WO2001034670A1 - Fluoropolymeres contenant des organo-silanes et procedes de fabrication de ceux-ci - Google Patents

Fluoropolymeres contenant des organo-silanes et procedes de fabrication de ceux-ci Download PDF

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WO2001034670A1
WO2001034670A1 PCT/US2000/031040 US0031040W WO0134670A1 WO 2001034670 A1 WO2001034670 A1 WO 2001034670A1 US 0031040 W US0031040 W US 0031040W WO 0134670 A1 WO0134670 A1 WO 0134670A1
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fluoropolymer
monomer
polymerization
silane
alkenyl
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PCT/US2000/031040
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English (en)
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WO2001034670A8 (fr
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Ramin Amin-Sanayei
Claude Christophe Granel
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Atofina Chemicals, Inc.
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Priority to JP2001537381A priority Critical patent/JP2003514085A/ja
Priority to US09/869,454 priority patent/US6710123B1/en
Priority to MXPA01007110A priority patent/MXPA01007110A/es
Priority to EP00978536A priority patent/EP1196465A4/fr
Publication of WO2001034670A1 publication Critical patent/WO2001034670A1/fr
Publication of WO2001034670A8 publication Critical patent/WO2001034670A8/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
    • C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
    • C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
    • C08F230/085—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon the monomer being a polymerisable silane, e.g. (meth)acryloyloxy trialkoxy silanes or vinyl trialkoxysilanes

Definitions

  • the present invention relates to fluoropolymers and uses for these fluoropolymers.
  • the present invention relates to fluoropolymers containing organo-silane functional groups.
  • the present invention further relates to methods of making the fluoropolymers.
  • fluorine-containing polymers are traditionally used for applications which require special properties such as low surface energy, high resistance to chemical attack, low dielectric loss, or extreme requirements on aging resistance.
  • these unusual properties are problems themselves in the use of fluoropolymers.
  • the lack of functional groups to promote: adhesion to substrates, to facilitate cross-linking, to provide sites for subsequent chemical modification, to introduce ion-exchange capacity or ionic conductivity severely limits the application of ordinary fluoropolymers.
  • fluorinated polymers with modified properties, such as reactive functional groups which can be modified are constantly being sought.
  • fluorine- containing polymers having an intact organo-silane moiety which can be reactive has yet to be made in aqueous media.
  • Buning et al. [Chemical Abstract Number 72:101262 and Die Ang. Mak. Chemie 13 (1970) pp. 89-96] describes, based on the English abstract, the co- polymerization of vinyl (tri-tert-butoxy) silane in emulsion or suspension with vinyl chloride or styrene in the presence of dilauroyl peroxide or Bz 2 O 2 to result in uncross-linked copolymers.
  • the abstract further reports that when vinyl (trimethoxy)-silane was used instead of vinyl (tri-tert-butoxy) silane, an insoluble, crosslinked copolymer was obtained containing poly(vinyl chloride).
  • 0 736 583 primarily relates to aqueous dispersions of a fluorine-containing polymer which are formed by post-mixing organo-silicon compounds in the fluorine-containing polymer-dispersed aqueous composition.
  • a co- polymerization involving an organosilane is discussed, but used as an intermediate product.
  • the organo-silicon compounds are mixed with the fluoropolymer dispersion after the polymerization to form the fluoropolymer dispersion.
  • U.S. Patent No. 5,621 ,038 to Chen et al. relates to curable compositions containing a water dispersible curable polymer containing a sterically hindered alkoxylated silane group, a water dispersible or water soluble, hydrolytically stable organometallic catalyst, and water.
  • Chen et al. states that these compositions are useful as adhesives, sealants, and paints.
  • Chen et al. further reports that the compositions have improved properties including solvent resistance, adhesion, hardness, abrasion resistance, and mar resistance.
  • Chen et al. does not mention the use of fluoropolymers and requires the presence of a hydrolytically stable organometallic catalyst.
  • a feature of the present invention is to provide fluoropolymers which are cross- linkable and/or can be chemically modified without substantially affecting the beneficial properties typically associated with fluoropolymers such as chemical resistance, high temperature stability, high tensile strength, and/or low refractive indices.
  • Another feature of the present invention is to provide fluoropolymers which are capable of being chemically bonded to a variety of substrates.
  • Another feature of the present invention is to provide fluoropolymers which can be functionalized. Another feature of the present invention is to provide methods of making these types of fluoropolymers.
  • the present invention relates to a fluoropolymer comprising a polymer reaction product of a) at least one first alkylene co- monomer containing at least one fluorine atom; b) optionally at least one monomer selected from 1 ) at least one second alkylene containing at least one fluorine atom; 2) at least one alkyl alkenyl ether containing at least one fluorine atom; 3) at least one aliphatic or cyclic ketone containing at least one fluorinated alpha-alpha position; or 4) non-fluorinated alkene, alkyl alkenyl ether, or alkenyl ester; and c) at least one sterically hindered alkenyl or alkenyl ether organo-silane co-monomer with or without at least one fluorine substituent.
  • the present invention further relates to the fluoropolymer described above which can be cross-linked and/or can contain one or more functional groups.
  • the present invention also relates to a process for the production of the polymers described above by free radical polymerization techniques known in the art, such as suspension polymerization, emulsion polymerization, interfacial polymerization, solution polymerization, or non-aqueous polymerization systems, wherein one or more of liquid or super-critical carbon dioxide, liquid or super-critical SF6, liquid or super-critical fluorinated or perfluorinated hydrocarbon(s) with 1 to about 6 carbons can be used as polymerization media.
  • free radical polymerization techniques known in the art, such as suspension polymerization, emulsion polymerization, interfacial polymerization, solution polymerization, or non-aqueous polymerization systems, wherein one or more of liquid or super-critical carbon dioxide, liquid or super-critical SF6, liquid or super-critical fluorinated or perfluorinated hydrocarbon(s) with 1 to about 6 carbons can be used as polymerization media.
  • the present invention further relates to a method of making the above-described fluoropolymers and involves conducting a polymerization of the co-monomers described above for a sufficient time and at a sufficient pressure and temperature to form the fluoropolymer.
  • the polymerization is a free radical polymerization, and more preferably is an emulsion polymerization.
  • the present invention relates to the use of the fluoropolymers in a variety of applications, including, but not limited to, foamed cross-linked fluoropolymers, fluoro- elastomers, adhesives, coatings and the like.
  • the fluoropolymers of the present invention can also be used as a membrane component as well as other applications.
  • the present invention relates to fluoropolymers containing one or more organo- silane functionalities or functional groups.
  • the organo-silane functionality or moiety is at least one sterically hindered group.
  • the sterically hindered group on the organo- silane moiety preferably prevents premature hydrolysis/condensation of the co-polymerized silane groups.
  • the fluoropolymer preferably is a polymer reaction product of: a) at least one first alkylene co-monomer containing at least one fluorine atom; b) optionally at least one co- monomer selected from 1) at least one second alkylene containing at least one fluorine atom which is different from the first alkylene co-monomer if present; 2) at least one alkyl alkenyl ether containing at least one fluorine atom; 3) at least one aliphatic or cyclic ketone containing at least one fluorinated alpha-alpha position; or 4) non-fluorinated alkene, alkyl alkenyl ether, or alkenyl ester; and c) at least one sterically hindered alkenyl or alkenyl ether organo-silane co-monomer with or without at least one fluorine substituent.
  • the alkylene co-monomer containing at least one fluorine atom can be present in any amount depending on the desired properties of the fluoropolymer.
  • at least one alkylene co-monomer is present in an amount of from about 50 mol% to about 99.9 mol%, and more preferably from about 80 mol% to about 99.9 mol%, and most preferably from about 90 mol% to about 95.5 mol%.
  • the alkylene co-monomer is an ethylene co-monomer and further preferably contains from about 1 to about 4 fluorine atoms.
  • fluorinated ethylenes include, but are not limited to, vinylidene fluoride (VF,), tetrafluoroethylene (TFE), trifluoroethylene, chlorotrifluoroethylene (CTFE) and vinyl fluoride. These fluorinated ethylenes may be used both individually and in combination with one another. These co-monomers are commercially available from such sources as ATOFINA Chemicals and DuPont. Most preferably, the ethylene co-monomer containing at least one fluorine atom is VF2, CTFE, and TFE. Mol.% as used herein refers to the percentage of the total monomers present.
  • this co- monomer when present, can be present in any amount and is preferably present in an amount of from about 0.1 mol% to about 50 mol%, and more preferably from about 0.1 mol% to about 40 mol%, and most preferably from about 0.1 moI% to about 30 mol%.
  • the second co-monomer is propenes containing from about 1 to about 6 fluorine atoms; alkyl vinyl ethers containing at least one fluorine atom; aliphatic or cyclic C 3 -C 6 ketones containing fluoronated alpha-alpha positions; or non-fluorinated C 2 -C 4 alkenes, alkyl vinyl ethers, or vinyl esters.
  • alkylene containing at least one fluorine atom examples include, but are not limited to, hexafluoropropylene (HFP), perfluoroisobutylene, and the like.
  • alkyl alkenyl ether containing at least one fluorine atom examples include, but are not limited to, perfluorovinylmethylether (PVME).
  • Additional examples include, linear or branched C 3 _ g alkenes containing at least one fluorine atom, hexafluoropropene, 2- hydropentafluoropropene, 3,3,3-trifluoropropene, mono- or polyfluorinated butanes, such as hexafluoroisobutylene, pentanes, hexenes, or octanes.
  • these co-monomers may also contain chlorine atoms.
  • These types of co-monomers are preferably C 3 _ 6 alkenes containing at least one fluorine atom and, more preferably C 3 4 alkenes containing at least one fluorine atom.
  • optional co-monomers include alkyl vinyl ethers containing at least one fluorine atom, for example, perfluoropropyl perfluorovinyl ether, perfluoromethyl perfluorovinyl ether, perfluoropropyl vinyl ether, n-butyl perfluorovinyl ether, and the like.
  • Additional co- monomers include non-fluorinated C 2 4 alkenes, such as ethylene, propene, 1 -butene, isobutylene, C 3 6 alkyl vinyl ethers, such as methyl vinyl ether, ethyl vinyl ether and the like, and C 4 6 vinyl esters, such as vinyl acetate, vinyl propionate, and others.
  • C 2 4 alkenes such as ethylene, propene, 1 -butene, isobutylene
  • C 3 6 alkyl vinyl ethers such as methyl vinyl ether, ethyl vinyl ether and the like
  • C 4 6 vinyl esters such as vinyl acetate, vinyl propionate, and others.
  • the alkenyl or alkenyl ether organo-silane co- monomer with or without at least one fluorine substituent is sterically hindered.
  • the sterically hindered organo-silane co-monomer prevents or substantially prevents premature hydrolysis/condensation of the co-polymerized groups which form the fluoropolymer.
  • the sterically hindered groups on the fluoropolymer of the present invention are such that there spatial arrangement prevents or retards a reaction with another molecule.
  • the sterically hindered organo-silane co-monomer can be present in any amount for purposes of the present invention.
  • the sterically hindered organo-silane co-monomer is present in an amount of from 0.1 mol% to about 50 mol%, more preferably from about 0.1 mol% to about 20 mol%, and most preferably from about 0.1 mol% to about 10 mol%.
  • the sterically hindered organo-silane co-monomer has the formula:
  • n is an integer of from 0 to 2, or has the formula:
  • m is an integer of from about 2 to about 10, k is 0 or 1 ; and R represents at least one C 3 or higher branched alkyl, cycloalkyl, or heterocyclic group with or without at least one fluorine substituent; R represents at least one alkenyl or allyl containing group; R represents at least one n- alkyl, at least one C 3 or higher branched alkyl, at least one C 3 or higher cycloalkyl, or heterocyclic (e.g., aromatic) group.
  • R represents at least one C " 3 --CC 6 branched alkyl or cycloalkyl group; R represents at least one vinyl, allyl, or vinyl ether containing group with or without at least one fluorine substituent; and/or R represents at least one C,-C 6 n-alkyl, C 3 -C 6 branched alkyl, C.-C 6 cycloalkyl, or C 6 -C 9 aryl.
  • n is preferably 0, m is preferably an integer of 2 to 5.
  • branched alkyl or cycloalkyl group include, but are not limited to, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, bicycloheptyl, iso-octyl, 3- methyl pentyl, iso-amyl, amyl, pentyl, iso-pentyl, 2,5-dimethythexyl, 4-methyI -2-pentyl, iso- propyl, sec-butyl, iso-butyl, t-butyl, iso-pentyl, and sec-pentyl, and the like.
  • n-alkyl, the branched alkyl, and the heterocyclic groups include, but are not limited to, n- butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, and the like.
  • Substituents to the R group may include a replacement for a carbon atom with atoms such as oxygen, nitrogen, or sulfur, with the proviso that the carbon atom adjacent to the silicon is not replaced.
  • Other substituents include replacement of the hydrogen atom attached to carbon with halogen atoms, nitrogen, sulfur, oxygen, and organofunctional groups, such as cyano, urea, esters, amides, oxo, and the like.
  • the alkenyl organo-silane co-monomers used in the present invention can further contain at least one functional group.
  • this functional group or groups are preferably present as part of the R group.
  • the functional group can be any group which still permits the formation of the fluoropolymer of the present invention and preferably provides the desired properties of the fluoropolymers or provides reactive sites for the fluoropolymer for subsequent modification or cross-linking.
  • Examples of functional groups include, but are not limited to, halogens, hydroxyl, nitrogen, amino, epoxy, carboxylic salts, esters, sulfur, oxygen, cyanos, ureas, amides, oxo, and the like.
  • the fluoropolymer can be uncross-linked or cross-linked.
  • the fluoropolymer of the present invention can further contain at least one metal oxide, silane, siloxane, or combinations thereof.
  • the metal oxide, silane, or siloxane are reacted with a silane present in the fluoropolymer.
  • Any material containing a silanol functional group may be reacted with the fluoropolymer of the present invention.
  • the fluoropolymers of the present invention are preferably a reaction product of a radical polymerization product such as an emulsion polymerization product.
  • One advantage of the present invention is that no hydrolytically stable organo metallic catalyst is necessary for purposes of conducting the polymerization to form the fluoropolymers of the present invention.
  • the sterically hindered organo silane monomers used in the formation of the fluoropolymers of the present invention are preferably directly co-polymerized into the polymer chain of the fluoropolymers of the present invention.
  • the fluoropolymer is prepared by conducting a polymerization of the co-monomers present for a sufficient time and at a sufficient pressure and temperature to form the fluoropolymer.
  • this polymerization is preferably a free radical polymerization, and more preferably an emulsion polymerization which preferably occurs in an aqueous medium.
  • the fluoropolymers of the present invention initially, deionized water, di-sodium phosphate, and at least one fluorinated surfactant are introduced into a reactor and then deoxygenated. Then, an initiator emulsion and a vinyl silane solution or emulsion can be introduced with or without solvent to start a reaction in the reactor.
  • the reaction media is an aqueous-based media.
  • the feed of the monomers can be stopped but the charge of the initiator is preferably maintained to consume any leftover monomers present.
  • the initiator charge can then be stopped preferably when the reactor pressure drops below about 300 psi and once the reactor is cooled.
  • the unreacted monomers can be vented and the fluoropolymer collected through a drain port or other collection means.
  • the polymer can then be isolated using standard isolation techniques such as, but not limited to, salts/acid coagulation, freeze-thaw, shear coagulation, or spray drying.
  • any reactor temperature can be used as long as the temperature is sufficient to permit the polymerization and formation of the fluoropolymer of the present invention.
  • suitable temperatures include, but are not limited to, from about 30 to about 120°C and more preferably from about 60 to about 100°C.
  • any pressure can be used as long as the pressure is sufficient to permit the polymerization and formation of the fluoropolymers of the present invention. Preferably, this pressure is from about 40 to about 50 atm. While it is preferred that the co-monomers are continuously fed into the reactor, the co-monomers can be introduced as a mixture or through separate feed lines or sequentially in any order.
  • the reactor is preferably a pressurized polymerization reactor equipped with a stirrer and heat control means.
  • the temperature of the polymerization can very depending on the characteristics of the initiator used, but it is typically from about 30°C to about 120°C, and most conveniently it is from about 60°C to about 105°C. The temperature is not limited to this range, however, and might be higher or lower if a high-temperature or low-temperature initiator is used.
  • the VDF/HFP ratios used in the polymerization can be dependent on the temperature chosen for reaction.
  • the pressure of the polymerization is typically from about 20 to about 80 bar, but it can be higher if the equipment permits operation at higher pressure. The pressure is most conveniently from about 30 to about 60 bar.
  • Surfactants which can be used in the polymerization are water-soluble, halogenated surfactants, especially fluorinated surfactants such as the ammonium, substituted ammonium, quaternary ammonium, or alkali metal salts of perfluorinated or partially fluorinated alkyl carboxylates, the perfluorinated or partially fluorinated monoalkyl phosphate esters, the perfluorinated or partially fluorinated alkyl ether or polyether carboxylates, the perfluorinated or partially fluorinated alkyl sulfonates, and the perfluorinated or partially fluorinated alkyl sulfates.
  • fluorinated surfactants such as the ammonium, substituted ammonium, quaternary ammonium, or alkali metal salts of perfluorinated or partially fluorinated alkyl carboxylates, the perfluorinated or partially fluorinated monoalkyl phosphate esters, the perflu
  • Some specific, but not limiting examples are the salts of the acids described in U.S. Patent No. 2,559,752 (incorporated in its entirety by reference herein) of the formula X(CF 2 ) n COOM, wherein X is hydrogen or fluorine, M is an alkali metal, ammonium, substituted ammonium (e.g., alkylamine of 1 to 4 carbon atoms), or quaternary ammonium ion, and n is an integer from 6 to 20; sulfuric acid esters of polyfluoroalkanols of the formula X(CF-) n CH 2 OSO-M, where X and M are as above; and salts of the acids of the formula CF- (CF 2 ) n (CX 2 ) m SO 3 M, where X and M are as above, n is an integer from 3 to 7, and m is an integer from 0 to 2, such as in potassium perfluorooctyl sulfonate.
  • the surfactant charge
  • the paraffin antifoulant is conventional, and any long-chain, saturated, hydrocarbon wax, fully or partially fluorinated wax, or oil may be used. Reactor loading of the paraffin are from about 0.01% to about 0.3% by weight on the total monomer weight used. After the reactor has been charged with deionized water, surfactant, and paraffin antifoulant, the reactor is either purged with nitrogen or evacuated to remove oxygen. The reactor is brought to temperature, and chain-transfer agent may optionally be added. The reactor is then pressurized with a mixture of fluoromonomers.
  • the reaction can be started and maintained by the addition of any suitable initiator known for the polymerization of fluorinated monomers including inorganic peroxides, "redox" combinations of oxidizing and reducing agents, and organic peroxides.
  • suitable initiator known for the polymerization of fluorinated monomers
  • inorganic peroxides include inorganic peroxides, "redox" combinations of oxidizing and reducing agents, and organic peroxides.
  • typical inorganic peroxides are the ammonium or alkali metal salts of persulfates, which have useful activity in the 65°C to 105°C temperature range.
  • Redox systems can operate at even lower temperatures and examples include combinations of oxidants such as hydrogen peroxide, t-butyl hydroperoxide, cumene hydroperoxide, or persulfate, and reductants such as reduced metal salts, iron (II) salts being a particular example, optionally combined with activators such as sodium formaldehyde sulfoxylate or ascorbic acid.
  • oxidants such as hydrogen peroxide, t-butyl hydroperoxide, cumene hydroperoxide, or persulfate
  • reductants such as reduced metal salts, iron (II) salts being a particular example, optionally combined with activators such as sodium formaldehyde sulfoxylate or ascorbic acid.
  • activators such as sodium formaldehyde sulfoxylate or ascorbic acid.
  • organic peroxides which can be used for the polymerization are the classes of dialkyl peroxides, peroxyesters, and peroxydicarbonates.
  • dialkyl peroxides is di-t-butyl peroxide
  • peroxyesters are t-butyl peroxypivalate and t-amyl peroxypivalae
  • peroxydicarbonates are di(n-propyl) peroxydicarbonate, di-isopropyl peroxydicarbonate, di(sec-butyl) peroxydicarbonate, and di(2-ethylhexyl) peroxydicarbonate.
  • di- isopropyl peroxydicarbonate for vinylidene fluoride polymerization and co-polymerization with other fluorinated monomers is taught in U.S. Patent No.
  • 3.475,396, and its use in making vinylidene fluoride/hexafluoropropylene copolymers is further illustrated in U.S. Patent No. 4,360,652.
  • the use of di(n-propyl) peroxydicarbonate in vinylidene fluoride polymerizations is described in the Published Unexamined Application (Kokai) JP 5806571 1.
  • the quantity of an initiator required for polymerization is related to its activity and the temperature used for the polymerization.
  • the total amount of initiator used is generally from about 0.05% to about 2.5% by weight on the total monomer weight used.
  • sufficient initiator is added at the beginning to start the reaction and then additional initiator may be optionally added to maintain the polymerization at a convenient rate.
  • the initiator may be added in pure form, in solution, in suspension, or in emulsion, depending upon the initiator chosen.
  • peroxydicarbonates are conveniently added in the form of an aqueous emulsion.
  • Water-soluble inorganic per compounds such as persulfates, perborates, percarbonates. etc.. generally in the form of their potassium, sodium or ammonium salts, can also be used as initiators for emulsion polymerization.
  • decomposition accelerators generally reducing agents
  • Suitable decomposition accelerators are sulfur compounds, such as for example, sodium sulfite, sodium pyrosulfite or Rongalit C (sodium formamidine sulfinic acid), and also organic reducing agents, such as ascorbic acid, metal salts, such as iron (II) or cobalt (II) salts, organometallic compounds, etc.
  • reaction temperatures for the co-polymerization are in the range from -15° to +120°C, preferably in the range from 20° to 1 15°C, and, more preferably, in the range from 30° to 1 10°C.
  • chain transfer agents such as methanol, isopropanol, isopentane, ethyl acetate, diethyl malonate and carbon tetrachloride, may be used to adjust the molecular weight of the polymers formed.
  • the process of the present invention can carry out the co-polymerization under an elevated pressure. This pressure should be at least 5 bar, but need not exceed 100 bar.
  • the preferred pressure range for the process according to the present invention is from 5 to 65 bar.
  • the co-polymers according to the present invention may be produced in batches, although they are preferably produced semi-continuously or continuously.
  • the stationary concentration of free monomer in component c) is kept low. This is achieved by initially introducing 0.02 to 15 mol% vinyl-silanes based on the total mols of co-monomers to be reacted, optionally together with other co-monomers of components a) and b), either in batches or semi-continuously and uniformly adding the rest of component c) in accordance with the advance of the co-polymerization.
  • the rest of component c) is of course added at the same time as the remainders of components a) and b).
  • the time for polymerization to be completed is based on the amount of co- monomers present, initiator amounts, and reactor conditions.
  • the time for the polymerization to be completed is when the desired solids content is achieved.
  • the collected fluoropolymers of the present invention can be formed into a powder and any unreacted co-monomers can be further removed by washings, for instance, with methanol or other suitable solvents.
  • An advantage of the present invention especially with conducting the polymerization as an emulsion polymerization is that essentially no premature cross-linking reactions occur between silane functionalities. Preserving the reactive silane groups as part of the fluoropolymer expands the range of applications of these fluoropolymers compared to conventional fluoropolymers.
  • the fluoropolymers of the present invention can be subjected to post-linking and any other desired post chemical modifications without compromising the superior properties of the fluoropolymers in terms of chemical resistance, high temperature stability, high tensile strength, low refractive indices, and the like.
  • buffering agents useful for silane emulsions are: organic and inorganic acids and bases, including salts thereof and preferably mono- or poly-alkali metal, alkaline earth metal or amine salts of carbonic acid, phosphoric acid, sulfuric acid, hydrofluoric acid, a C,-C 6 organo-, mono-, or poly-carboxylic acid, or a C--C 30 alkyleniminopolycarboxylic acid, ammonia, a C,-C 30 organic base, or a mixture of any of the foregoing.
  • Illustrative are: sodium bicarbonate, sodium carbonate, ammonium carbonate, sodium borate, mono-, di-, or trisodium phosphate, mono-, di-, or tripotassium phosphate, ammonium sodium phosphate, mono-, or disodium sulfate, sodium acetate, potassium acetate, ammonium acetate, calcium acetate, sodium formate, mono-, or disodium sulfide, ammonia, mono-, di-, or triethylamine, mono-, di-, or triethanolamine, (ethylenedinitrilo) tetraacetic acid sodium salt (sodium E.D.T.A.), pyridine, aniline, and sodium silicate.
  • buffering agents Combinations of these materials with other buffers, acids, or bases, such as the use of ammonium hydroxide and acetic acid together, will also be effective.
  • Trisodium phosphate Na 3 P0 4
  • disodium phosphate Na2HP0
  • ammonium hydroxide NH 4 OH
  • sodium bicarbonate NaHC0 3
  • it is easy to handle it consistently gives emulsions with a pH of 7.5; it is environmentally safe; and it is inexpensive.
  • the amount of buffering agent to be employed can vary widely. In general, however, less than 0.01 percent will not be enough to be useful, and more than 5 percent by weight of the total composition will be uneconomical.
  • the fluoropolymers of the present invention can be used in a variety of applications, such as, in polymer foams, elastomeric compositions, adhesive compositions, membranes, and other polymeric compositions.
  • the fluoropolymers of the present invention preferably have a variety of physical and/or chemically properties.
  • the fluoropolymers of the present invention can provide foamed cross-linked polymers with low densities such as less than about 1.8 g/ml, more preferably from less than about 1.0 g/ml and more preferably less than 0.6 g/ml.
  • the fluoropolymers of the present invention can have an improved or increased heat deflection temperature.
  • the fluoropolymers of the present invention can have improved solvent resistance.
  • the fluoropolymers can be fluoro-elastomers having improved and/or different characteristics than the Viton® and Fluorel®-elastomers commercially available.
  • the ability of the fluoropolymer to react permits improved chemical bonding to substrates, such as improved adhesion with inorganic substrates, such as glass and metal oxides as well as other substrates.
  • the fluoropolymers of the present invention can serve as precursors for nano-composites, such as clay/fluoropolymers; sol-gel organo-silanes/fluoropolymers; or organo-silanes-functionalized nanoparticle/fluoropolymers.
  • the fluoropolymers can be used as coatings or can be incorporated into coatings and preferably avoid the need for the use of primers.
  • the chemical bonding ability of the fluoropolymers of the present invention will permit bonding with silicon rubber which can permit the production of alloys and IPNs between fluoropolymers and silicone rubbers.
  • the fluoropolymers of the present invention can be a component in polymer blends. Any compatible polymer can be combined to form the blend.
  • the fluoropolymer can be added to, for instance, acrylates, methacrylates, polyacetals, polyacrylates, polyamides, polyamines, polybutadienes, polycarbonate, polyesters, polyalkylenes, polyimides, polyolefms, polystyrenes, polyurethane, and poly(vinyl alcohol).
  • the fluoropolymers can also be co-polymerized with other polymers.
  • fluoropolymers of the present invention include, but are not limited to, their use as a component for Nafion type membranes which have applications with electrodes such as Li ion batteries and fuel cells and the like.
  • the fluoropolymers can also have controlled functionalities as well as be used as a tie layer and multi-layer polymer composites.
  • the fluoropolymers can also be used as a compatibilizer with other polymers.
  • the polymerization was begun by adding 55 ml of an initiator emulsion consisting of 3 wt % di-n-propyl peroxydicarbonate and 2/3 wt % mixed perfluoroalkanoate salts dispersed in deionized water.
  • the pressure first went up and then dropped upon initiation and it was then maintained at 660 psia by continuous addition of mentioned initiator emulsion at a rate of 2 ml/min, 109.5 ml of 4.5 wt % di-sodium phosphate in dionized water at a rate of 1.5 ml/min and addition of mixture of VF2 and 25 wt % vinyl-tris-iso-propoxy silane in methanol with a ratio of 185.4 ml VF2 to 31.7 ml vinyl-tris-t-butoxy silane solution over a period of 80 min.
  • Monomer feeds were stopped and residual monomers were consumed by maintaining the initiator feed for 35 min at a rate of 3 ml/min after which the reaction mixture was stirred for 35 min at 90°C. After cooling, the residual pressure was 339 psia at 32°C. The autoclave was vented, and then it was emptied of latex. The pH of the latex was 6.2 and the solid content after drying over night in an oven at 1 10°C was 17 %.
  • VTiPS vinyl-tri-iso-propoxy silane
  • VTtBS vinyl-tris-t-butoxy silane

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

L'invention concerne un fluoropolymère étant un produit de réaction polymère d'un fluoropolymère contenant un produit de réaction polymère de a) au moins un premier comonomère d'alkylène contenant au moins un atome de fluor, b) éventuellement au moins un monomère sélectionné parmi 1) au moins un deuxième alkylène contenant au moins un atome de fluor, 2) au moins un éther d'alkyle alcényle contenant au moins un atome de fluor, 3) au moins une cétone aliphatique ou cyclique contenant au moins une position fluorée alpha-alpha, ou 4) des alcènes non-fluorés, de l'éther alkyle alcényle, ou des esters d'alcényle, et c) au moins un alcényle ou un comonomère d'organo-silane d'éther d'alcényle à encombrement stérique comprenant ou non un composant fluoré. Le fluoropolymère peut être réticulé ou réagir ultérieurement. L'invention concerne également des procédés de fabrication de ces fluoropolymères ainsi que des applications de ces fluoropolymères.
PCT/US2000/031040 1999-11-12 2000-11-10 Fluoropolymeres contenant des organo-silanes et procedes de fabrication de ceux-ci WO2001034670A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
JP2001537381A JP2003514085A (ja) 1999-11-12 2000-11-10 オルガノシランを含有するフルオロポリマー及びその製造方法
US09/869,454 US6710123B1 (en) 1999-11-12 2000-11-10 Fluoropolymers containing organo-silanes and methods of making the same
MXPA01007110A MXPA01007110A (es) 1999-11-12 2000-11-10 Fluoropolimeros que contienen organo-silanos y metodos para hacer los mismos.
EP00978536A EP1196465A4 (fr) 1999-11-12 2000-11-10 Fluoropolymeres contenant des organo-silanes et procedes de fabrication de ceux-ci

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US16512399P 1999-11-12 1999-11-12
US60/165,123 1999-11-12

Publications (2)

Publication Number Publication Date
WO2001034670A1 true WO2001034670A1 (fr) 2001-05-17
WO2001034670A8 WO2001034670A8 (fr) 2001-09-27

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EP (1) EP1196465A4 (fr)
JP (1) JP2003514085A (fr)
CN (1) CN1336938A (fr)
MX (1) MXPA01007110A (fr)
RU (1) RU2001122579A (fr)
WO (1) WO2001034670A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1335007A1 (fr) * 2002-02-12 2003-08-13 Atofina Chemicals, Inc. Dispersions aqueuses de polymères fluorés réticulables, contenant des silanes
EP1553111A1 (fr) * 2002-06-14 2005-07-13 Daikin Industries, Ltd. Procede de production de fluorocopolymeres, fluorocopolymeres obtenus, et articles moules y relatifs
US7652115B2 (en) * 2003-09-08 2010-01-26 3M Innovative Properties Company Fluorinated polyether isocyanate derived silane compositions
US7803894B2 (en) 2003-12-05 2010-09-28 3M Innovatie Properties Company Coating compositions with perfluoropolyetherisocyanate derived silane and alkoxysilanes
US9139668B2 (en) 2009-07-31 2015-09-22 3M Innovative Properties Company Fluoropolymer compositions containing a polyol compound and methods of making them
CN112759766A (zh) * 2021-01-20 2021-05-07 威海新元化工有限公司 一种高乙烯基活性氟硅橡胶生胶及其制备方法

Families Citing this family (5)

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CN101210059B (zh) * 2006-12-29 2011-06-15 北京航空航天大学 一种含氟、硅的多元共聚物树脂水分散体
US8138274B2 (en) * 2009-12-08 2012-03-20 Le Centre National De La Recherche Scien Process for preparation of fluorosilicon polymer
CN103881030B (zh) * 2012-12-19 2016-05-18 张家港市国泰华荣化工新材料有限公司 一种含氟氨基硅油乳液的制备方法
CN106632793B (zh) * 2016-10-24 2019-01-08 内蒙古奥特普氟化学新材料开发有限公司 耐低温含氟弹性体及其制备方法
CN106496397B (zh) * 2016-10-24 2019-01-08 内蒙古奥特普氟化学新材料开发有限公司 含氟弹性体、具有该含氟弹性体的树脂组合物及制备方法

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US4886862A (en) * 1985-10-09 1989-12-12 Dainippon Ink And Chemicals, Inc. Resin composition
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US5973090A (en) * 1997-10-31 1999-10-26 Toagosei Co., Ltd. Cold-setting coating composition

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EP1054047B1 (fr) * 1999-05-21 2003-03-26 JSR Corporation Composition de revêtement et films et verre revêtus par cette composition

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US4751114A (en) * 1984-12-14 1988-06-14 Mitsui Sekiyu Kagaku Kogyo Kabushiki Kaisha Solvent soluble fluorine-containing polymer, coating composition containing the same and coating process thereof
US4886862A (en) * 1985-10-09 1989-12-12 Dainippon Ink And Chemicals, Inc. Resin composition
US5179181A (en) * 1988-12-02 1993-01-12 Mitsui Petrochemical Industries, Ltd. Process for producing fluorine-containing copolymer and fluorine-containing copolymer composition
US5859123A (en) * 1995-11-15 1999-01-12 Central Glass Company, Limited Water-based fluorine-containing emulsion
US5973090A (en) * 1997-10-31 1999-10-26 Toagosei Co., Ltd. Cold-setting coating composition

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1335007A1 (fr) * 2002-02-12 2003-08-13 Atofina Chemicals, Inc. Dispersions aqueuses de polymères fluorés réticulables, contenant des silanes
US6833414B2 (en) 2002-02-12 2004-12-21 Arkema Inc. Cross-linkable aqueous fluoropolymer based dispersions containing silanes
EP1553111A1 (fr) * 2002-06-14 2005-07-13 Daikin Industries, Ltd. Procede de production de fluorocopolymeres, fluorocopolymeres obtenus, et articles moules y relatifs
EP1553111A4 (fr) * 2002-06-14 2008-09-24 Daikin Ind Ltd Procede de production de fluorocopolymeres, fluorocopolymeres obtenus, et articles moules y relatifs
US7652115B2 (en) * 2003-09-08 2010-01-26 3M Innovative Properties Company Fluorinated polyether isocyanate derived silane compositions
US7803894B2 (en) 2003-12-05 2010-09-28 3M Innovatie Properties Company Coating compositions with perfluoropolyetherisocyanate derived silane and alkoxysilanes
US9139668B2 (en) 2009-07-31 2015-09-22 3M Innovative Properties Company Fluoropolymer compositions containing a polyol compound and methods of making them
CN112759766A (zh) * 2021-01-20 2021-05-07 威海新元化工有限公司 一种高乙烯基活性氟硅橡胶生胶及其制备方法
CN112759766B (zh) * 2021-01-20 2022-07-15 新元化学(山东)股份有限公司 一种高乙烯基活性氟硅橡胶生胶及其制备方法

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Publication number Publication date
EP1196465A4 (fr) 2004-12-29
EP1196465A1 (fr) 2002-04-17
MXPA01007110A (es) 2002-03-20
RU2001122579A (ru) 2003-06-20
CN1336938A (zh) 2002-02-20
JP2003514085A (ja) 2003-04-15
WO2001034670A8 (fr) 2001-09-27

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