WO2011071599A2 - Procédé de préparation d'un polymère de fluorosilicone - Google Patents

Procédé de préparation d'un polymère de fluorosilicone Download PDF

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WO2011071599A2
WO2011071599A2 PCT/US2010/053319 US2010053319W WO2011071599A2 WO 2011071599 A2 WO2011071599 A2 WO 2011071599A2 US 2010053319 W US2010053319 W US 2010053319W WO 2011071599 A2 WO2011071599 A2 WO 2011071599A2
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group
oxy
methyl
trifluoroethenyl
monomer
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PCT/US2010/053319
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WO2011071599A3 (fr
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Ming-Hong Hung
Bruno Ameduri
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Dupont Performance Elastomers L.L.C.
Le Centre National De La Recherche Scientifique...
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Priority to EP10836370.6A priority Critical patent/EP2510045A4/fr
Priority to KR1020127017616A priority patent/KR20120129883A/ko
Priority to CN201080055743.9A priority patent/CN102782015B/zh
Priority to JP2012543099A priority patent/JP5635124B2/ja
Publication of WO2011071599A2 publication Critical patent/WO2011071599A2/fr
Publication of WO2011071599A3 publication Critical patent/WO2011071599A3/fr

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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
    • 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
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/24—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing groups
    • 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
    • C08F14/00—Homopolymers and 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
    • C08F14/18—Monomers containing fluorine
    • 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
    • C08F214/184—Monomers containing fluorine 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
    • C08F214/22—Vinylidene fluoride
    • 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
    • C08F214/22—Vinylidene fluoride
    • C08F214/222—Vinylidene fluoride 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
    • C08F216/00—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 an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F216/12—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 an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
    • C08F216/14—Monomers containing only one unsaturated aliphatic radical
    • C08F216/1408—Monomers containing halogen
    • 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
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
    • 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
    • C08F8/00—Chemical modification by after-treatment
    • 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
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/04—Reduction, e.g. hydrogenation
    • 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
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/26—Removing halogen atoms or halogen-containing groups from the molecule
    • 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
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/42—Introducing metal atoms or metal-containing groups

Definitions

  • This invention relates to preparation of crosslinked fluorosilicon polymers by a process that comprises acid catalyzed hydrolysis and step growth polycondensation of silicon-containing polymeric adducts that comprise copolymerized units of a perfluoro(alkyl vinyl ether) and a monomer selected from the group consisting of vinylidene fluoride and tetrafluorpethylene.
  • High molecular weight fluorinated copolymers that are made up of copolymerized units of perfluoro(methyl vinyl ether) (PMVE) and either vinylidene fluoride (VF 2 ) or tetrafluoroethylene (TFE) are known in the art and have been utilized to form vulcanized elastomer parts having relatively low glass transition temperatures (Tg), for example as disclosed in US Patent Publication 2005/0215741 A1.
  • the copolymers may be
  • Fluorosilicon polymers have also been prepared using similar low molecular weight oligomers.
  • U.S. Patent 5,081 ,192 discloses the reaction of unsaturated silicon-containing compounds of Formula I, shown below,. with iodinated reactants of Formula II to form fluorinated copolymers of Formula III. Such fluorinated iodinated copolymers may be converted into polymer networks by reaction with zinc.
  • CH 2 CY-(CH 2 ) n -SiRxX ⁇ x
  • X is a monovalent functional group
  • Y is a hydrogen atom or a lower alkyl group
  • R is a hydrogen atom or an inactive monovalent organic group
  • x is an integer of 0 to 3
  • n is 0, 1 , or 2
  • PC is a polymer chain and m is a positive integer which is not larger than the number of ends of the polymer chain PC.
  • the polymer of formula III has a molecular weight of 5 x 10 2 - 5 x 10 6 .
  • X in formula III is a halogenated atom
  • the iodo group(s) present can be removed by treating iodinated oligomer III with an alcohol and an element in the II or III group of the periodic table, preferably zinc.
  • the polymer forms siloxane bonds by dehydration condensation of silanols that are formed by hydrolysis of the SiR x X3 -x groups, whereby the molecular weight increases and further three dimensional crosslinking occurs.
  • Crosslinked fluorosilicon polymer networks of the type described above are compositions having good sealing properties and low T g .
  • the present invention is a process for producing a crosslinked fluorinated polymer comprising the steps of :
  • comonomer can only be tetrafluoroethylene when said first monomer is vinylidene fluoride and said comonomer can only be hexafluoropropyiene when said first monomer is tetrafluoroethylene;
  • iodinated oligomer has a number average molecular weight of 1000 to 25,000 g/mole and wherein said oligomer has an iodine group at each chain end;
  • CH 2 CY-(CH 2 )n-SiRR'R"
  • Y is a hydrogen atom or a C1-C3 alkyl group
  • R is a methoxy or ethoxy group
  • R' and R" are independently selected from the group consisting of methyl groups, methoxy groups and ethoxy groups, under conditions wherein the molar ratio of said iodinated oligomer to said vinyl silane is 1 to at least 2.5 to form a silicon-containing polymeric adduct that is a composition of the formula
  • PC is the polymer chain of said iodinated oligomer, n is 0- 2 and m is 2;
  • comonomer can only be tetrafluoroethylene when said first monomer is vinylidene fluoride and said third monomer can only be hexafluoropropylene when said first monomer is tetrafluoroethylene;
  • ethanesulfonyl fluoride 2-[1-[difluoro[(1,2,2- trifluoroethenyl)oxy]methyl]-1 ,2,2,2-tetrafluoroethoxy]- 1 ,1,2,2-tetrafluoro- ;
  • 1-propanol 3-[1-[difluoro[(trifluoroethenyl)oxy]methyl]- 1 ⁇ -tetrafluoroethoxyJ ⁇ .S.S-tetrafluoro- ;
  • propanenitrile 3-[1-[difluoro[(1 ,2,2- trifluoroethenyl)oxy]methyl]-1 ,2,2,2-tetrafluoroethoxy]- 2,2,3,3-tetrafIuoro- ;
  • iodinated oligomer has a number average molecular weight of 1000 to 25,000 g/mole and wherein said oligomer has an iodine group at each chain end;
  • CH 2 eY-(CH 2 )n-SiRR'R"
  • Y is a hydrogen atom or a C 1 -C3 alkyl group
  • R is a methoxy or ethoxy group
  • R' and R" are independently selected from the group consisting of methyl groups, methoxy groups and ethoxy groups, under conditions wherein the molar ratio of said iodinated oligomer to said vinyl silane is 1 to at least 2.5 to form a silicon-containing polymeric adduct that is a composition of the formula PC-[CH 2 CYI-(CH2)nSiRR'R"] m
  • PC is the polymer chain of said iodinated oligomer, n is 0- 2 and m is 2;
  • the present invention relates to an improved process for synthesis of crosslinked silicon-containing fluorinated elastomeric polymers having low glass transition temperatures.
  • the polymers are synthesized from difunctionai iodinated oligomers that themselves typically have glass transition temperatures of less than -30°C.
  • difunctionai is meant that, on average, both ends of each oligomer chain have a reactive (i.e.
  • a difunctionai iodinated (i.e. diiodinated) fluoro-oligomer is reacted with a vinyl silane of formula IV.
  • CH 2 CY-(CH 2 )n-SiRR , R"
  • Y is a hydrogen atom or a C1-C3 alkyl group
  • R is a methoxy or ethoxy group
  • R' and R" are independently selected from the group consisting of methyl groups, methoxy groups and ethoxy groups
  • the molar ratio of said diiodinated oligomer to said vinyl silane is 1 to at least 2.5, preferably 5-15, more preferably 7.5-10.
  • the resultant iodinated silicon-containing polymeric adduct is then reacted with an acid to form a crosslinked fluorinated polymer.
  • a difunctional iodinated oligomer i.e.
  • a diiodinated oligomer is contacted with a vinyl silane of formula IV above to form an iodinated silicon- containing polymeric adduct.
  • the iodinated adduct is contacted with a reducing agent to form a non-iodinated silicon-containing polymeric adduct which is subsequently reacted with an acid to form a crosslinked fluorinated polymer.
  • the difunctional diiodinated oligomers (which may also be referred to as telechelic difunctional diiodinated oligomers) that may be utilized in the process of the invention have a number average molecular weight of 1000 to 25,000 g/mole and an iodine group at each end of the oligomer chain.
  • the oligomer chain consists essentially of a) 40 to 90 (preferably 50 to 85, most preferably 60 to 75) mole percent copolymerized units of a first comonomer selected from the group consisting of vinylidene fluoride (VF 2 ); and tetrafluoroethylene (TFE); b) 10 to 60, preferably 15 to 50, most preferably 25 to 40, mole percent copolymerized units of a second fluorinated comonomer that is a perfluoro(alkyl vinyl ether), i.e.
  • R f OCF CF 2 , where R f is a perfluoroalkylene group of 1-5 carbon atoms; c) 0 to 10 mole percent copolymerized units of a fluorinated comonomer selected from the group consisting of hexafluoropropylene (HFP) and tetrafluoroethylene (TFE), with the proviso that c) can only be
  • HFP hexafluoropropylene
  • TFE tetrafluoroethylene
  • tetrafluoroethylene when a) is vinylidene fluoride and c) can only be hexafluoropropylene when a) is tetrafluoroethylene; d) 0 to 10 mole percent copolymerized units of a perfluoro vinyl ether of the formula CF 2 CFO(R f -0) n (R f 0) m R f , where R f and R r are different linear or branched perfluoroalkylene groups of 2-6 carbon atoms, m and n are independently 0-10, and R j is a perfluoroalkyl group of 1-6 carbon atoms; and e) 0 to 10 mole percent copolymerized units of a functional fluorovinyl ether selected from the group consisting of i) propanoic acid, 3-[1- [difluoroKI ⁇ -trifluoroetheny oxyjmethylJ-l ⁇ -tetra
  • the perfluoro (vinyl ether) of d) will be different, i.e. chemically distinct, from the second monomer, by which is meant that the molecular weights of the two perfluoro(vinyl) ethers will be different.
  • a preferred class of perfluoro (vinyl ether) that may be employed as the second comonomer or the optional additional perfluoro(vinyl ether) comonomer includes compositions of the formula where X is F or CF3, n is 0-5, and Rf is a perfluoroalkyl group of 1-6 carbon atoms.
  • the second monomer is a member of the above class of perfluoroalkyl(vinyl ethers) and includes those ethers wherein n is 0 and R f contains 1-3 carbon atoms.
  • perfluorinated ethers are perfluoro(methyl vinyl ether) (PMVE), perfluoro(ethyl vinyl ether) and perfluoro(propyl vinyl ether) (PPVE).
  • Such comonomers may also be utilized as the optional perfluoro(ethyl vinyl) ether comonomer of d).
  • the second monomer may be perfluoro(methyl vinyl) ether and the optional additional perfluoro(vinyl ether) may be perfluoro(propyl vinyl) " ether.
  • oligomers range from viscous oils to solids (for example, in some instances, the solids are gums) at room temperature and have a number average molecular weight of 1000 to 25,000; preferably 1200 to 12,000; most preferably 1500 to 5000. In addition, the oligomers have a narrow molecular weight distribution, i.e. les than 1.5, preferably less than 1.2.
  • the oligomers may be synthesized by a solution, suspension or emulsion polymerization process. Such processes are well known in the art.
  • an emulsion process is employed wherein an inorganic peroxide (e.g. sodium or ammonium persulfate) is the initiator.
  • an inorganic peroxide e.g. sodium or ammonium persulfate
  • a surfactant particularly a fluorosurfactant, may be included in order to improve the stability of the emulsion.
  • the polymerization reaction is conducted in the presence of a chain transfer agent of the formula l-Rf-l, wherein Rf is a perfluoroalkylene or an oxygen atom-containing perfluoroalkylene group containing between 3 and 12 carbon atoms.
  • the preferred chain transfer agents are 1 ,2- diiodoperfluoroethane, 1 ,4-diiodoperfluorobutane and 1,6- diiodoperfluorohexane and may be a mixture of diiodoperfluoroalkanes.
  • the chain transfer agent is typically introduced to the reactor prior to initiation of the polymerization reaction and is present at a sufficient level so as to result in production of oligomers having an iodine atom endgroup at each end of the oligomer chains.
  • oligomers having an iodine atom endgroup at each end of the oligomer chains typically, about 4-12 mol%, preferably 5-10 mol%, based on the total molar amounts of monomer, of chain transfer agent is utilized.
  • NMR spectroscopy may be used to confirm that, on average, two iodine atoms are present on each polymer chain.
  • iodinated oligomers that may be used in the process of the invention include, but are not limited to l-(VF2-co-PMVE)-l; l-CH2CH2-(VF2-co-PMVE)-CH 2 CH 2 -l; l-(TFE-co-PMVE)-!; I-CH2CH 2 - (TFE-co-PMVE)-CH 2 CH 2 -l; l-(TFE-co-PMVE-co-HFP)-l; l-CH 2 CH 2 -(TFE- co-PMVE-co-HFP)-CH 2 CH 2 -l; l-(TFE-co-PMVE-co-VF 2 )-l; and l-CH 2 CH 2 - (TFE-co-PMVE-co-VF 2 )-CH 2 CH 2 -l.
  • the designation "-co-" indicates that the monomers listed are copolymerized units that form part of the polymer backbone chain. The copolymerized units are distributed
  • the telechelic difunctional iodinated oligomers are contacted with a vinyl alkoxysilane of the formula
  • CH 2 CY-(CH 2 ) n -SiRR'R"
  • Y is a hydrogen atom or a Ci-C 3 alkyl group
  • R is a methoxy or ethoxy group
  • R' and R" are independently selected from the group consisting of d-C 6 alkyl and alkoxy groups.
  • Preferred species include methyl groups, methoxy groups and ethoxy groups.
  • the molar ratio of telechelic diiodinated oligomer to the vinyl silane is 1 to at least 2.5. The diiodinated oligomers and the silanes react to form an iodinated silicon- containing polymeric adduct.
  • Vinyl alkoxysilanes may be prepared by catalyzed hydrosilylation reactions of alkoxysilanes and acetylene. Another approach involves reaction of vinylchlorosilane with an alcohol. Methods of preparation are described in U.S. Patents 2,637,738; 4,579,965; 5,041 ,595 and European Patent 477894. Vinyl alkoxysilanes are also commercially available, for example from Sigma-Aldrich Co. and Gelest Inc.
  • these compounds are well known in the art and include, but are not limited to vinyl triethoxy silane, vinyl dimethylmethoxy silane, vinyl dimethylethoxy silane, vinyl methyl dimethoxy silane, vinyl methyldiethoxy silane, vinyl ethyl diethoxysilane and vinyl trimethoxysilane.
  • the silane is vinyl triethoxysi!ane or vinyl trimethoxysilane because the compounds readily react with the difunctional iodinated oligomers (i.e. telechelic diiodinated oligomers) to form adducts that may be further converted to three dimensional polymer networks.
  • the reaction of the difunctional iodinated oligomers and the vinyl silane is typically carried out at a temperature of 40°C to 180°C, preferably 50°C to 140°C, in a solvent.
  • Suitable solvents include, but are not limited to acetonitrile, tetrahydrofuran, butyronitrile, ethyl acetate, methyl ethyl ketone and dioxane.
  • a free radical initiator is present in the reaction mixture.
  • Suitable radical generating compounds include t- butyperoxypivalate, t-amylperoxypivalate, di-t-butylperoxide,
  • the vinyl alkoxysilane should be present in an amount of at least 1.5 equivalents per equivalent of iodine in the diiodinated (i.e. difunctional or telechelic) oligomer reactant.
  • the amount of vinyl alkoxysilane will be present in an amount of from 2.0 to 5.0 equivalents per equivalent of iodine in the iodinated difunctional oligomer reactant.
  • the reaction is preferably conducted in an inert atmosphere to reduce the inhibition period caused by the presence of oxygen, which is a radical scavenger
  • the reaction product obtained is a polymeric silicon-containing adduct that is a telechelic DD-diiodinated silylated fluorooligomer having alkoxysilane endgroups. That is, the reaction product is a difunctional, diiodinated, silylated fluorooligomer.
  • the polymeric silicon- containing adduct is utilized without further treatment as a starting material to form a crosslinked fluorinated polymer. That is, the silicon-containing adduct is hydrolyzed in an acid catalyzed reaction which results in hydrolysis of the alkoxysilane endgroups present in the adduct with formation of SiOH endgroups. These endgroups then react to form a high molecular weight network structure.
  • the network is formed by a chemical crosslinking reaction wherein covalent bonds (i.e. the crosslinks) are formed by reaction of the polymeric adduct molecules with simultaneous elimination of alcohols.
  • the crosslinks contain Si-O-Si groups.
  • the product of the hydrolysis reaction is a fluorosilicon polymer that has elastomeric properties and excellent low temperature properties that are due to the T g , i.e. below -35°C, of the product.
  • the acid catalyzed reaction may carried out at temperatures of from ambient temperature to about 120°C, generally from ambient temperature to 60°C, and may take place in an organic solvent.
  • Suitable solvents include tetrahydrofuran, methyl ethyl ketone, dioxane, butyronitrile, ethyl acetate, dimethylformamide, and dimethyl acetamide.
  • Acids that are suitable for use as catalysts include, but are not limited to methanesuifonic acid, triflic acid, paratoluenesulfonic acid, hydrochloric acid, nitric acid and sulfuric acid.
  • the concentration of the acid in the solvent generally ranges from 10 "7 to 10 ⁇ 1 moles per liter, preferably 10 "6 to 5x10 "3 moles per liter.
  • the morphology of the crosslinked network produced by the acid catalyzed crosslinking reaction will vary depending on the particular vinyl alkoxysilane utilized. For example, if a tri-substituted vinyl alkoxysilane, such as vinyl triethoxysilane, is used as a reactant to form the telechelic silylated oligomer, the network will be more highly crosslinked than if vinyl methyldimethoxysilane is utilized as a reactant to form the silylated oligomer.
  • the particular vinyl alkoxysilane selected will depend on the particular physical properties desired in the crosslinked polymer product.
  • silicon compounds and polymers such as tetraethoxysilane,
  • tetraethyoxydimethylsilane tetramethyldisiloxane, hexamethyldisiloxane, tetramethyldiethoxysilane or poly(dimethylsiloxane) may be added.
  • the silicon- containing polymeric adduct is contacted with a reducing agent to form a non-iodinated silicon-containing polymeric adduct which is utilized as the starting material to form the crosslinked fluoropolymer product.
  • reducing agents such as tributyl tin hydride, zinc in non- protonic solvents, lithium aluminum hydride, sodium borohydride, sodium amalgams, diborane, and hydrogen over various catalysts may be utilized.
  • the non-iodinated silicon-containing adduct may be readily prepared by contacting the iodinated silicon-contacting adduct with the selected reducing agent, such as tin hydride, in a solvent such as acetonitrile at elevated temperature, e.g. 50°C-100°C, in the presence of a free radical generator such as azobisisobutyronitrile.
  • the selected reducing agent such as tin hydride
  • a solvent such as acetonitrile
  • a free radical generator such as azobisisobutyronitrile
  • the solvent-containing reaction mixture of diiodinated difunctional oligomers (also referred to as telechelic diiodinated oligomers) and vinyl silane may be used to form crosslinked polymeric films by casting. That is, the oligomers and vinyl silane will react to form a polymeric adduct. A film of the adduct is cast and hydrolysis occurs by exposure of the polymeric adduct in the film to the acid catalyst or traces of acid in the air contacting the film. Alternatively, excess vinyl alkoxysilane and solvent may be removed by evaporation to yield the fluorosilicon polymer product. The product may be dried at room temperature or in an oven, generally at a temperature of up to 70°C - 120°C.
  • the drying step takes place in an oven under an inert atmosphere.
  • Fluorosilicon elastomers prepared according to the process of the invention can be used to prepare articles such as flexible tubes, hose, o- rings, gaskets and other rubber articles, especially for applications that where exposure to extreme conditions is encountered, for example at temperatures below -20°C.
  • the polymers are particularly useful to form items for automotive and aerospace applications, such as seals, o-rings, gaskets, and diaphragms.
  • Number average molecular weight (Mn) was determined by size exclusion chromatography (SEC). Samples were dissolved in
  • DSC measurements were conducted using a Perkin Elmer Pyris 1 instrument. Each sample (approximately 10 mg) was initially cooled to a temperature of-105°C for 10 minutes, then heated from -100°to 50°C at a heating rate of 20°C/minute. The sample was then cooled to -105° and the cycle was repeated. Values reported were obtained after a second heating. The values of T g reported correspond to the inflection point in the DSC curve. Decomposition temperature (Td) was determined by thermal gravimetric analysis (TGA). TGA was performed with a Texas Instrument ATG 51-133 apparatus in air at the heating rate of either 10° or
  • TGA 20°C/minute from room temperature up to a maximum 550°C.
  • Deoxygenated water 400 ml_
  • sodium persulfate (1.84 g)
  • 1 ,4- diiodoperfluorobutane 35.75 g
  • the reactor was sealed, cooled to -40°C and evacuated.
  • the following monomers were then transferred to the reactor: perfiuoro(methyl vinyl ether) (PMVE, 83 g) and vinylidene fluoride (VF 2 , 48 g).
  • the reactor was again sealed and the reaction mixture was slowly heated to 80°C over a period of approximately one hour. The reaction was allowed to proceed at a temperature of 80°C for 8 hrs.
  • lodinated Oligomer A was determined to be 71.8/28.2 (mol%) VF 2 /PMVE by 19 F-NMR in acetone-d6.
  • the glass transition temperature of this oligomer was determined to be - 58°C by DSC, and the Mn was determined to be approximately 2,490 g/mol
  • lodinated Oligomer A was reacted with triethoxyvinylsilane as follows, lodinated Oligomer A (10g; 0.004 mole), triethoxyvinylsilane (1.90 g; 0.01 mole) and tert-butylperoxy pivalate (0.2 g; 0.0012 mole) were dissolved in an amount of acetonitrile approximately four times the weight of the iodinated oligomer in a 200 ml. round bottom flask. The acetonitrile had been previously dried over sodium sulfate. The solution was purged with argon for 5 minutes to remove residual oxygen. The temperature of the reaction mixture was raised to 74+3°C while agitating the reaction mixture.
  • Silicon-containing Polymeric Adduct 1 (2.0g, 8 x 10 "4 mole), methanesulfonic acid (0.015g; 1.6 x 10 "4 s) and tetrahydrofuran (0.585 g) were agitated until a solution was formed. A thin film was cast from the solution. The film was held at ambient temperature for several hours during which time tetrahydrofuran evaporated and crosslinking occurred. The crosslinked fluoropolymer film had T g of -30°C and T 10 of 290°C.
  • Example 2
  • Silicon-containing Polymeric Adduct 1 (2.0 g; 8 x 10 "4 mole), hydrochloric acid (0.2g; 1 x 10 "4 mole), tetraethoxysilane (0.2g; 1 x 10 "4 mole), and tetrahydrofuran (1.0 g) were agitated until a solution was formed. A 2 to 3 mm thick film was cast from the solution. The film was held at ambient temperature for several hours during which time tetrahydrofuran evaporated and crosslinking occurred. The crosslinked f luoropolymer film had T g of -15°C and Ti 0 of 300°C.
  • lodinated Oligomer A was reacted with diethoxyvinylmethylsilane generally according to the procedure described above for preparation of
  • Silicon-containing Polymeric Adduct 1 The reactants were as follows: lodinated Oligomer A (10g; 0.004 mole), diethoxyvinylmethylsilane (1.6 g;
  • Silicon-containing Polymeric Adduct 2 (2.0g, 8 x 10 " mole), methanesulfonic acid (0.015g; 1.6 x 10 "4 mole) and methyl ethyl ketone (0.585 g) were agitated until a solution was formed to form Casting Mixture 3.
  • a thin film was immediately cast from this casting mixture. The film was held at ambient temperature for several hours during which time methyl ethyl ketone evaporated and crosslinking occurred.
  • the crosslinked film had T g of -28°C and T 10 of 310°C.
  • Swelling rates in n- octane at room temperature for 24hrs (1 %); in n-octane at 60 °C for 24 hrs (2 %). Loss of 2.5 wt % at 200 °C after 60 °C under air.
  • Casting Mixture 3 of Example 3 was agitated at 60°C for 60 minutes. A 2-3 mm thick film was then cast from the resultant mixture. The film was held at ambient temperature for several hours during which time methyl ethyl ketone evaporated and crosslinking occurred.
  • the crosslinked film had T g of -28°C and T 10 of 310°C which were unchanged from the comparable physical property values of the crosslinked film of Example 3. Swelling rates in n-octane of the crosslinked film was 0% after 24 hours at room temperature and 0% after 24 hours at 60°C.
  • Silicon-containing Polymeric Adduct 2 (2.0g, 8 x 1 ⁇ " 4 mole), methanesulfonic acid (0.0 5g; 1.6 x 10 "4 mole) and fumed silica (1.5 g) were mixed to form Casting Mixture 5.
  • a thin film was immediately cast from this casting mixture. The film was held at ambient temperature for several hours.
  • the crosslinked film had T g of-25°C and T 0 of 307°C. Swelling rates in n-octane of the crosslinked film were 1 % after 24 hours at room temperature and 2 % after 24 hours at 60°C.
  • Silicon-containing Polymeric Adduct 2 (2.0g, 8 x 10 " mole), methanesulfonic acid (0.015g; 1.6 x 10 "4 mole), tetraisopropyl titanate (0.023 g; 8 x 10 ⁇ 5 mole) and methyl ethyl ketone (0.585 g) were agitated until dissolved at ambient temperature to form Casting Mixture 6.
  • a thin film was immediately cast from this casting mixture. The film was held at ambient temperature for several hours.
  • the crosslinked film had T g of - 27°C and Ti 0 of 310°C. Swelling rates in n-octane were 1% after 24 hours at room temperature and 2% after 24 hours at 60°C.
  • Silicon-containing Polymeric Adduct 2 (2.0g, 8 x 10 "4 mole), methanesulfonic acid (0.015g; 1.6 x 10 "4 mole), tetraisopropyl titanate (0.023 g; 8 x 0 "5 mole) and methyl ethyl ketone (0.585 g) were agitated until completely mixed at 60°C to form Casting Mixture 7.
  • a 2-3 mm thick film was immediately cast from this casting mixture. The film was held at ambient temperature for several hours.
  • the crosslinked film had T g of - 30°C and a T 10 of 300°C. Swelling rates were 8% in ethanol after 24 hours at room temperature and 91% in acetone after 24 hours at room temperature.
  • Silicon-containing Polymeric Adduct 2 (2.0g, 8 x 0 " " mole),
  • Silicon-containing Polymeric Adduct 2 (2.0g, 8 x 10 "4 mole), polydimethylsilane having a degree of polymerization of 100 (0.32g; 4 x 10 ⁇ 5 mole), triphenylboron (200 mg) and fumed silica (0.03 g) were agitated until completely mixed at ambient temperature to form Casting Mixture 9.
  • a thin film was immediately cast from this casting mixture. The film was held at ambient temperature for several hours The crosslinked film had T g of -40 and a Tio of 310°C. Swelling rates in n-octane were 0% after 24 hours at room temperature and 1% after 24 hours at 60°C.
  • lodinated Oligomer A was reacted with ethoxyvinyldimethylsilane generally according to the procedure described above for preparation of Siligon-containing Polymeric Adduct 1.
  • the reactants were as follows: lodinated Oligomer A (10g; 0.004 mole), ethoxyvinyldimethylsilane (1.6 g; 0.01 mole) and tert-butylperoxy pivalate (0.2 g; 0.0012 mole).
  • Silicon-containing Polymeric Adduct 2 (1.0g, 4 x 10 ⁇ mole), Silicon- containing Polymeric Adduct 3 (1.0g, 4 x 10 "4 mole) methanesulfonic acid (0.015g; 1.6 x 10 "4 mole) and methyl ethyl ketone (0.585 g) were agitated for 60 minutes at 60°C to form Casting Mixture 10.
  • a thin film was immediately cast from the casting mixture. The film was held at ambient temperature for several hours during which time methyl ethyl ketone evaporated and crosslinking occurred.
  • the crosslinked film had T g of - 29°C and T 10 of 300°C.
  • Silicon-containing Polymeric Adduct 2 (1.6g, 6.4 x 10 "4 mole),
  • Silicon-containing Polymeric Adduct 2 (0.4g, 1.6 x 10 "4 mole), Silicon- containing Polymeric Adduct 3 (1.6g, 6.4 x 10 ⁇ mole), methanesulfonic acid (0.015g; 1.6 x 10 " mole) and methyl ethyl ketone (0.585 g) were agitated for 60 minutes at 60°C to form Casting Mixture 12.
  • a thin film was immediately cast from the casting mixture. The film was held at ambient temperature for several hours during which time methyl ethyl ketone evaporated and crosslinking occurred.
  • the crosslinked film had T g of -31 °C and T i0 of 300°C.
  • Silicon-containing Polymeric Adduct 2 (1.0g, 4 x 10 " mole), Silicon- containing Polymeric Adduct 3 (1.0g, 4 x 10" mole) and methanesulfonic acid (0.015g; 1.6 x 10 "4 moles) were agitated to form Casting Mixture 13.
  • a thin film was immediately cast from the casting mixture.
  • the crosslinked film had T g of -35°C and Ti 0 of 305°C. Swelling rates in n-octane of the crosslinked film were 1 % after 24 hours at room temperature and 3 % after 24 hours at 60°C.
  • Silicon-containing Polymeric Adduct 2 (1.6g, 6.4 x 10 "4 mole), Silicon- containing Polymeric Adduct 3 (0.4g, 1.6 x 10 "4 mole) and methanesulfonic acid (0.015g; 1.6 x 10 " mole) were agitated to form Casting Mixture 14.
  • a thin film was immediately cast from the casting mixture.
  • the crosslinked film had T g of -21 "C and T 10 of 305°C. Swelling rates in n-octane of the crosslinked film were 0 % after 24 hours at room temperature and 2 % after 24 hours at 60°C. Loss of 11 wt % after 2 hrs at 200 °C under air.
  • Example 15 Example 15
  • Silicon-containing Polymeric Adduct 2 (0.4g, 1.6 x 10 "4 mole), Silicon- containing Polymeric Adduct 3 (1.6g, 6.4 x 10 "4 mole) and methanesulfonic acid (0.015g; 1.6 x 10 "4 mole) were agitated to form Casting Mixture 15.
  • a thin film was immediately cast from the casting mixture.
  • the crosslinked film had T g of -31 °C and T 10 of 305°C.
  • Silicon-containing Polymeric Adduct 2 (1.2g, 4.8 x 10 "4 mole), Silicon-containing Polymeric Adduct 3 (0.8 g, 3.2 x 10 "4 mole) and
  • Silicon-containing Polymeric Adduct 2 (1.32g, 5.28 x 10 " mole), Silicon-containing Polymeric Adduct 3 (0.72 g, 2.88 x 10 "4 mole) and
  • methanesulfonic acid (0.015g; 1.6 x 10"* mole) were agitated to form Casting Mixture 17.
  • a thin film was immediately cast from the casting mixture.
  • the crosslinked film had T g of -28°C and Ti 0 of 310°C. Swelling rates in n-octane were 0 % after 24 hours at room temperature and 2 % after 24 hours at 60°C).

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Abstract

L'invention porte sur des polymères de fluorosilicone qui sont préparés par un procédé consistant à faire réagir a) des oligomères iodés ayant des unités copolymérisées de perfluoro(méthyl vinyl éther) et de fluorure de vinylidène ou de tétrafluoroéthylène qui contiennent 40-90 pour cent en moles d'unités copolymérisées de fluorure de vinylidène ou de tétrafluoroéthylène et 10-60 pour cent en moles d'unités copolymérisées de perfluoro(méthyl vinyl éther), lesdits oligomères ayant deux groupes terminaux fonctionnels et ayant une masse moléculaire moyenne en nombre entre 1000 et 25 000 avec b) un méthoxyvinyl silane ou un éthoxyvinyl silane pour former un produit d'addition polymère contenant du silicium qui est encore mis à réagir avec un acide pour former un polymère fluoré réticulé.
PCT/US2010/053319 2009-12-08 2010-10-20 Procédé de préparation d'un polymère de fluorosilicone WO2011071599A2 (fr)

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EP10836370.6A EP2510045A4 (fr) 2009-12-08 2010-10-20 Procédé de préparation d'un polymère de fluorosilicone
KR1020127017616A KR20120129883A (ko) 2009-12-08 2010-10-20 플루오로규소 중합체의 제조 방법
CN201080055743.9A CN102782015B (zh) 2009-12-08 2010-10-20 用于制备氟硅聚合物的方法
JP2012543099A JP5635124B2 (ja) 2009-12-08 2010-10-20 フルオロシリコンポリマーの調製方法

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WO2021094884A1 (fr) * 2019-11-13 2021-05-20 3M Innovative Properties Company Procédé de fonctionnalisation de polymères fluorés, polymère fluoré fonctionnalisé et compositions de revêtement à base de ceux-ci

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WO2021094884A1 (fr) * 2019-11-13 2021-05-20 3M Innovative Properties Company Procédé de fonctionnalisation de polymères fluorés, polymère fluoré fonctionnalisé et compositions de revêtement à base de ceux-ci

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