potassium persulfate and ammonium persulfate used can be purchased through Sinopharm Group; N 2 F 2 gas can be purchased from Dongyue Chemical Co., Ltd.
  • the comonomer tetrafluoroethylene used in the synthesis process of the present invention is purchased from Shandong Dongyue High Molecular Material Co., Ltd.; the short-side sulfonyl fluoride monomer can be referred to US Patent 3560568 and the US patent.
  • the reaction kettle was washed and 5.0 L of deionized water, 100 g of sodium dodecylbenzenesulfonate and 12 nonylphenol polyoxyethylene ether NP-10 emulsifier were added, and the stirring device was started, and vacuum-filled with high-purity nitrogen was replaced three times.
  • the reaction kettle is cooled by the cooling circulation system, and the unreacted tetrafluoroethylene monomer is recovered by the recovery system, and the milky white slurry in the kettle is placed in the post-treatment system through the lower discharge valve, and after high-speed shearing, the filtration is separated.
  • a white polymer powder was obtained, which was dried in a 100 ° C container to obtain a perfluoro ion exchange resin having a short-side sulfonyl fluoride and a bromine side group.
  • the sulfonyl fluoroether ether monomer and the bromine side olefin ether monomer in the filtrate are recovered by a recovery system and reused.
  • Polymer data It was confirmed by F 19 NMR and IR analysis that it was a multi-component copolymer.
  • the fluorine core magnetic integral value showed that the polymer structure contained a polymerized unit having a molar percentage of 62.71%, containing a sulfonyl fluoride side olefin ether monomer.
  • the polymer unit has a mole percentage of 16.5%
  • the sulfonyl fluoride side olefin ether monomer (2) has a polymer unit molar percentage of 16.3%
  • the bromine side olefin ether polymer unit has a mole percentage of 4.49%
  • the total ion exchange capacity is It is: 1.77 mmol/g dry resin.
  • the reaction kettle was washed and added with 5.0 L of deionized water, 220 g of sodium dodecylbenzenesulfonate, and the stirring device was started.
  • the vacuum was filled with high-purity nitrogen for three times. After the oxygen content in the reactor was below 1 ppm, the vacuum was applied.
  • Add 500g of sulfonyl fluoride pendant ethyl ether monomer (1) (F 2 C CF-0-CF 2 CF 2 -S0 2 F ) and 405g sulfonyl fluoride side olefin to the reactor through the liquid feed valve.
  • Example 3
  • the reaction kettle was washed and 5.0 L of deionized water, 120 g of sodium dodecyl benzoate and 95 g of nonylphenol ethoxylate NP-10 emulsifier were added, and the stirring device was started, and the vacuum was filled with high-purity nitrogen for three times.
  • the white polymer powder was dried in an oven at 100 ° C to obtain a perfluoro ion exchange resin having a short-side acyl fluoride group and a bromine side group.
  • the cellulose fluoroether ether monomer and the bromine side olefin ether monomer in the filtrate are recovered by a recovery system and reused.
  • the reaction kettle was washed and 5.0 L of deionized water, 180 g of sodium dodecylbenzenesulfonate and 45 g of nonylphenol polyoxyethylene ether NP-10 emulsifier were added, and the stirring device was started, and vacuum-filled with high-purity nitrogen was replaced three times.
  • N 2 F 2 after the reaction 2h, reactor pressure was 3.0MPa, the initiator addition is stopped, allowing the reaction to proceed after lmin, tetrafluoroethylene monomer was stopped.
  • the reaction kettle is cooled by the cooling circulation system, and the unreacted tetrafluoroethylene monomer is recovered by the recovery system, and the milky white slurry in the kettle is placed in the aftertreatment system through the lower discharge valve, and after high-speed shearing, the filtration is separated.
  • the white polymer powder was dried in an oven at 100 ° C to obtain a perfluoro ion exchange resin having a short side acyl fluoride and a bromine side group.
  • the sulfonyl fluoroether ether monomer and the bromine side olefin ether monomer in the filtrate are recovered by a recovery system and reused.
  • Polymer data It was confirmed by F 19 NMR and IR (as shown in FIG. 3 ) that it was a multi-component copolymer.
  • the fluorine core magnetic integral value showed that the polymer structure contained a polymerized unit having a molar percentage of 74.5%, containing a sulfonyl group.
  • the fluorine side olefin ether monomer (1) has a polymer unit molar percentage of 10.5%
  • the sulfonyl fluoride side olefin ether monomer (2) has a polymer unit molar percentage of 13.79%
  • the bromine side olefin ether polymer unit has a molar percentage of 1.21%
  • the overall ion exchange capacity was: 1.54 mmol / g dry resin.
  • Example 5 Example 5:
  • the reaction kettle was washed and 5.0 L of deionized water and 215 g of sodium dodecylbenzene sulfonate emulsifier were added, and the stirring device was started, and the vacuum was filled with high-purity nitrogen for three times.
  • the oxygen content in the reactor was tested at 1 ppm.
  • reaction vessel was charged with tetrafluoroethylene monomer to a pressure of 2.8 MPa, and the temperature was raised to 25 ° C, and the flow rate was controlled by a gas flow meter to introduce N into the reactor.
  • the reaction pressure At 3.2 MPa, the addition of the initiator was stopped, and after the reaction was continued for 1 min, the addition of the tetrafluoroethylene monomer was stopped.
  • the reaction kettle is cooled by the cooling circulation system, and the unreacted tetrafluoroethylene monomer is recovered by the recovery system, and the milky white slurry in the kettle is placed in the aftertreatment system through the lower discharge valve, and after high-speed shearing, the filtration is separated.
  • the white polymer powder was dried in an oven at 100 ° C to obtain a perfluoro ion exchange resin having a short side fluorenyl fluoride group and a bromine side group.
  • the sulfonyl fluoroether ether monomer and the bromine side olefin ether monomer in the reaction liquid are recovered by a recovery system and reused.
  • the fluorine core nucleus integral value shows that the polymer structure contains 47.1% of the polymerized unit of tetrafluoroethylene, containing the acyl group.
  • the fluorine side olefin ether monomer (1) has a polymer unit molar percentage of 14.2%
  • the sulfonyl fluoride side olefin ether monomer (2) has a polymer unit molar percentage of 11.46%
  • the bromine side olefin ether polymer unit has a molar percentage of 7.24%
  • the overall ion exchange capacity is: 1.44mmol / g dry resin.
  • the reaction kettle was washed and 5.0 L of deionized water and 225 g of sodium dodecylbenzene sulfonate emulsifier were added, and the stirring device was started, and the vacuum was filled with high-purity nitrogen for three times.
  • the reaction kettle is cooled by the cooling circulation system, and the unreacted tetrafluoroethylene monomer is recovered by the recovery system, and the milky white slurry in the kettle is placed in the aftertreatment system through the lower discharge valve, and after high-speed shearing, the filtration is separated.
  • the white polymer powder was dried in an oven at 100 ° C to obtain a perfluoro ion exchange resin having a short pendant sulfonyl fluoride and a bromine side group.
  • the sulfonyl fluoroether ether monomer and the bromine side olefin ether monomer in the filtrate are recovered by a recovery system and reused.
  • Polymer data It was confirmed by F 19 NMR and IR analysis that it was a multi-component copolymer.
  • the fluorine core magnetic integral value showed that the polymer structure contained 80% of the polymerized unit of tetrafluoroethylene, and contained the sulfonyl fluoride side olefin ether monomer.
  • the polymer unit has a molar percentage of 8.2%
  • the sulfonyl fluoride-containing olefin ether monomer (2) has a polymer unit molar percentage of 9.92%
  • the bromine-containing olefin ether polymer unit has a molar percentage of 1.88%
  • the total ion exchange capacity is It is: 1.27 mmol/g dry resin.
  • the decomposition temperature (T d ) of the TGA test resin under nitrogen atmosphere is 387 ° C;
  • This example is intended to illustrate the process of preparing an ion exchange membrane using the perfluoro ion exchange resin of Examples 1 to 6, and the mechanical properties of the prepared membrane.
  • Pellet preparation The white powder products obtained in Examples 1 to 6 were respectively extruded through a small melt extruder to prepare pellets, and the extrusion temperature of the melt extruder was set as follows: screw area 250 ° C, screw 2 The area is 255 °C, the screw three zone is 260 °C, the extruder die temperature is 270 °C, the extruder die diameter is 3mm, and the melted extruded columnar transparent material is sheared to prepare the length 2 by adjusting the shear rate. -4mm transparent resin pellets, and the pellets are sealed in a double PE plastic bag.
  • Melt extrusion extrusion film The melt extruder die is replaced by a film extrusion die, the screw zone is set at the same temperature as above, and the prepared transparent pellets are prepared by melt extrusion to form a film, and the film thickness can be adjusted by adjusting the die.
  • the width and width of the mouth are usually adjusted to a film thickness of 20-100 ⁇ m.
  • Membrane mechanical property test The test method was adopted as GB/T1040-92, and the ion exchange membrane 1-film 6 prepared by using the perfluoro ion exchange resin prepared in Example 1-6, and the sulfonic acid of the model NRE 211 by DuPont were measured. The mechanical properties of the film are shown in Table 1.
  • the 1.0 L reactor was washed and 500 ml of deionized water, 10 g of sodium dodecylbenzenesulfonate and 13 g of nonylphenol ethoxylate NP-10 emulsifier were added, and the stirring device was started, and the vacuum was filled with high-purity nitrogen for three times.

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Description

高交换容量全氟离子交换树脂及其制备方法和用途 技术领域
本发明属于含氟高分子材料领域， 涉及一种具有高交换容量全氟离子交 换树脂及其制备方法和用途， 尤其涉及多元共聚高交换容量全氟离子交换树 脂及其制备方法和用途。 背景技术
自上世纪 70年代杜邦公司将全氟横酸树脂加工成全氟横酸型离子交换膜 并且这种膜在氯碱工业及质子交换膜燃料电池中应用后， 全氟离子交换树脂 在世界各国得到了广泛的研究。
含有离子交换基团， 尤其是含有磺 和羧酸基的含氟离子交换膜由于 其耐化学降解性而更适合用作燃料电池和氯碱电解槽的离子交换膜。
US3282875是杜邦公司公开的第一个关于磺酰氟单体合成及碩酸树脂制备 的文献， 采用的是水体系中乳液聚合反应， 含有磺酰氟侧基的功能性单体结 构为： F02SCF2CF2OCF(CF3)CF2OCF=CF2,该单体结构目前已经被普遍采用。 US3560568是杜邦公司公开的一篇关于短侧基磺酰氟单体及磺酸树脂的制 备及性能的专利， 所报道的磺酰氟单体结构为 F02SCF2CF2OCF=CF2， 制备 路线复杂并且收率比较低。 US3884885、 US 3041317中介绍了由新型结构全 氟碌酰氟单体制备的磺酸树脂， 采用的磺酰氟单体的结构为 RfCF=CFS02F， 这种单体的反应活性比较低。 US4358545、 US4417969是美国 Dow化学公司 公开的专利， 该专利主要涉及采用短侧基单体（ CF2=CFOCF2CF2S02F )与四 氟乙烯等含氟乙烯基单体共聚形成的共聚物的性质和应用，通过这种方法制 备的磺酸树脂由于是釆用溶液制膜， 很难制备出薄膜， 并且膜的力学强度不 够高， 如专利 US4661411、 US5718947专利内所述。 US4940525公开了一种 使用偏氟乙烯单体与短侧基的磺酰氟单体共聚树脂的制备方法，这种树脂已 经不具备全氟结构， 在耐腐蚀性方面要差一些。 EP0289869中公布了低 EW 值磺酸树脂的制备， 采用的磺酰氟单体为目前普遍所采用的单体结构， 其 EW值在 575-800之间。 EP1451233报道了通过细乳液制备低 EW值树脂的 方法。 专利 US7022428、 US7041409、 US6S614894艮道了低 EW值的磺酸树 脂的制备， 采用细乳液聚合反应， 并且在聚合过程中加入了含有双烯醚的单 体， 双烯醚单体结构为 CF2=CF-0-CF2CF2CF2-OCF=CF2， EW值在 625-850 之间。 GB1034197公开了含横酸基的全氟碩酸聚合物， EP1091435公开了一 种嵌段磺酸树脂的结构。上述聚合物都是以使用四氟乙烯单体与磺酰氟侧基 烯醚（比如 CF2=CFOCF2CF(CF3)OCF2CF2S02F )共聚制备或者进一步在上述 聚合体系中引入其他不具有离子交换功能的侧基含有双键的单体成分如 US4940525, 聚合方法可以采用本领域已经公知的技术， 如溶液聚合
( US2393967, US3041317等）、 乳液聚合 (US4789717、 US4864006等)、 微 乳液聚合 (如 US6639011、 EP1172382, US5608022等)、 分散聚合、 悬浮聚 合、 细乳液聚合（EP1451233 )等等。 这些具有磺酰氟侧基的聚合物可以经 过磺酰氟的适当水解反应得到游离的磺酸基， 作为离子交换膜用于燃料电 池、 电解池、 扩散渗析、 催化、 贵金属回收等领域。
全氟磺酸树脂的一个最重要的用途就是其作为膜材料在燃料电池中的 应用， 对这类离子交换膜的一个非常重要的要求是它的离子导电性， 为了提 高电导率， 公知的一种做法是提高磺酸树脂的离子交换容量， 但是随着离子 交换容量的增加， 其机械性能下降， 极端情况下， 高交换容量的离子交换树 脂甚至可以溶解在水中。 专利 EP0031724中提及： 对于在电槽中使用的膜的 离子交换容量总量要在 0.5-1.6mmol/g (干树脂）之间， 优选 0.8-1.2mmol/g。 若离子交换容量总量小于 0.5 mmol/g, 则膜的电阻率太高， 电解槽电压和能 耗都会比较高， 不能满足工业化应用， 若离子交换容量总量大于 1.6mmol/g， 则膜材料的机械性能不好， 寿命及使用方面受限制。 为了提高交换容量并且 尽量减少机械性能的损失， 另外一些做法是采用复合膜， 如 US5654109、 US5246792采用的做法是双层或者三层膜材料复合，内部的膜具有高 EW值， 承担机械强度作用， 外部的膜为低 EW值， .起离子传导作用； US5981097采 用多层不同离子交换容量膜进行复合；而 US5082472是采用了双向拉伸的聚 四氟乙烯多孔膜与低 EW值的树脂复合得到复合膜进行使用。这些做法虽然 一定程度上保持了膜的机械强度，但是在离子传导的均匀性及电导率的提高 上还是有一定的欠缺。
为提高交换膜的机械强度及尺寸稳定性，在对树脂结构进行改性的做法 中， 公知的做法有在树脂结构中引入可以交联的基团如 US20020014405、 US6767977在树脂结构中引入了双烯单体， 中国专利申请 ^Ο ΟΟ όΟ Ι 公开了一种在聚合体系中引入腈基的做法， 通过处理后使腈基进行交联， 增 加膜的机械强度。中国专利申请 200480033631.8公开了一种在聚合体系中引 入溴、 氯、 碘基， 通过电子束进行交联。 目:前现有的另外一种做法是缩短共 聚单体磺酰氟的侧基， 在增加离子交换容量的同时提升膜材料的机械强度， 但是在专利 US6680346提到：由短侧基磺酰氟单体合成的聚合物由于聚合条 件的不同会产生环化反应， 导致了聚合反应的链转移， 从而分子量降低， 材 料的力学强度降低， 并且随着短侧基磺酰单体与四氟乙烯单体摩尔比例增加 会进一步促进这类副反应的发生， 限制了离子交换容量的提升及材料的稳定 性。
全氟磺酸树脂的一个最重要的用途就是其作为膜材料在燃料电池中的 应用，对这类由离子交换膜及催化剂层所形成的膜电极的一个重要的要求是 它的化学稳定性及增强电极催化剂抗一氧化碳（CO ) 中毒性能力。 当前广 泛研究和示范的燃料电池膜电极的工作温度在 25-80°C之间， 在 CO含量达到 lOppm环境中膜电极的催化剂层即会发生中毒行为， 为了克服目前低温燃料 电池膜电极许多难以解决的困难， 如提高催化剂活性和利用率， 增强电极催 化剂抗一氧化碳中毒性能等， 有效的解决办法是提高燃料电池的使用温度， 在超过 100°C时， 膜电极中催化剂对 CO的耐受性会提高到 l，000ppm左右。 开 发高温质子交换膜可更好地提高燃料电池的电效率， 降低电池***的成本， 更加适应燃料电池商业化的要求。 目前国际上燃料电池研究的主要国家开始 投入大量的人力物力进行研究。 目前燃料电池领域公知具有长侧基礒酰氟的 磺酸树脂已经不能满足高温使用要求。 发明内容
本发明的一个目的在于， 提供一种高交换容量全氟树脂， 该高交换容量 全氟树脂带有两种不同结构的短侧基磺酰氟及溴基侧基， 具有高的离子交换 容量及良好的机械性能。 本发明的另一个目的在于， 提供一种上述高交换容 量全氟树脂的制备方法。 本发明的又一目的在于， 提供一种由上述高交换容 量全氟树脂制备而成的离子交换膜。 本发明的再一目的在于， 提供一种包含 上述离子交换膜的燃料电池或电解池。 本发明的再一个目的在于， 提供一种 上述高交换容量全氟树脂的用途。
本发明的上述目的采用如下技术方案来实现：
一方面，本发明提供一种高交换容量全氟离子交换树脂，是由四氟乙烯、 两种不同结构短侧基礒酰氟烯醚单体、 一种溴侧基烯醚单体多元共聚合而 成， 该树脂主要含有以下式（I )所示的重复单元：
Figure imgf000005_0001
( I )
其中 n=0-3的整数， 优选 n=0; m=2-4的整数； a、 b、 c = 3-15的整数, a，、 b，、 c'=l-3的整数； x/(x+y+z)=0.2-0.7, y/(x+y+z)=0.2-0.79,
z/(x+y+z)=0.01-0.1 , 摩尔比。
优选地， 所述的两种不同短侧基结构磺酰氟烯醚单体的结构式分别为：
Γ2 Γ2
C=C-0-C -C -SO,F
Figure imgf000005_0002
构式为
Figure imgf000005_0003
式中 n=0-3 , 优选 n=0; m=2-4的整数。
优选地， 所述树脂中各聚合单元所占的摩尔含量百分数为： 四氟乙烯聚 合单元总体摩尔分数为 50~85%， 两种不同结构的短侧基磺酰氟烯醚聚合单 元总体摩尔分数为 5〜49%, 溴侧基烯醚聚合单元总体摩尔分数为 1〜10%。
优选地， 所述树脂中各聚合单元所占的摩尔含量百分数优选： 四氟乙烯 聚合单元总体摩尔分数为 70〜80%, 两种不同结构的短侧基磺酰氟烯醚聚合 单元总体摩尔分数为 15〜29%, 溴侧基烯醚聚合单元总体摩尔分数为 1〜5%。
优选的， 所述树脂中两种不同结构的短侧基礒酰氟烯醚单体（ 1 )和（ 2 ) 的聚合单元的摩尔比为 0.2-0.8: 0.8-0.2; 优选为 0.4-0.6: 0.6-0.4。
另一方面， 本发明提供上述高交换容量全氟树脂的制备方法， 该制备方 法包括使四氟乙烯、 两种不同结构的短侧基磺酰氟烯醚单体、 一种溴基侧基 烯醚单体在引发剂作用下进行聚合反应， 优选地， 所述聚合反应的反应时间 为 1〜8小时， 反应温度为 10 ~ 80°C , 反应压力为 2〜10MPa。 优选地， 所述引发剂选自 N2F2、全氟烷基过氧化物和过硫酸盐中的一种 或多种。
优选地， 所述全氟烷基过氧化物为选自过氧化全氟烷基酰基化合物、 过 氧化全氟烷氧基酰基化合物、过氧化部分含氟烷基酰基化合物和过氧化部分 含氟烷氧基酰基化合物中的一种或多种； 所述过硫酸盐为选自过硫酸铵盐、 碱金属过硫化物和碱土金属过硫化物中的一种或多种。
更优选地， 所述全氟烷基过氧化物为选自全氟丙酰基过氧化物、 3-氯氟 丙酰过氧化物、全氟曱氧基乙酰过氧化物、 ώ-Η-全氟丁酰过氧化物、 c -S02F- 全 氟 -2,5，8- 三 曱 基 -3，6，9- 三 氧 杂 - 十 一 烷 基 过 氧化 物 、 CF3CF2CF2CO-00-COCF2CF2CF3、
CF3CF2CF2OCFCF3CO-00-COCFCF3OCF2CF2CF、
CF3CF2CH2CO-00-COCH2CF2CF3和
CF3OCF2CF2CO-00-COCF2CF2OCF3中的一种或多种； 所述过硫酸盐为选自 过硫酸铵和过 交钾中的一种或多种。 优选地， 在乳液聚合反应步骤中， 乳化剂选自阴 子型乳化剂 例如脂 肪酸钠、 十二烷基硫酸钠、 烷基横酸钠和烷基芳基磺酸钠； 以及非离子型乳 化剂， 例如烷基酚聚醚醇类， 如壬基酚聚氧乙烯醚、 聚氧乙烯脂肪酸和聚氧 乙烯脂肪酸醚中的一种或多种。
更优选地， 在乳液聚合反应步骤中， 乳化剂在水中的质量百分比浓度为
0.1-20%, 两种不同结构的短侧基磺酰氟烯醚单体在水中的质量百分比浓度 为 5-30%, 溴基侧基烯醚单体在水中的质量百分比浓度为 1 ~ 12%。
又一方面， 本发明提供一种由上述的高交换容量全氟树脂制备而成的离 子交换膜。
再一方面， 本发明提供一种包含上述离子交换膜的燃料电池或电解池装 置； 所述燃料电池优选为质子膜燃料电池或高温燃料电池， 更优选为高温质 子膜燃料电池； 所述电解池优选为氯碱电解池。
再一方面， 本发明提供上述高交换容量全氟树脂用于制造燃料电池或电 解池装置中离子交换膜的用途； 所述燃料电池优选为质子膜燃料电池或高温 燃料电池， 更优选为高温质子膜燃料电池； 所述电解池优选为氯碱电解池； 优选地， 使用之前， 先将溴基侧基通过化学方法环化交联。 与现有技术相比， 本发明至少具有以下优点：
1、 本发明的全氟树脂带有两种不同结构的短侧基磺酰氟及溴基侧基' 解决了现有技术中离子交换容量与机械强度相对立的矛盾，提供了同时具有 高的离子交换容量及艮好的机械性能的全氟树脂。
2、本发明的全氟树脂带有两种不同结构的短侧基磺酰氟及氰基侧基，解 决了短侧基碩酰氟烯醚单体在聚合过程中发生链转移反应 ,得到的树脂分子 量不够高的问题， 具体反应机理可知如下： 其一、 聚合过程中采用了两种具 有不同结构短侧基磺酰氟烯醚单体， 这两种单体相互协同作用； 其二聚合体 系中存在溴基烯醚， 这 些不同种类烯醚的存在使得聚合反应协同向高分子量方向进行， 消除了链转 移环化反应。
3、 本发明采用四氟乙烯（TFE )与两种带有不同结构短侧基礒酰氟烯醚 单体及溴侧基烯醚单体进行多元共聚， 得到高分子量高交换容量全氟树脂， 这种多元共聚物具有高的化学稳定性、 高的离子交换容量及良好的高温机械 稳定性。
本发明高交换容量的全氟树脂可以用于制备燃料电池（例如高温燃料电 池）和氯碱电解槽等装置中的离子交换膜。 应用这种树脂制备的膜材料具有 高的电流效率、 低的膜电阻、 高的尺寸稳定性以及较高的机械强度。 以下是本发明的详细描述：
本发明提供一种带有两种不同结构的短侧基磺酰氟及溴基侧基的高交换 容量全氟树脂， 该全氟树脂是由四氟乙烯、 两种不同结构的短侧基碌酰氟烯 醚单 一种溴侧基烯醚单体多元共聚合而成， 聚合物链的分子式为：
Figure imgf000007_0001
( I )
其中 n=0-3的整数， 优选 n=0; m=2-4的整数； a、 b、 c = 3-15的整数, a，、 b，、 c，=l-3的整数； x/(x+y+z)=0.2-0.7， y/(x+y+z)=0.2-0.79,
z/(x+y+z)=0.01-0.1。
聚合物中各种聚合单元所占的摩尔含量百分数： 四氟乙烯聚合单元总体 摩尔分数 为 50〜85%, 短侧基礒酰氟烯醚聚合单元总体摩尔分数为 5〜49%， 溴侧基烯醚聚合单元总体摩尔分数为 1〜10%；
优选的， 聚合物中各种聚合单元所占的摩尔含量百分数： 四氟乙烯聚合 单元总体摩尔分数为 70〜80%， 磺酰氟侧基烯醚聚合单元总体摩尔分数为 15-29%, 溴侧基烯醚聚合单元总体摩尔分数为 1〜5%。
所述的两种不同结构的短侧基碩酰氟烯醚单体的结构式分别为：
广 2 1- 2
F2C=C-0-C -C -SO
F2 F2 F2 F2
2C=C— 0— C -C -C -C -S02F 构式为：
Figure imgf000008_0001
式中 n=0-3 , 优选 n=0; m=2-4的整数。
优选的， 树脂中四氟乙烯、 短侧基结构磺酰氟烯醚单体和溴侧基烯醚单 体的比例为： 50〜85： 5-49: 1-10; 摩尔比。 两种不同短侧基结构磺酰氟烯 醚单体（1 )和（2 )聚合单元在树脂中的比例为 0.2-0.8: 0.8-0.2, 摩尔比； 优选的， 两种不同短侧基结构磺酰氟烯醚单体（ 1 )和（2 )聚合单元在树脂 中的比例为 0.4-0.6: 0.6-0.4, 摩尔比。
上述高交换容量全氟树脂的数均分子量是 10〜60万， 优选为 15〜30万， 最优选为 18-25万。 上述高交换容量全氟树脂的分子量分布数值（指重均分 子量比数均分子量） 为 1.5-2.0。
本发明提供上述带有两种不同结构的短侧基磺酰氟及溴侧基的全氟离 子交换树脂的制备方法， 该制备方法是通过四氟乙烯、 两种不同结构短侧基 磺酰氟烯醚单体、一种溴侧基烯醚单体在 10 ~ 80°C、在引发剂的作用下进行 共聚反应 （聚合反应）来制备的， 该共聚反应的反应时间为 1 ~ 8小时， 反 应压力为 2 ~ 10MPa。
上述制备方法中， 引发剂可以使用本领域公知的引发剂， 也可以使用自 制的引发剂。
所述引发剂选自： N2F2、 全氟烷基过氧化物或过硫酸盐。
优选的， 所述全氟烷基过氧化物包括： 过氧化全氟烷基酰基化合物、 过 氧化全氟烷氧基酰基化合物、 过氧化部分含氟烷基酰基化合物、 过氧化部分 含氟烷氧基酰基化合物。 进一步优选全氟丙酰基过氧化物、 3-氯氟丙酰过氧 化物、全氟曱氧基乙酰过氧化物、 ώ-Η-全氟丁酰过氧化物、 d)-S02F-全氟 -2,5,8- 三曱基 -3,6,9-三氧杂-十一烷基过氧化物、 CF3CF2CF2CO-00-COCF2CF2CF3、 CF3CF2CF2OCFCF3CO-00-COCFCF3OCF2CF2CF3、
CF3CF2CH2CO- 00-COC¾CF2CF3或 CF3OCF2CF2CO-00-COCF2CF2OCF3。
优选的， 所述过硫酸盐包括过硫酸铵盐、 碱金属过硫化物或碱土金属过 硫化物； 进一步优选过硫酸铵或过硫酸钾等。
优选地， 树脂中四氟乙烯聚合单元、 两种不同结构的短侧基磺酰氟烯醚 聚合单元和溴基侧基烯醚聚合单元的摩尔比为： 50〜85： 5-49: 1〜10。
优选地， 两种不同结构的短侧基碩酰氟烯醚聚合单元（1 )和（2 )在树 脂中的摩尔比 0.2-0.8: 0.8-0.2; 更优选地， 两种不同结构的短侧基磺酰氟烯 醚聚合单元 ( 1 )和（2 )在树脂中的摩尔比为 0.4-0.6: 0.6-0.4。 优选的，上述共聚反应在水相中进行乳液聚合。具体的乳液聚合法如下：
1 ) 、 将反应釜洗净后， 加入纯水、 不同比例的两种短侧基磺酰氟烯醚 单体、 溴侧基烯醚单体和乳化剂， 乳化剂在水中的总体质量百分比浓度为 0.1-20%, 总体短侧基碩酰氟烯醚在水中的质量百分比浓度为 5-30%, 溴侧 基烯醚单体在水中的质量百分比浓度为 1 ~ 12%;
所述乳化剂包括一种或多种阴离子型乳化剂和 /或非离子型乳化剂。阴离 子型乳化剂包括脂肪酸钠、 十二烷基硫酸钠、 烷基礒酸钠、 烷基芳基磺酸钠 等； 非离子型乳化剂包括烷基酚聚醚醇类， 如壬基酚聚氧乙烯醚、 聚氧乙浠 脂肪酸、聚氧乙烯脂肪酸醚。上述乳化剂可以单独使用也可以多种复配使用。
2 ) 、 通过气体计量槽向反应釜内充四氟乙烯单体至压力为 2-10MPa;
3 ) 、 反应釜升温至 10 ~ 80°C , 通过计量泵向反应体系中加入引发剂引 发反应进行， 持续向反应釜补加四氟乙浠单体和引发剂， 保持反应釜反应压 力 2-10MPa, 反应时间为 1 ~ 8小时；
4 ) 、 反应结束时， 停止向反应釜内加入引发剂和四氟乙烯单体， 通过 反应釜放空管路及回收槽放空回收未反应的四氟乙烯单体； 得到乳白色的聚 合物浆料， 将液体浆料通过放料***进入后处理设备中， 高速剪切， 过滤分 离得到白色聚合物粉末， 于 100。C烘箱中供干， 得到带有两种不同结构的短 侧基横酰氟及溴侧基的高离子交换容量全氟离子交换树脂。 过滤液中的磺酰 氟烯醚单体和溴侧基烯醚单体通过回收***回收利用。
步骤 1 ) 中两种不同结构的短侧基磺酰氟烯醚单体（1 )和（2 ) 聚合单 元的比例为 0.2-0.8: 0.8-0.2, 摩尔比； 优选的， 两种不同结构的短侧基磺酰 氟烯醚单体（1 )和（2 ) 聚合单元的比例为 0.4-0.6: 0.6-0.4, 摩尔比。
所述引发剂选自： N2F2、 全氟烷基过氧化物或过硫酸盐； 本领域的技术 人员可以根据本领域的公知常识选择引发剂的浓度。
所述全氟烷基过氧化物包括： 过氧化全氟烷基酰基化合物、 过氧化全氟 烷氧基酰基化合物、过氧化部分含氟烷基酰基化合物或过氧化部分含氟烷氧 基酰基化合物；
所述过硫酸盐包括过硫酸铵、 碱金属过硫酸盐或碱土金属过硫酸盐； 优 选过 υ酸铵或过^ L酸钾。
本发明所述的带有两种不同结构的短侧基磺酰氟及溴基侧基的高离子交 换容量全氟离子交换树脂的应用，可用于制造燃料电池或高温燃料电池的离 子交换膜。
本发明所述的带有两种不同结构的短侧基横酰氟及溴基侧基的高离子交 换容量全氟离子交换树脂的应用， 具体地说是用于质子膜燃料电池、 高温质 子膜燃料电池或氯碱电解槽等装置中作为离子交换膜。这类离子交换膜具有 高的化学稳定性、 高的电流效率、 低的膜电阻、 高的尺寸稳定性以及较高的 机械强度等。
本发明所述的带有两种不同结构的短侧基磺酖氟及溴基侧基的高离子 交换容量全氟离子交换树脂的应用，该树脂可采用溶液浇注工艺制成合适厚 度的全氟磺酸离子交换膜或者采用熔融挤出设备通过高温熔融挤出制备出 合适厚度的膜材料。而后将膜材料通过公知的做法如辐射交联、热处理交联、 加入光引发剂引发交联或者通过自由基引发剂引发交联将溴基侧基进行脱 溴交联； 其后将磺酰氟侧基转型为磺酸侧基， 制成的全氟离子交换膜不但具 有耐各种化学介质性， 还具有高的导电性、 高机械强度及高的尺寸稳定性， 低的膜电阻， 非常适合在燃料电池、 高温燃料电池或氯碱电解池中使用。
本发明所述的带有两种不同结构的短侧基碌酰氟及溴基侧基的高离子 交换容量全氟离子交换树脂在燃料电池中的应用，基于溴侧基脱溴交联可以 进一步提高离子交换膜的保水能力、 尺寸稳定性和机械强度， 有效提高膜材 料的使用性， 进一步增加膜材料的使用期限。 本发明的有益效果是：
本发明所合成的全氟离子交换树脂的离子交换容量介于 0.5-2.6mmol/g (干树脂） ， 离子交换容量越小， 其机械强度越大， 其中离子交换容量介于 1.28-1.95mmol/g 的未交联树脂的机械强度超过 20MPa， 制备的膜材料具有 非常好的热稳定性能， 膜材料经过交联处理后， 其机械强度超过 30MPa。 室 温测定膜材料的电导率大于 0.2S/cm, 在 100°C、 45%湿度情况下测定的电导 率仍然高于 0.05S/cm, 完全能满足燃料电池质子膜和氯碱电解膜材料的需 求。 附图说明
图 1 表示本发明中的一个实施方式的全氟树脂的 F19 NMR谱图。
图 2表示本发明中的一个实施方式的全氟树脂的红外谱图。
图 3 表示本发明中的一个实施方式的全氟树脂的红外谱图。
图 4表示本发明中的一个实施方式的全氟树脂的 F19 NMR谱图。 实施发明的最佳方式
以下实施例是对本发明的进一步说明， 但本发明并不局限于此。 如无特 别说明， 各实施例中所用的反应釜均为 10L不锈钢高压反应釜， 并配有温度 传感器、 压力传感器、 加热循环***、 冷却循环***、 搅拌电机、 内部冷却 水管、 液体计量泵、 气体进料阀门、 液体进料阀门、反应釜内物料出料阀门。
以下实施例中无特别说明外， 离子交换容量全部为磺酰氟水解为磺酸后 测定结果。
本发明在合成过程中所采用的全氟烷基引发剂可以按照本领域公知技 术制备， 本发明推荐的制备方法参见 J. Org. Chem. , 1982, 47(1 1):
2009-2013
本发明在合成过程中所采用的过硫酸钾、 过硫酸铵、 N2F2气体全部可以 购买得到。 其中所采用的过硫酸钾、 过硫酸铵可以通过国药集团购买； N2F2 气体可以在东岳化工有限公司购买得到。
本发明在合成过程中所采用的共聚单体四氟乙烯购买自山东东岳高分 子材料有限公司； 短侧基磺酰氟单体可以参考美国专利 3560568和美国专利
6624328所述制备的方法， 本发明专利采用中国专利申请号为：
CN200910229444.1、 CN 200910229446.0、 CN 200910230218.5所述制备的方 法获得， 溴基侧基烯醚单体参考 EP0380129和 EP0194862所述制备的方法。 实施例 1:
将反应釜洗净并加入 5.0L去离子水、 100g十二烷基苯磺酸钠和 12 壬 基酚聚氧乙烯醚 NP-10乳化剂，开动搅拌装置，抽真空充高纯氮气置换三次， 经测试反应釜内氧含量在 lppm以下后， 抽真空， 通过液体进料阀门向反应 釜内加入 500g横酰氟侧基烯醚单体 (1) ( F2C-CF-0-CF2CF2-S02F )及 650g 磺酰氟侧基烯醚单体 (2) ( F2OCF-0-CF2CF2CF2CF2-S02F )及 405g溴侧基烯 醚单体（F2OCF-0-CF2CF2-Br )后， 向反应釜内充四氟乙烯单体至压力为 2.9MPa, 升温至 20°C , 用计量泵加入 2.6g过氧化全氟丁酰基化合物
( CF3CF2CF2CO-00-CCF2CF2CF3 ) 引发聚合反应， 持续通入四氟乙烯 ( CF2=CF2 )单体保持反应压力在 2.9MPa， 每隔 15min向体系中加入引发剂 0.75g， 反应 2h后， 停止加入引发剂， 让反应继续进行 15min后， 停止加入 四氟乙烯单体。 通过冷却循环***给反应釜降温， 同时通过回收***回收未 反应的四氟乙浠单体，将釜内的乳白色浆料通过下放料阀门放入后处理*** 中， 通过高速剪切后， 过滤分离得到白色聚合物粉末， 于 100°C洪箱中烘干， 得到带有短侧基磺酰氟及溴侧基的全氟离子交换树脂。 过滤液中的磺酰氟烯 醚单体和溴侧基烯醚单体通过回收***回收后重复利用。
聚合物数据： 经 F19 NMR、 IR分析证实为多元共聚物， 通过氟核磁积分 值可知聚合物结构中含有四氟乙烯聚合单元的摩尔百分数为 62.71%, 含有 磺酰氟侧基烯醚单体 (1)聚合单元摩尔百分数为 16.5%,含有磺酰氟侧基烯醚 单体 (2)聚合单元摩尔百分数为 16.3%，含有溴侧基烯醚聚合单元摩尔百分数 为 4.49%， 总体离子交换容量为： 1.77mmol/g干树脂。 TGA测试树脂氮气气 氛下的分解温度（Td ) 为 401 °C ; IR谱图： 1468cm 为磺酰氟中 S = 0振动 吸收峰； 1200和 1148cm-l两个最强吸收由 CF振动引起; 720cm"1, 641cm"1 由四氟乙烯共聚后的 -CF2-CF2-振动吸收引起。 实施例 2:
将反应釜洗净并加入 5.0L去离子水、 220g十二烷基苯磺酸钠， 开动搅 拌装置， 抽真空充高纯氮气置换三次， 经测试反应釜内氧含量在 lppm以下 后， 抽真空， 通过液体进料阀门向反应釜内加入 500g磺酰氟侧基婦醚单体 (1) ( F2C=CF-0-CF2CF2-S02F )及 405g磺酰氟侧基烯醚单体 (2)
( F2C=CF-0-CF2CF2CF2CF2-S02F ) 以及 225g溴侧基烯醚单体
( F2C=CF-0-CF2CF2CF2Br )后， 向反应釜内充四氟乙烯单体至压力为 2.9MPa, 升温至 35°C , 用计量泵加入 8.0g过氧化全氟丙氧基丙基化合物 ( CF3CF2CF2OCF(CF3)COOO-CCF(CF3)OCF2CF2CF3 ) ？ ]发聚合反应 , 持续 通入四氟乙烯（ CF2=CF2 )单体保持反应压力在 2.9MPa， 每隔 min向体系 中加入引发剂 2.3g， 反应 2.5h后， 停止加入引发剂， 让反应继续进行 25min 后， 停止加入四氟乙烯单体。 通过冷却循环***给反应釜降温， 同时通过回 收***回收未反应的四氟乙烯单体，将釜内的乳白色浆料通过下放料阀门放 入后处理***中，通过高速剪切后，过滤分离得到白色聚合物粉末，于 ioo°c 烘箱中烘干， 得到带有短侧基磺酰氟及溴侧基的全氟离子交换树脂。 过滤液 中的磺酰氟烯醚单体和溴侧基烯醚单体通过回收***回收后重复利用。
聚合物数据： 经 F19 NMR (如图 1所示） 、 IR分析证实为多元共聚物， 通过氟核磁积分值可知聚合物结构中含有四氟乙烯聚合单元的摩尔百分数 为 73.8%, 含有磺酰氟侧基烯醚单体 (1)聚合单元摩尔百分数为 15%， 含有磺 酰氟侧基烯醚单体 (2)聚合单元摩尔百分数为 9%, 含有溴侧基烯醚单体摩尔 百分数为 2.2%, 总体离子交换容量为： 1.53mmol/g干树脂。 TGA测试树脂 氮气气氛下的分解温度（Td ) 为 405°C ; IR谱图： 1468cm 为磺酰氟中 S = 0振动吸收峰； 1200和 1148cm-1两个最强吸收由 CF振动引起； 720cm-1、 641cm-1由四氟乙烯共聚后的 -CF2-CF2-振动吸收引起。 实施例 3:
将反应釜洗净并加入 5.0L去离子水、 120g十二烷基苯 酸钠及 95g壬 基酚聚氧乙烯醚 NP-10乳化剂，开动搅拌装置，抽真空充高纯氮气置换三次， 经测试反应釜内氧含量在 lppm以下后， 抽真空， 通过液体进料阀门向反应 釜内加入 300g磺酰氟侧基烯醚单体 (1) ( F2C=CF-0-CF2CF2-S02F )及 610g 磺酰氟侧基烯醚单体 (2) ( F2C=CF-0-CF2CF2CF2CF2-S02F ) 以及 250g溴侧基 烯醚单体（ F2OCF-0-CF2CF2 CF2CF2Br )后， 向反应釜内充四氟乙烯单体至 压力为 3.2MPa,升温至 80°C , 用计量泵加入 10%过石克酸铵水溶液 320g引发 聚合反应， 持续通入四氟乙烯（CF2=CF2 )单体保持反应压力在 3.2MPa， 反 应 3h后， 停止加入四氟乙烯单体。 通过冷却循环***给反应釜降温， 同时 通过回收***回收未反应的四氟乙烯单体，将釜内的乳白色浆料通过下放料 阀门放入后处理***中， 通过高速剪切后， 过滤分离得到白色聚合物粉末， 于 100°C烘箱中烘干，得到带有短侧基碌酰氟、溴侧基的全氟离子交换树脂。 过滤液中的碩酰氟烯醚单体和溴侧基烯醚单体通过回收***回收后重复利 用。
聚合物数据： 经 F19 NMR、 IR (如图 2所示）分析证实为多元共聚物， 通过氟核磁积分值可知聚合物结构中含有四氟乙烯聚合单元的摩尔百分数 为 75.7%, 含有磺酰氟侧基烯醚单体 (1)聚合单元摩尔百分数为 8.9%, 含有 磺酰氟侧基烯醚单体 (2)聚合单元摩尔百分数为 12.28%, 含有溴侧基烯醚聚 合单元摩尔百分数为 3.12%,总体离子交换容量为： l.34mmol/g干树脂。 TGA 测试树脂氮气气氛下的分解温度（Td )为 395°C ; IR谱图： 1468cm-1为磺酰 氟中 S = 0振动吸收峰； 984cm— 1为 -CF3振动引起的; 1200和 1148cm-1两个 最强吸收由 CF振动引起; 720cm"1 , 641cm 由四氟乙烯共聚后的 -CF2-CF2- 振动吸收引起。 实施例 4:
将反应釜洗净并加入 5.0L去离子水、 180g十二烷基苯磺酸钠及 45g壬 基酚聚氧乙烯醚 NP-10乳化剂，开动搅拌装置，抽真空充高纯氮气置换三次， 经测试反应釜内氧含量在 lppm以下后， 抽真空， 通过液体进料阔门向反应 釜内加入 300g磺酰氟侧基烯醚单体 (1) ( F2C=CF-0-CF2CF2-S02F )及 400g 磺酰氟侧基烯醚单体 (2) ( F2C=CF-0-CF2CF2CF2CF2-S02F )以及 250g溴侧基 烯醚单体（ F2C=CF-0-CF2CF(CF3)OCF2 CF2Br )后， 向反应釜内充四氟乙烯 单体至压力为 2.7MPa, 升温至 20°C , 用气体流量计控制流量向反应釜内引 入由 N2F2引发聚合反应， 持续通入四氟乙烯（CF2=CF2 )单体， 保持反应压 力从 2.7MPa緩慢上升 , 持续向体系中加入引发剂 N2F2 , 反应 2h后， 反应 釜压力为 3.0MPa， 停止加入引发剂， 让反应继续进行 lmin后， 停止加入四 氟乙烯单体。 通过冷却循环***给反应釜降温， 同时通过回收***回收未反 应的四氟乙烯单体， 将釜内的乳白色浆料通过下放料阀门放入后处理*** 中， 通过高速剪切后， 过滤分离得到白色聚合物粉末， 于 100°C烘箱中供干， 得到带有短侧基碌酰氟及溴侧基的全氟离子交换树脂。过滤液中的磺酰氟烯 醚单体和溴侧基烯醚单体通过回收***回收后重复利用。
聚合物数据： 经 F19 NMR、 IR (如图 3所示）分析证实为多元共聚物， 通过氟核磁积分值可知聚合物结构中含有四氟乙烯聚合单元的摩尔百分数 为 74.5%, 含有磺酰氟侧基烯醚单体 (1)聚合单元摩尔百分数为 10.5%, 含有 磺酰氟侧基烯醚单体 (2)聚合单元摩尔百分数为 13.79%, 含有溴侧基烯醚聚 合单元摩尔百分数为 1.21%,总体离子交换容量为： 1.54mmol/g干树脂。 TGA 测试树脂氮气气氛下的分解温度（Td )为 387°C ; IR谱图： 1468cm— 1为磺酰 氟中 S = 0振动吸收峰； 1200和 1148cm 两个最强吸收由 CF振动引起； 720cm'1 , 641cm-1由四氟乙烯共聚后的 -CF2- CF2-振动吸收引起。 实施例 5:
将反应釜洗净并加入 5.0L去离子水、 215g十二烷基苯磺酸钠乳化剂， 开动搅拌装置，抽真空充高纯氮气置换三次，经测试反应釜内氧含量在 lppm 以下后， 抽真空， 通过液体进料阀门向反应釜内加入 780g磺酰氟侧基烯醚 单体 (1) ( F2C=CF-0-CF2CF2-S02F )及 720g磺酰氟侧基烯醚单体 (2)
( F2C=CF-0-CF2CF2CF2CF2-S02F ) 以及 650g溴侧基烯醚单体
( F2OCF-0-CF2CF2Br )后， 向反应釜内充四氟乙烯单体至压力为 2.8MPa, 升温至 25°C，用气体流量计控制流量向反应釜内引入由 N2F2引发聚合反应， 持续通入四氟乙烯（CF2=CF2 )单体， 保持反应压力从 2.8MPa緩慢上升， 持 续向体系中加入引发剂 N2F2， 反应 2h后， 反应压力为 3.2MPa, 停止加入引 发剂， 让反应继续进行 lmin后， 停止加入四氟乙烯单体。 通过冷却循环系 统给反应釜降温， 同时通过回收***回收未反应的四氟乙烯单体， 将釜内的 乳白色浆料通过下放料阀门放入后处理***中， 通过高速剪切后， 过滤分离 得到白色聚合物粉末， 于 100°C烘箱中供干， 得到带有短侧基礒酰氟及溴侧 基的全氟离子交换树脂。反应液体中的磺酰氟烯醚单体和溴侧基烯醚单体通 过回收***回收后重复利用。
聚合物数据： 经 F19 NMR (如图 4所示） 、 IR分析证实为多元共聚物， 通过氟核磁积分值可知聚合物结构中含有四氟乙烯聚合单元的摩尔百分数 为 67.1%, 含有横酰氟侧基烯醚单体 (1)聚合单元摩尔百分数为 14.2%， 含有 磺酰氟侧基烯醚单体 (2)聚合单元摩尔百分数为 11.46%, 含有溴侧基烯醚聚 合单元摩尔百分数为 7.24%，总体离子交换容量为： 1.44mmol/g干树脂。 TGA 测试树脂氮气气氛下的分解温度（Td ) 为 384°C ; IR谱图： 1468cm-1为磺酰 氟中 S = 0振动吸收峰; 984cm— 1为 -CF3振动引起的; 1200和 1148cm 两个 最强吸收由 CF振动引起； YZOcm-1 641cm 由四氟乙烯共聚后的 -CF2-CF2- 振动吸收引起。 实施例 6:
将反应釜洗净并加入 5.0L去离子水、 225g十二烷基苯磺酸钠乳化剂， 开动搅拌装置，抽真空充高纯氮气置换三次，经测试反应釜内氧含量在 lppm 以下后， 抽真空， 通过液体进料阔门向反应釜内加入 420g磺酰氟侧基烯醚 单体 (1) ( F2C=CF-0-CF2CF2-S02F )及 265g磺酰氟侧基烯醚单体 (2)
( F2C=CF-0-CF2CF2CF2CF2-S02F ) 以及 350g溴侧基烯醚单体
( F2C=CF-0-CF2CF2CF2CF2Br )后， 向反应釜内充四氟乙烯单体至压力为 5.2MPa, 升温至 45°C , 用计量泵加入 20.2g cb-S02F-全氟 -2，5,8-三曱基 -3,6,9- 三氧杂-十一烷基过氧化物引发聚合反应， 持续通入四氟乙烯（CF2=CF2 )单 体保持反应压力在 5.2MPa， 每隔 45min向体系中加入引发剂 6g, 反应 2h 后， 停止加入引发剂， 让反应继续进行 45min后， 停止加入四氟乙烯单体。 通过冷却循环***给反应釜降温， 同时通过回收***回收未反应的四氟乙烯 单体， 将釜内的乳白色浆料通过下放料阀门放入后处理***中， 通过高速剪 切后， 过滤分离得到白色聚合物粉末， 于 100°C烘箱中烘干， 得到带有短侧 基磺酰氟及溴侧基的全氟离子交换树脂。过滤液中的磺酰氟烯醚单体和溴侧 基烯醚单体通过回收***回收后重复利用。
聚合物数据： 经 F19 NMR、 IR分析证实为多元共聚物， 通过氟核磁积分 值可知聚合物结构中含有四氟乙烯聚合单元的摩尔百分数为 80%，含有磺酰 氟侧基烯醚单体 (1)聚合单元摩尔百分数为 8.2%， 含有磺酰氟侧基烯醚单体 (2)聚合单元摩尔百分数为 9.92%, 含有溴侧基烯醚聚合单元摩尔百分数为 1.88%, 总体离子交换容量为： 1.27mmol/g干树脂。 TGA测试树脂氮气气氛 下的分解温度（Td ) 为 387°C ; IR i普图： 1468cm-1为磺酰氟中 S = 0振动吸 收峰; 1200和 1148cm-1两个最强吸收由 CF振动引起； 720cm-1 , 641cm 由 四氟乙烯共聚后的 -CF2-CF2-振动吸收引起。 实施例 7
本实施例用于说明使用实施例 1 -6的全氟离子交换树脂制备离 子交换膜的过程，以及所制备的膜的力学性能。
离子交换膜的制备过程：
粒料制备： 将实施例 1 -6中得到的白色粉末产物分别经小型熔 融挤出机挤出制备粒料， 熔融挤出机的挤出温度设定为： 螺杆一区 250°C、 螺杆二区 255 °C、 螺杆三区 260 °C、 挤出机模口温度 270 °C， 挤出机口模直径 3mm , 通过调整剪切速率， 将熔融挤出的柱状透 明物料剪切制备出长度 2-4mm的透明树脂粒料， 将粒料用双层 PE 塑料袋密闭保存。
熔融挤出挤膜： 将熔融挤出机口模更换为薄膜挤出模头， 螺杆 区域设定温度同上，将制备的透明粒料采用熔融挤出的方式制备成 薄膜， 薄膜厚度可以通过调整模口的宽窄调节， 通常制备的薄膜厚 度为 20- 100μηι。
熔融挤出模转型： 将薄膜的磺酰氟（ -S02F )侧基转为磺酸离子（ -S03H ) 形式，将制备的薄膜依次通过 80°C质量百分浓度 30%的氢氧化钠溶液、 30°C 质量百分比浓度 30%的硫酸溶液 (H2S04)、 流动的去离子水洗漆槽。 薄膜在 碱液中停留时间 30min、 在硫酸溶液中停留时间为 10min， 在去离子水槽中 用去离子水冲洗 lOmin, 其后将膜材料收卷， 密闭保存， 即得到膜产品， 由 实施例 1-6的全氟离子交换树脂制备的离子交换膜分别相应地记作膜 1-膜 6。
膜力学性能测试： 测试方式采用方法为 GB/T1040-92, 测定使用实施例 1-6制备的全氟离子交换树脂制备离子交换膜 1-膜 6, 以及杜邦公司的型 号为 NRE 211的磺酸膜的力学性能， 结果列于表 1。
Figure imgf000017_0001
测定结果显示本发明的树脂制备的膜产品与现有技术相比具有更 高的分子量、 化学稳定性、 高的耐热温度、 高的离子交换容量以及良好 的高温机械性能。 实施例 8
将 1.0L反应釜洗净并加入 500ml去离子水、 10g十二烷基苯磺酸钠和 13g 壬基酚聚氧乙烯醚 NP-10乳化剂， 开动搅拌装置， 抽真空充高纯氮气置换三 次， 经测试反应釜内氧含量在 Ippm以下后， 抽真空， 通过液体进料阀门向 反应釜内加入 50g磺酰氟侧基烯醚单体 (1)( F2C=CF-0-CF2-CF2-S02F )及 60g 磺酰氟侧基烯醚单体 (2) ( F2C=CF-0-CF2-CF2-CF2CF2-S02F )及 40g溴基侧基 烯醚单体（ F2C=CF-0-CF2CF2- Br )后， 向反应釜内充四氟乙烯单体至压力 为 3.9MPa, 升温至 80°C， 向反应釜内加 5.2g过硫酸铵引发剂， 保持压力在 3.9MPa聚合 2hr后停止反应， 破乳后得到白色聚合物粉末， 洗涤干燥后， 将 白色聚合物粉末溶于 DMF溶剂中配制成 10mg/ml浓度的溶液，进行 GPC测 试， 结果显示数均分子量在 22.5万、 重均分子量在 36万， 红外测试结果中 未检测到异常的振动吸收峰。
采取以上同样的条件，唯一改变的是通过液体进料阀门向反应釜内加入 145g磺酰氟侧基烯醚单体 (1) ( F2C=CF-0-CF2-CF2-S02F ) , 保证体系内总的 双键的浓度与以上条件一致， 所得聚合物的粉末溶于测定 GPC结果显示出 数均分子量在 12.3万、 重均分子量在 20.5万， 并且红外测试结果中检测到 了 -S-0-C-单键的反对称伸缩振动吸收峰， 出现在 830cnf'处。
这些结果显示， 采用一种磺酰氟侧基烯醚单体 (1), 在聚合过程中确实会 出现短侧基环化， 而本发明由于釆用两种磺酰氟侧基烯醚单体（1 )和（2 ) 以及其他烯醚单体的相互作用， 环化反应会减弱或者消除。

Claims

权 利 要 求
1. 一种高交换容量全氟树脂， 是由四氟乙烯、 两种不同结构短侧基磺 酰氟烯醚单体、 一种溴基侧基烯醚单体多元共聚合而成， 该树脂主要含有以 下式（I )所示的重复单元：
Figure imgf000019_0001
其中 n=0-3的整数， 优选 n=0; m=2-4的整数； a、 b、 c = 3-15的整数， a，、 b，、 c'=l-3的整数； x/(x+y+z)=0.2-0.7, y/(x+y+z)=0.2-0.79,
z/(x+y+z)=0.01-0.1 , 摩尔比。
2. 如权利要求 1所述的高交换容量全氟树脂， 其中所述的两种不同结 构短侧基横酰氟烯醚单体的结构式分别为：
F2 F2
F2C=C-0-C -C -S02F
F2 F2 2 F2
F2C=C - 0— C -C -C C -S02F
F (2)
：
Figure imgf000019_0002
式中 n=0-3 , 优选 n=0; m=2-4的整数。
3. 如权利要求 1或 2所述的高交换容量全氟树脂， 其中聚合物中各聚 合单元所占的摩尔含量百分数为： 四氟乙烯聚合单元总体摩尔分数 为 50-85%, 短侧基礒酰氟烯醚聚合单元总体摩尔分数为 5〜49%, 溴侧基烯醚 聚合单元总体摩尔分数为 1〜10%；
优选地， 聚合物中各聚合单元所占的摩尔含量百分数为： 四氟乙烯聚合 单元总体摩尔分数为 70~80%， 磺酰氟侧基烯醚聚合单元总体摩尔分数为 15-29%, 溴侧基烯醚聚合单元总体摩尔分数为 1〜5%。
4.如权利要求 1到 3任一项权利要求所述的高交换容量全氟树脂，其中 所述的两种不同结构的短侧基璜酰氟烯醚（ 1 )和（2 )聚合单元在树脂中的 摩尔比为 0.2-0.8: 0.8-0.2, 摩尔比； 优选为 0.4-0.6: 0.6-0.4, 。
5. 如权利要求 1至 4任一项所述的高交换容量全氟树脂的制备方法， 该制备方法包括使四氟乙烯、 两种不同结构的短侧基磺酰氟烯醚单体、 一种 溴基侧基烯醚单体在引发剂的作用下进行共聚反应， 优选地， 所述聚合反应 的反应时间为 8小时， 反应温度为 10 ~ 80°C , 反应压力为 2〜10MPa。
6. 如权利要求 5所述的制备方法， 其中所述引发剂选自： N2F2、 全氟 烷基过氧化物或过硫酸盐中的一种或多种；
优选地， 所述全氟烷基过氧化物选自： 过氧化全氟烷基酰基化合物、 过 氧化全氟烷氧基酰基化合物、过氧化部分含氟烷基酰基化合物和过氧化部分 含氟烷氧基酰基化合物中的一种或多种； 所述过硫酸盐选自过硫酸铵盐、 碱 金属过硫化物或碱土金属过硫化物中的一种或多种；
进一步优选所述全氟烷基过氧化物为选自全氟丙酰基过氧化物、 3-氯氟丙酰 过氧化物、 全氟曱氧基乙酰过氧化物、 ώ-Η-全氟丁酰过氧化物、 d)-S02F-全 氟 -2，5,8- 三 曱 基 -3,6，9- 三 氧 杂 - 十 一 烷 基 过 氧 化 物 、 CF3CF2CF2CO-00-COCF2CF2CF3 、 CF3CF2CF2OCFCF3CO- 00-COCFCF3OCF2CF2CF3 、 CF3CF2CH2CO-00-COCH2CF2CF3或 CF3OCF2CF2CO- 00-COCF2CF2OCF3中 的一种或多种； 所述过石克酸盐为选自过硫酸铵和过硫酸钾中的一种或多种。
7. 如权利要求 5或 6所述的制备方法， 其中所述制备方法还包括在水 相中进行乳液聚合反应的步骤；
优选地， 在乳液聚合反应步骤中， 乳化剂选自阴离子型乳化剂， 例如包 括脂肪酸钠、 十二烷基硫酸钠、 烷基横酸钠、 烷基芳基磺酸钠； 和非离子型 乳化剂， 例如烷基酚聚醚醇类， 如壬基酚聚氧乙烯醚、 聚氧乙烯脂肪酸、 聚 氧乙烯脂肪酸醚中的一种或多种； 更优选地， 在乳液聚合反应步驟中， 乳化剂在水中的质量百分比浓度为
0.1-20%, 两种不同结构的短侧基磺酰氟烯醚单体在水中的质量百分比浓度 为 5-30%， 溴基侧基烯醚单体在水中的质量百分比浓度为 1 ~ 12%。
8. 如权利要求 1到 4任一项所述的高交换容量全氟树脂制造的离子交 换膜。
9. 一种包含权利要求 8所述的离子交换膜的燃料电池或电解池装置； 所述燃料电池优选为质子膜燃料电池或高温燃料电池， 更优选为高温质子膜 燃料电池； 所述电解池优选为氯碱电解池。
10. 权利要求 1至 4任一项所述的高交换容量全氟树脂用于制造燃料电 池或电解池装置中离子交换膜的用途； 所述燃料电池优选为质子膜燃料电池 或高温燃料电池， 更优选为高温质子膜燃料电池； 所述电解池优选为氯碱电 解池； 优选地， 使用之前， 先将溴基侧基通过化学方法环化交联。
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EP2514773B1 (en) 2014-12-03
JP5486693B2 (ja) 2014-05-07
CA2784539A1 (en) 2011-06-23
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