WO2001016215A1 - Procede de production d'une composition a base de fluorocopolymere elastique - Google Patents
Procede de production d'une composition a base de fluorocopolymere elastique Download PDFInfo
- Publication number
- WO2001016215A1 WO2001016215A1 PCT/JP2000/005906 JP0005906W WO0116215A1 WO 2001016215 A1 WO2001016215 A1 WO 2001016215A1 JP 0005906 W JP0005906 W JP 0005906W WO 0116215 A1 WO0116215 A1 WO 0116215A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- kneading
- copolymer
- vulcanizing agent
- salt
- drying
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 34
- 239000000203 mixture Substances 0.000 title claims abstract description 28
- 229920001577 copolymer Polymers 0.000 claims abstract description 60
- 238000004073 vulcanization Methods 0.000 claims abstract description 36
- 238000001035 drying Methods 0.000 claims abstract description 32
- 238000004898 kneading Methods 0.000 claims abstract description 32
- 239000006185 dispersion Substances 0.000 claims abstract description 25
- 239000003795 chemical substances by application Substances 0.000 claims description 27
- 150000001875 compounds Chemical class 0.000 claims description 22
- 239000000463 material Substances 0.000 claims description 19
- 239000006104 solid solution Substances 0.000 claims description 18
- -1 compound salt Chemical class 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 150000004714 phosphonium salts Chemical group 0.000 claims description 9
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 8
- 239000000155 melt Substances 0.000 claims description 8
- 150000004010 onium ions Chemical group 0.000 claims description 5
- ZFVMWEVVKGLCIJ-UHFFFAOYSA-N bisphenol AF Chemical compound C1=CC(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C=C1 ZFVMWEVVKGLCIJ-UHFFFAOYSA-N 0.000 claims description 3
- USFRYJRPHFMVBZ-UHFFFAOYSA-M benzyl(triphenyl)phosphanium;chloride Chemical group [Cl-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)CC1=CC=CC=C1 USFRYJRPHFMVBZ-UHFFFAOYSA-M 0.000 claims description 2
- 229920001480 hydrophilic copolymer Polymers 0.000 claims 1
- 125000004464 hydroxyphenyl group Chemical group 0.000 claims 1
- QYSGYZVSCZSLHT-UHFFFAOYSA-N octafluoropropane Chemical compound FC(F)(F)C(F)(F)C(F)(F)F QYSGYZVSCZSLHT-UHFFFAOYSA-N 0.000 claims 1
- 229960004065 perflutren Drugs 0.000 claims 1
- 229920001973 fluoroelastomer Polymers 0.000 abstract description 32
- 230000001112 coagulating effect Effects 0.000 abstract description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 11
- 229910052731 fluorine Inorganic materials 0.000 description 11
- 239000011737 fluorine Substances 0.000 description 11
- 239000003999 initiator Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 238000002156 mixing Methods 0.000 description 10
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 10
- 239000003995 emulsifying agent Substances 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 230000015271 coagulation Effects 0.000 description 6
- 238000005345 coagulation Methods 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 150000001491 aromatic compounds Chemical class 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 235000011054 acetic acid Nutrition 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- 229940000489 arsenate Drugs 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 239000000701 coagulant Substances 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 150000008040 ionic compounds Chemical class 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 239000003039 volatile agent Substances 0.000 description 2
- XLAIWHIOIFKLEO-UHFFFAOYSA-N (E)-4-<2-(4-hydroxyphenyl)ethenyl>phenol Natural products C1=CC(O)=CC=C1C=CC1=CC=C(O)C=C1 XLAIWHIOIFKLEO-UHFFFAOYSA-N 0.000 description 1
- 125000006201 3-phenylpropyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- YWACAHLWCZJQBK-UHFFFAOYSA-N 4-[1,1-dichloro-1,3,3,3-tetrafluoro-2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical compound C1=CC(O)=CC=C1C(C(F)(Cl)Cl)(C(F)(F)F)C1=CC=C(O)C=C1 YWACAHLWCZJQBK-UHFFFAOYSA-N 0.000 description 1
- HTVITOHKHWFJKO-UHFFFAOYSA-N Bisphenol B Chemical compound C=1C=C(O)C=CC=1C(C)(CC)C1=CC=C(O)C=C1 HTVITOHKHWFJKO-UHFFFAOYSA-N 0.000 description 1
- SDDLEVPIDBLVHC-UHFFFAOYSA-N Bisphenol Z Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)CCCCC1 SDDLEVPIDBLVHC-UHFFFAOYSA-N 0.000 description 1
- VKOUCJUTMGHNOR-UHFFFAOYSA-N Diphenolic acid Chemical compound C=1C=C(O)C=CC=1C(CCC(O)=O)(C)C1=CC=C(O)C=C1 VKOUCJUTMGHNOR-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- JPYHHZQJCSQRJY-UHFFFAOYSA-N Phloroglucinol Natural products CCC=CCC=CCC=CCC=CCCCCC(=O)C1=C(O)C=C(O)C=C1O JPYHHZQJCSQRJY-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 235000011126 aluminium potassium sulphate Nutrition 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 150000003868 ammonium compounds Chemical class 0.000 description 1
- ZSZOOASCTWVDJA-UHFFFAOYSA-N benzene-1,4-diol;methane Chemical compound C.OC1=CC=C(O)C=C1.OC1=CC=C(O)C=C1.OC1=CC=C(O)C=C1 ZSZOOASCTWVDJA-UHFFFAOYSA-N 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 230000002431 foraging effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000002440 hydroxy compounds Chemical class 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 235000011147 magnesium chloride Nutrition 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- 239000012768 molten material Substances 0.000 description 1
- FZZQNEVOYIYFPF-UHFFFAOYSA-N naphthalene-1,6-diol Chemical compound OC1=CC=CC2=CC(O)=CC=C21 FZZQNEVOYIYFPF-UHFFFAOYSA-N 0.000 description 1
- ZUVBIBLYOCVYJU-UHFFFAOYSA-N naphthalene-1,7-diol Chemical compound C1=CC=C(O)C2=CC(O)=CC=C21 ZUVBIBLYOCVYJU-UHFFFAOYSA-N 0.000 description 1
- DFQICHCWIIJABH-UHFFFAOYSA-N naphthalene-2,7-diol Chemical compound C1=CC(O)=CC2=CC(O)=CC=C21 DFQICHCWIIJABH-UHFFFAOYSA-N 0.000 description 1
- 239000004081 narcotic agent Substances 0.000 description 1
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229940050271 potassium alum Drugs 0.000 description 1
- GRLPQNLYRHEGIJ-UHFFFAOYSA-J potassium aluminium sulfate Chemical compound [Al+3].[K+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRLPQNLYRHEGIJ-UHFFFAOYSA-J 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000004023 quaternary phosphonium compounds Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- IBWGNZVCJVLSHB-UHFFFAOYSA-M tetrabutylphosphanium;chloride Chemical compound [Cl-].CCCC[P+](CCCC)(CCCC)CCCC IBWGNZVCJVLSHB-UHFFFAOYSA-M 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- XLAIWHIOIFKLEO-OWOJBTEDSA-N trans-stilbene-4,4'-diol Chemical compound C1=CC(O)=CC=C1\C=C\C1=CC=C(O)C=C1 XLAIWHIOIFKLEO-OWOJBTEDSA-N 0.000 description 1
Classifications
-
- 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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
-
- 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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/203—Solid polymers with solid and/or liquid additives
-
- 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
Definitions
- the present invention relates to a method for producing a fluorine-containing elastic copolymer composition.
- the present invention relates to a method for producing a fluorinated elastic copolymer composition containing a fluorinated elastic copolymer (hereinafter, also simply referred to as “fluororubber”).
- fluororubber also simply referred to as “fluororubber”.
- the present invention relates to a method for producing a fluorine-containing elastic copolymer composition containing a salt as a vulcanizing component.
- Fluorororubber obtained from vinylidene fluoride and at least one other fluoromonomer has excellent heat, chemical and oil resistance and is used in a variety of industries. In order to satisfy the above properties under severe conditions, it is necessary to cure the polymer by vulcanization.
- Fluorororubber is produced by copolymerizing monomers with one or both of a water-soluble initiator and an oil-soluble initiator.
- Japanese Patent Publication No. 56-29895 / Japanese Patent Publication No. 56-34909 discloses the first stage of polymerization.
- an emulsifier is added to the medium to uniformly disperse the oil-soluble initiator.
- the obtained fluororubber is mixed with a vulcanizing agent (for example, a polyhydroxy compound) and a vulcanization accelerator (for example, a quaternary ammonium salt) to obtain a vulcanizing composition.
- a vulcanizing agent for example, a polyhydroxy compound
- a vulcanization accelerator for example, a quaternary ammonium salt
- the method of mixing a vulcanizing agent and a vulcanization accelerator with fluororubber can be roughly classified into a method of adding a vulcanizing agent and a vulcanization accelerator to an aqueous dispersion of a fluororubber and coagulating the fluorine rubber, There is a method in which the dispersion is taken out by coagulation, dried, and then kneaded with a vulcanizing agent and a vulcanization accelerator.
- kneading has poor workability, and it is difficult to uniformly mix a vulcanizing agent and a vulcanization accelerator with fluororubber.
- a large amount of energy is required to knead high-viscosity fluororubber.
- the quaternary ammonium compound is hygroscopic and absorbs moisture in the atmosphere, so that it is difficult to handle.
- a quaternary ammonium compound and Z or a quaternary phosphonium compound are added as vulcanization accelerators to an aqueous emulsion or aqueous dispersion of fluororubber, and coagulated to form a composition for vulcanization of fluororubber.
- a method for obtaining a product is disclosed in Japanese Patent Application Laid-Open No. 56-147480. According to this method, the fluororubber can be uniformly mixed with the vulcanizing agent and the vulcanization accelerator, which is more efficient than kneading.
- the quaternary ammonium compound since the quaternary ammonium compound is hygroscopic, it tends to be taken into the aqueous medium when coagulating with the fluoroelastomer from the aqueous dispersion, so that a predetermined amount of the quaternary ammonium compound is converted into fluorine.
- the rubber When compounding the rubber, it is necessary to add a predetermined amount or more of the quaternary ammonium compound to the aqueous dispersion, and the amount incorporated into the fluororubber is unstable.
- Both the aqueous fluorororubber dispersion and the aqueous fluororubber emulsion obtained using the oil-soluble initiator contain an emulsifier. However, the action of quaternary ammonium compounds has been found to be inhibited by emulsifiers.
- Japanese Patent Publication No. 57-147775 discloses that a solid solution of a quaternary ammonium compound and a polyhydroxyaromatic compound is used as a fluorine solution. Kneading with rubber is disclosed. However, in this method, poor dispersion of the solid solution occurs, and as a result, the vulcanization properties of the molded product are not stable.
- Japanese Patent Application Laid-Open No. 50-22048 discloses that a water content of about 15 to 35% by weight and a fluorine content
- the wet fluorinated elastic copolymer agglomerate which is the coagulation product of the elastic copolymer latex, is continuously supplied to the mixing area, and the vulcanizing agent and the vulcanization accelerator are supplied in fine powder form.
- a process for producing a fluorine-containing copolymer composition which comprises mixing while maintaining the particle size of the fluorinated elastic copolymer block.
- the vulcanizing agent and the vulcanization accelerator are supplied to the mixing section in the form of an aqueous dispersion in the form of fine powder, and the fluorinated elastic copolymer and the curing component or other additives present in the mixture are added.
- the temperature should be kept low enough so that no harmful reactions with the product take place.
- the quaternary phosphonium salt of the hardening component is water-soluble and easily dissolved, it is lost together with the separated water when it is treated with an apparatus such as an extruder.
- the uniformity of the composition is also limited.
- a fluorinated elastic copolymer composition is produced by kneading fluororubber with a vulcanizing agent, a vulcanization accelerator and the like using a two-and-one apparatus.
- kneading at 21st level requires a large amount of energy, and in addition, the work required for workers, such as charging raw materials to the kneader, is a problem.
- vulcanizing agents and vulcanization accelerators are usually powders, and there is also a concern that workers may be harmed when they are charged in a niche.
- One object of the present invention is to provide a method for efficiently producing a composition for vulcanizing fluororubber.
- Another object of the present invention is to provide a method in which a vulcanizing agent and a vulcanization accelerator are uniformly dispersed in a fluororubber so that a fluororubber composition having stable vulcanization properties can be obtained. It is.
- the present invention relates to a method for producing a fluorinated ⁇ -like copolymer composition
- a fluorinated elastic copolymer comprising a fluorinated elastic copolymer, a vulcanizing agent and a vulcanization accelerator
- the method includes a step of kneading and drying an agglomerate of a copolymer obtained by stiffening the copolymer from an aqueous dispersion of a fluorinated elastic copolymer,
- Fluorine-containing elastic copolymer in which a compatible substance of vulcanizing agent and vulcanization accelerator is added to the aggregate A method of making the composition is provided. Detailed description of the invention
- Fluorororubber is an elastic copolymer of vinylidene fluoride and at least one other fluorinated monomer.
- fluorine-containing monomers include, for example, tetrafluoroethylene, trifluorene-chloroethylene, trifluoroenoethylene, hexafluoropropylene, pentafluoropropylene, and no.
- Fluoro methyl vinyl ether
- ⁇ 0 Fluorole mouth
- Echinorebini, ⁇ etenore ⁇ 0 —Funole mouth (propyl buluretel) and the like.
- the aqueous dispersion of fluororubber may be obtained by any of the polymerization methods known in the art.
- the method of the present invention may comprise the step of using a water-soluble initiator in the first stage of polymerization and the step of using the oil-soluble initiator in the second stage, wherein the aqueous dispersion obtained by the two-stage polymerization may contain an emulsifier. It can be applied to aqueous dispersion obtained by polymerization.
- a vulcanizing agent is a polyhydroxy compound.
- the polyhydroxy compound used as the vulcanizing agent is preferably a polyhydroxy aromatic compound.
- the polyhydroxy aromatic compound any compound known as a vulcanizing agent for fluororubber can be used.
- Preferred examples are 2, 2-bis (4-arsenate Dorokishifueniru) propane (bis phenol one A), 2, 2-bis (4-arsenate Dorokishifueniru) Pas one Furuoropurono ⁇ 0 emissions (bisphenol one AF), Rezonoreshin, 1 , 3,5-trihydroxybenzene, 1,7-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 4,4'-dihydroxydipheny ⁇ , 4 , 4'-dihydroxystilbene, 2,6-dihydroxyxanthracene, hydroquinone, tecohol, 2,2-bis (4-hydroxyphenyl) butane (bisphenol-II), 4,4-bis (4 —Hydroxyphenyl) valeric acid, 2,2-bis (4-hydroxyphenyl) tetrafluorodichloropropane, propane, 4, 4 ′ —dihydroxydiphenylsulfone
- Examples of vulcanization accelerators are onium compounds.
- the ammonia compound there are an ammonium compound, a phosphonium compound, an oxonium compound, a sulfonium compound and the like, and a quaternary ammonium salt and a quaternary phosphonium salt are preferable.
- any of those known as vulcanization accelerators for fluororubber can be used. Preferred examples are as follows.
- 8-Methyl-1,8-diazabicyclolo [5.4.0] —7-indesenidimuc mouth lid, 8-methyl-1,8-diazabicyclo [5.4.0] —7-indesenidiom iodide, 8-methyl-1,8— Diazavicik mouth [5.4.0] —7-Pendedium hydroxide, 8-Methyl-1,8-Diazabicik mouth [5.4.0] —7—Pendesenium-methylsulfate, 8-Ethyl-1,8-diazabicyclo [5.
- Tetrabutylphosphonium chloride Tetrabutylphosphonium chloride, benzyltriphenylphosphonium chloride, benzylinoletrimethy / lephosphonium chloride, benzyltributynolephosphonium chloride and the like.
- an ionic compound and a polyhydroxy compound or a salt thereof are used.
- a compatible material of Compatibles are solid solutions or melts.
- Solid solutions can be prepared in conventional manner.
- the solid solution used in the present invention can be obtained from an ionic compound and a polyhydroxy compound or a salt thereof, and the respective components may be made to be in a uniform state by a conventional method. It is easily protected by heating and melting both components until they are liquefied and uniformly mixed, or by heating and melting both components with stirring and then uniformly cooling ⁇ 3. .
- the molten material is obtained by heating an onium compound and a polyhydroxy compound or a salt thereof, or a solid solution thereof to a temperature higher than its melting point to obtain a molten state.
- the blending amount of the two components constituting the compatible material is 5 to 400 parts by weight, particularly 100 to 100 parts by weight of the onium compound with respect to 100 parts by weight of the polyhydroxy compound or a salt thereof. It is preferred that the adjustment be made as follows.
- the ratio of both components constituting the above-mentioned compatible material is preferably set to an appropriate blending ratio from the beginning.
- the mixing ratio of both components can be adjusted by adding a hydroxy compound or a salt thereof. By doing so, it is possible to cope with various weight ratios of onium compound / polyhydroxy compound with only one kind of the compatible substance.
- the compatibilizer two or more compatibilizers may be used in combination.For example, a compatibilizer of a quaternary ammonium salt and a polyhydroxy compound, a quaternary phosphonium salt and a polyhydroxy compound, Can be used in combination.
- the solid solution is used as a powder for uniform mixing with the aggregates of the copolymer.
- the average particle size is preferably from 10 to 2000 / m, more preferably from 10 to 100 / m, for example from 20 to 300 ⁇ m, especially from 20 to 50 ⁇ m It is.
- the content of the compatible substance in the vulcanizing composition is usually 0.1 to 10 parts by weight, preferably 1 to 5 parts by weight, per 100 parts by weight of the fluorinated elastic copolymer.
- the copolymer is coagulated from the aqueous dispersion and the coagulated copolymer is removed from the aqueous medium by a conventional method.
- Coagulation may be performed by a conventional method.
- a suitable inorganic or organic acid eg, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, formic acid, acetic acid, oxalic acid, etc.
- inorganic or organic coagulants such as aluminum sulfate, magnesium chloride, ammonium chloride, potassium alum, polyalkylamines or salts thereof can also be used.
- An acid and a coagulant may be used in combination.
- the compatible material is added to the coagulated aggregate before, during, or after the coagulated aggregate is dried.
- the copolymer and the compatible material are sufficiently kneaded to obtain a fluororubber composition comprising the copolymer and the compatible material.
- the step of drying while kneading the aggregate can be performed in an extruder. Addition of the compatibilizer is performed by a metering pump in the case of a melt, or by a metering feeder in the case of a solid solution.
- the compatible material is added to the aggregate before the step of drying the aggregate.
- the compatible material Prior to the step of drying the aggregate of the copolymer, the compatible material is continuously supplied to the aggregate removed from the aqueous dispersion, and the mixture is dried while kneading.
- the compatible material is preferably a solid solution, particularly a powdered solid solution.
- the compatible substance can be added to the wet copolymer after coagulation just before the drying step, and the copolymer and the compatible substance can be dried while being melt-kneaded.
- the compatible material (melt or solid solution) can be continuously fed to the extruder.
- the solid solution powder can be supplied from the hopper of the extruder. If the extruder is sufficiently kneaded and dried, the next extruder need not be used.
- the compatible substance is added to the aggregate during the step of drying the aggregate. It is preferable to add a compatible material in a molten state to the copolymer in a molten state. While the copolymer in the middle of the drying step is melt-kneaded by an extruder (for example, a twin-screw extruder), a melted compatibilizer can be added. It is preferable to add the compatibilizer in a state where the agglomerated matter has a low volatile content (for example, water, an emulsifier, a oligomer) (that is, a state near the completion of the drying step). Volatile content (especially water content), for example at 0.01 wt% or more
- a compatible substance may be added to the aggregate having a ratio of / 0 .
- the amount of volatiles means the weight ratio of volatiles to the total aggregate.
- the copolymer agglomerate may be continuously supplied to the drying step, and in the middle of the drying step, the compatible substance may be continuously supplied in a molten state, and drying may be continued while kneading.
- One extruder It may have a drying zone for dewatering and drying the aggregate, and a kneading zone for kneading the dehydrated and dried aggregate and the compatible material. “Dewatering” generally means that water is squeezed out of the aggregates between the screws.
- the extruder may be provided with a metering pump (for example, a plunger pump) for supplying the compatible material so that the weight ratio of the copolymer and the compatible material in the extruder becomes constant.
- a metering pump for example, a plunger pump
- the next extruder need not be employed.
- the compatible material is added to the aggregate.
- the method of the present invention also has a kneading step after the step of drying while kneading, and the melt or solid solution may be added after the drying step and before the kneading step.
- the drying step and the kneading step are performed by two extruders, and a first extruder that shares the drying step and a second extruder that shares the kneading step can be used.
- the second extruder may be, for example, a surface-renewal-type kneader.
- the first extruder is a twin-screw extruder
- the second extruder may be either a single-screw or a twin-screw extruder.
- a gear pump is provided between the first extruder and the second extruder, a more uniform copolymer composition can be obtained.
- the aqueous dispersion of the fluorinated elastic copolymer used in the present invention contains an emulsifier, especially when an oil-soluble initiator is used, due to its production method. Since the narcotics may inhibit the action of the quaternary ammonium compound, an acid can be added before coagulation of the copolymer to reduce the emulsifying action of the emulsifier.
- the acid is preferably added in such an amount that the pH of the aqueous dispersion becomes 2 or less.
- the acid may be either an inorganic acid or an organic acid.
- examples of the former include hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid, and examples of the latter include carboxylic acids such as formic acid, acetic acid and oxalic acid.
- Aqueous dispersions may be acidic due to the type of compound used as initiator.
- the base can be added to the aqueous dispersion to neutralize it before coagulation of the copolymer.
- the base is preferably added in such an amount that the pH of the aqueous dispersion is between 7 and 9.
- Amin, ammonia, alkali metal hydroxides, although alkaline earth metals hydroxides and the like can be used, preferably NH 4 OH, Na 2 C 0 3.
- an additive which is usually added to the fluororubber composition may be added to the aqueous dispersion in advance.
- additives that may be added to the aqueous dispersion include fillers and reinforcing agents such as bonbon black, clay, diatomaceous earth, and talc. If necessary, a plasticizer and a coloring agent can be added. Preferred embodiments of the invention
- the feed rate of the wet agglomerate was about 5 O kg / hr.
- the agglomerates supplied to the twin-screw extruder were sent to a dehydration / drying zone by a twin-screw screw, and a large amount of water was separated and discharged.
- the agglomerate from which a large amount of water has been dehydrated is further kneaded by two screws, and is in a molten state due to a rise in temperature due to the energy given from the screw shaft and a rise in the amount of heat given to the heater attached to the barrel.
- the fluorinated elastic copolymer in the molten state is kneaded by two screws, and the volatile components (eg, water, emulsifier, oligomer) contained therein are removed by suction from the vacuum vent while repeating surface renewal. Was done.
- the residence time of the copolymer in the dehydration drying zone was 5 minutes.
- the fluorinated elastic copolymer (temperature: 185 ° C, water content: 0.1%) from which low volatile components had been removed was sent to the kneading zone.
- bisphenol AF bisphenol AF
- DBU-B 8-benzyl-1.8-diazabicyclo [5,4,0]
- the melt (bend ratio between BIS-AF and DBU-B, 2Z0.35) was mixed with a continuous pump. Fixed ratio of fluorinated elastic copolymer and melt
- the dispersibility is as follows: Raw rubber (temperature of 100 ° C for 5 minutes or 120. CX for 5 minutes) is molded into a 0.1 mm thick film and vulcanized with a 40x magnifying glass.
- the roll processability is defined as “good” when the compound can be kneaded smoothly without separating into rolls before and after kneading, and “poor” when it cannot. Table 1 shows the results.
- a predetermined amount of a vulcanizing agent and a vulcanization accelerator can be easily and uniformly blended into a fluorine-containing elastic copolymer with low energy.
- the compounding amount of the vulcanizing agent may be small, and the vulcanization properties of the molded article are improved and stabilized.
- the amount of vulcanizing agent and vulcanization accelerator can be reduced.
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- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP00956833A EP1219669B1 (en) | 1999-09-01 | 2000-08-31 | Process for producing elastic fluorocopolymer composition |
US10/069,940 US6790915B1 (en) | 1999-09-01 | 2000-08-31 | Process for producing elastic fluorocopolymer composition |
DE60034583T DE60034583T2 (de) | 1999-09-01 | 2000-08-31 | Verfahren zur herstellung einer elastischen fluorcopolymerzusammensetzung |
JP2001520767A JP4779280B2 (ja) | 1999-09-01 | 2000-08-31 | 含フッ素弾性状共重合体組成物の製造方法 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP24733299 | 1999-09-01 | ||
JP11/247332 | 1999-09-01 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2001016215A1 true WO2001016215A1 (fr) | 2001-03-08 |
Family
ID=17161841
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2000/005906 WO2001016215A1 (fr) | 1999-09-01 | 2000-08-31 | Procede de production d'une composition a base de fluorocopolymere elastique |
Country Status (6)
Country | Link |
---|---|
US (1) | US6790915B1 (ja) |
EP (1) | EP1219669B1 (ja) |
JP (1) | JP4779280B2 (ja) |
CN (1) | CN1203112C (ja) |
DE (1) | DE60034583T2 (ja) |
WO (1) | WO2001016215A1 (ja) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
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US20050155690A1 (en) * | 2004-01-16 | 2005-07-21 | Park Edward H. | Bonding of dynamic vulcanizates of fluorocarbon elastomers |
US20090270573A1 (en) * | 2008-04-29 | 2009-10-29 | Christopher John Bish | Process for coagulating perfluoroelastomers |
EP2640781B1 (en) | 2010-11-18 | 2016-12-28 | 3M Innovative Properties Company | Method of coagulating an amorphous fluoropolymer latex |
CN112409585B (zh) * | 2020-12-07 | 2022-09-20 | 万华化学(四川)有限公司 | 一种共聚碳酸酯及其制备方法 |
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US3876616A (en) * | 1973-05-29 | 1975-04-08 | Du Pont | Wet blending of fluoroelastomer compositions |
JPS5545734A (en) * | 1978-09-26 | 1980-03-31 | Daikin Ind Ltd | Fluororubber composition |
JPS5690836A (en) * | 1979-12-24 | 1981-07-23 | Daikin Ind Ltd | Production of composition for vulcanization of fluorine- containing rubber |
JPH07157584A (ja) * | 1993-12-10 | 1995-06-20 | Shin Etsu Chem Co Ltd | 発泡性フッ素ゴム組成物の製造方法 |
JPH1036570A (ja) * | 1996-07-19 | 1998-02-10 | Yokohama Rubber Co Ltd:The | 熱可塑性エラストマー組成物の製造方法及び製造装置 |
JPH10176090A (ja) * | 1996-12-17 | 1998-06-30 | Jsr Corp | フッ素ゴム組成物の製造方法 |
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US3997705A (en) * | 1974-07-11 | 1976-12-14 | Dynamit Nobel Aktiengesellschaft | Method of coagulating a fluoro-elastomer from an aqueous dispersion thereof |
US4141874A (en) | 1975-11-15 | 1979-02-27 | Daikin Kogyo Co., Ltd. | Fluorine-containing elastomeric copolymers, process for preparing the same and composition containing the same |
JPS5276359A (en) | 1975-12-20 | 1977-06-27 | Daikin Ind Ltd | Fluorine-containing rubber compositions |
JPS5936658B2 (ja) * | 1975-12-22 | 1984-09-05 | ダイキン工業株式会社 | リユウジヨウフツソゴム ナラビニ ソノセイゾウホウホウ |
US4132845A (en) * | 1977-05-27 | 1979-01-02 | E. I. Du Pont De Nemours And Company | Mechanical dewatering process for elastomer slurries |
JPS56147840A (en) | 1980-04-16 | 1981-11-17 | Daikin Ind Ltd | Production of fluorine rubber-vulcanizing composition |
JPH069825B2 (ja) | 1988-02-08 | 1994-02-09 | 東芝機械株式会社 | 2軸押出機によるゴム状重合体の脱水乾燥方法 |
US5371143A (en) * | 1989-11-16 | 1994-12-06 | Minnesota Mining And Manufacturing Company | Polymer blend composition of fluorinated elastomers, thermoplastic polymers and thermoplastics elastomers |
IT1269846B (it) * | 1994-05-27 | 1997-04-15 | Ausimont Spa | Composizioni fluoroelastomeriche vulcanizzabili |
DE69508275T2 (de) | 1994-12-06 | 1999-09-30 | Daikin Ind Ltd | Elastisches fluorcopolymer mit ausgezeichneter formverarbeitbarkeit, verfahren zu dessen herstellung und vulkanisierbare zusammensetzung mit ausgezeichneter formverarbeitbarkeit |
US6239223B1 (en) * | 1997-09-05 | 2001-05-29 | Chemfab Corporation | Fluoropolymeric composition |
US6310141B1 (en) * | 2000-06-27 | 2001-10-30 | Dyneon Llc | Fluoropolymer-containing compositions |
JP5629895B2 (ja) | 2007-09-07 | 2014-11-26 | ジャパンマリンユナイテッド株式会社 | 溶接構造体 |
JP5714775B2 (ja) | 2012-04-23 | 2015-05-07 | アジアン モス カンパニー リミテッドAsian Mos Co.Ltd. | 使い捨て哺乳瓶キット |
-
2000
- 2000-08-31 DE DE60034583T patent/DE60034583T2/de not_active Expired - Fee Related
- 2000-08-31 US US10/069,940 patent/US6790915B1/en not_active Expired - Lifetime
- 2000-08-31 JP JP2001520767A patent/JP4779280B2/ja not_active Expired - Fee Related
- 2000-08-31 EP EP00956833A patent/EP1219669B1/en not_active Expired - Lifetime
- 2000-08-31 CN CN00815264.0A patent/CN1203112C/zh not_active Expired - Fee Related
- 2000-08-31 WO PCT/JP2000/005906 patent/WO2001016215A1/ja active IP Right Grant
Patent Citations (6)
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US3876616A (en) * | 1973-05-29 | 1975-04-08 | Du Pont | Wet blending of fluoroelastomer compositions |
JPS5545734A (en) * | 1978-09-26 | 1980-03-31 | Daikin Ind Ltd | Fluororubber composition |
JPS5690836A (en) * | 1979-12-24 | 1981-07-23 | Daikin Ind Ltd | Production of composition for vulcanization of fluorine- containing rubber |
JPH07157584A (ja) * | 1993-12-10 | 1995-06-20 | Shin Etsu Chem Co Ltd | 発泡性フッ素ゴム組成物の製造方法 |
JPH1036570A (ja) * | 1996-07-19 | 1998-02-10 | Yokohama Rubber Co Ltd:The | 熱可塑性エラストマー組成物の製造方法及び製造装置 |
JPH10176090A (ja) * | 1996-12-17 | 1998-06-30 | Jsr Corp | フッ素ゴム組成物の製造方法 |
Also Published As
Publication number | Publication date |
---|---|
CN1203112C (zh) | 2005-05-25 |
CN1387547A (zh) | 2002-12-25 |
DE60034583D1 (de) | 2007-06-06 |
EP1219669A4 (en) | 2002-11-13 |
EP1219669A1 (en) | 2002-07-03 |
EP1219669B1 (en) | 2007-04-25 |
JP4779280B2 (ja) | 2011-09-28 |
DE60034583T2 (de) | 2007-12-27 |
US6790915B1 (en) | 2004-09-14 |
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