WO2005007707A1 - 含フッ素重合体の製造方法、含フッ素重合体水性分散液、2−アシルオキシカルボン酸誘導体及び界面活性剤 - Google Patents
含フッ素重合体の製造方法、含フッ素重合体水性分散液、2−アシルオキシカルボン酸誘導体及び界面活性剤 Download PDFInfo
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- WO2005007707A1 WO2005007707A1 PCT/JP2004/010214 JP2004010214W WO2005007707A1 WO 2005007707 A1 WO2005007707 A1 WO 2005007707A1 JP 2004010214 W JP2004010214 W JP 2004010214W WO 2005007707 A1 WO2005007707 A1 WO 2005007707A1
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- Prior art keywords
- carboxylic acid
- acid derivative
- integer
- carbon atoms
- fluoropolymer
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- MGEBVSZZNFOIRB-UHFFFAOYSA-N 2-(6-amino-2-iodopurin-9-yl)-5-(hydroxymethyl)oxolane-3,4-diol Chemical compound C1=NC=2C(N)=NC(I)=NC=2N1C1OC(CO)C(O)C1O MGEBVSZZNFOIRB-UHFFFAOYSA-N 0.000 description 1
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 description 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- RFJVDJWCXSPUBY-UHFFFAOYSA-N 2-(difluoromethylidene)-4,4,5-trifluoro-5-(trifluoromethyl)-1,3-dioxolane Chemical compound FC(F)=C1OC(F)(F)C(F)(C(F)(F)F)O1 RFJVDJWCXSPUBY-UHFFFAOYSA-N 0.000 description 1
- VUIWJRYTWUGOOF-UHFFFAOYSA-N 2-ethenoxyethanol Chemical compound OCCOC=C VUIWJRYTWUGOOF-UHFFFAOYSA-N 0.000 description 1
- QMIWYOZFFSLIAK-UHFFFAOYSA-N 3,3,3-trifluoro-2-(trifluoromethyl)prop-1-ene Chemical group FC(F)(F)C(=C)C(F)(F)F QMIWYOZFFSLIAK-UHFFFAOYSA-N 0.000 description 1
- GVEUEBXMTMZVSD-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,6-nonafluorohex-1-ene Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C=C GVEUEBXMTMZVSD-UHFFFAOYSA-N 0.000 description 1
- OJXVWULQHYTXRF-UHFFFAOYSA-N 3-ethenoxypropan-1-ol Chemical compound OCCCOC=C OJXVWULQHYTXRF-UHFFFAOYSA-N 0.000 description 1
- YSYRISKCBOPJRG-UHFFFAOYSA-N 4,5-difluoro-2,2-bis(trifluoromethyl)-1,3-dioxole Chemical group FC1=C(F)OC(C(F)(F)F)(C(F)(F)F)O1 YSYRISKCBOPJRG-UHFFFAOYSA-N 0.000 description 1
- MKTOIPPVFPJEQO-UHFFFAOYSA-N 4-(3-carboxypropanoylperoxy)-4-oxobutanoic acid Chemical compound OC(=O)CCC(=O)OOC(=O)CCC(O)=O MKTOIPPVFPJEQO-UHFFFAOYSA-N 0.000 description 1
- HMBNQNDUEFFFNZ-UHFFFAOYSA-N 4-ethenoxybutan-1-ol Chemical compound OCCCCOC=C HMBNQNDUEFFFNZ-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
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- 239000004254 Ammonium phosphate Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
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- XTJFFFGAUHQWII-UHFFFAOYSA-N Dibutyl adipate Chemical compound CCCCOC(=O)CCCCC(=O)OCCCC XTJFFFGAUHQWII-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
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- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
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- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
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- 238000005299 abrasion Methods 0.000 description 1
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- 125000003545 alkoxy group Chemical group 0.000 description 1
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- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 235000015278 beef Nutrition 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 239000000337 buffer salt Substances 0.000 description 1
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- 239000001273 butane Substances 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- GKRALBJDXHXFNB-UHFFFAOYSA-N butoxycyclohexane Chemical compound CCCCOC1CCCCC1 GKRALBJDXHXFNB-UHFFFAOYSA-N 0.000 description 1
- SCVZKPKDMFXESQ-VSAQMIDASA-N butyl (2e,4e)-hexa-2,4-dienoate Chemical compound CCCCOC(=O)\C=C\C=C\C SCVZKPKDMFXESQ-VSAQMIDASA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
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- 238000006297 dehydration reaction Methods 0.000 description 1
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- 238000006392 deoxygenation reaction Methods 0.000 description 1
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Natural products CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- XSBSXJAYEPDGSF-UHFFFAOYSA-N diethyl 3,5-dimethyl-1h-pyrrole-2,4-dicarboxylate Chemical compound CCOC(=O)C=1NC(C)=C(C(=O)OCC)C=1C XSBSXJAYEPDGSF-UHFFFAOYSA-N 0.000 description 1
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 1
- WBZKQQHYRPRKNJ-UHFFFAOYSA-L disulfite Chemical compound [O-]S(=O)S([O-])(=O)=O WBZKQQHYRPRKNJ-UHFFFAOYSA-L 0.000 description 1
- POULHZVOKOAJMA-UHFFFAOYSA-M dodecanoate Chemical compound CCCCCCCCCCCC([O-])=O POULHZVOKOAJMA-UHFFFAOYSA-M 0.000 description 1
- 229920001198 elastomeric copolymer Polymers 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- XJELOQYISYPGDX-UHFFFAOYSA-N ethenyl 2-chloroacetate Chemical compound ClCC(=O)OC=C XJELOQYISYPGDX-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 150000005607 ethylarylethers Chemical class 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical group FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- IPCSVZSSVZVIGE-UHFFFAOYSA-M hexadecanoate Chemical compound CCCCCCCCCCCCCCCC([O-])=O IPCSVZSSVZVIGE-UHFFFAOYSA-M 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical class II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 150000002497 iodine compounds Chemical class 0.000 description 1
- 150000005613 iso-butylarylethers Chemical class 0.000 description 1
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 1
- 229940070765 laurate Drugs 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 238000010068 moulding (rubber) Methods 0.000 description 1
- 229940105132 myristate Drugs 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 125000006353 oxyethylene group Chemical group 0.000 description 1
- 239000006179 pH buffering agent Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- UQGPCEVQKLOLLM-UHFFFAOYSA-N pentaneperoxoic acid Chemical compound CCCCC(=O)OO UQGPCEVQKLOLLM-UHFFFAOYSA-N 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 125000005342 perphosphate group Chemical group 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 150000005608 propylarylethers Chemical class 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- TUNFSRHWOTWDNC-UHFFFAOYSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- GPRLSGONYQIRFK-MNYXATJNSA-N triton Chemical compound [3H+] GPRLSGONYQIRFK-MNYXATJNSA-N 0.000 description 1
- 229940070710 valerate Drugs 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
-
- 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
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/10—Esters
- C08F20/22—Esters containing halogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/62—Halogen-containing esters
- C07C69/63—Halogen-containing esters of saturated acids
-
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
Definitions
- the present invention relates to a method for producing a fluoropolymer, an aqueous dispersion of the fluoropolymer, a 2-acinoleoxycarboxylic acid derivative, and a surfactant.
- a tetra- or fluorinated carboxylic acid having a linear or partially branched chain and having 7 to 10 carbon atoms is used as a surfactant in an aqueous medium.
- Methods for polymerizing polyethylene [TFE] are described in many documents (for example, see Patent Document 1, Patent Document 2, and Patent Document 3).
- heptafluoroisobutenyl alkyl ether (CF) C obtained by using octafluoroisobutene by-produced during the production of hexafluoropropene as a starting material is used.
- CF ⁇ R CF ⁇ R, R is a hydrocarbon radical
- Non-Patent Document 1 While producing by-products from KMnO
- Fluoro-2-hydroxycarboxylic acid esters further include [CF (CF)] [CF (C
- fluoro-2-hydroxycarboxylic acid can be obtained from this fluoro-2-hydroxycarboxylic acid ester (for example, see Patent Document 7).
- ester compounds in which an acyl group has been introduced into the OH group of this fluoro-2-hydroxycarboxylic acid are known.
- Patent Document 1 JP-A-61-207413
- Patent Document 2 JP-A-61-228008
- Patent Document 3 JP-A-10-212261
- Patent Document 4 U.S. Pat.No. 6,429,258
- Patent Document 5 JP-A-2003-119204
- Patent Document 6 JP-A-61-286348 (Claim 1)
- Patent Document 7 JP-A-2002-234860 (Claim 1)
- Non-patent document l Utebaev U. et al .; Izv. Akad. Nauk SSSR Ser. Kh im., 2 (1974) 387)
- an object of the present invention is to use a surfactant having an extremely small residual amount in a fluoropolymer particle after heat treatment such as aggregation without impairing the stability during polymerization.
- An object of the present invention is to provide a fluoropolymer aqueous dispersion using the same. It is another object of the present invention to provide a 2-hydroxycarboxylic acid derivative and a surfactant comprising the above 2-aminocarboxylic acid derivative.
- the present invention relates to a process for producing a fluoropolymer, which comprises polymerizing a fluoropolymer using a carboxylic acid ester bond-containing carboxylic acid derivative as a surfactant in an aqueous medium.
- An acid ester bond-containing carboxylic acid derivative has a carboxylic acid ester bond optionally substituted by a fluorine atom and C ⁇ OM (M is H, NH
- a method for producing a fluoropolymer comprising:
- the present invention is an aqueous dispersion of a fluoropolymer comprising particles made of a fluoropolymer, a carboxylic acid ester-containing carboxylic acid derivative, and an aqueous medium, wherein the carboxylic acid ester-containing carboxylic acid is used.
- the derivative is a carboxylic acid ester bond optionally substituted by a fluorine atom, and CO ⁇ M (M is H, NH
- the present invention provides the following general formula (1)
- Rf 1 and Rf 2 are the same or different and represent H, F, a fluoroalkyl group having 120 carbon atoms or a fluoroalkyl group containing an ether oxygen having 112 carbon atoms; Represents a fluoroalkyl group having 1 to 20 carbon atoms or a fluoroalkyl group containing 1 to 20 carbon atoms and containing ether oxygen, M is H, NH 2, and a and b are 0 to 2
- the present invention provides a surfactant having a surfactant activity U, which is composed of the above-mentioned 2-acyloxycarboxylic acid derivative.
- the present invention provides the following general formula (5)
- Rf 1 and Rf 2 are the same or different and represent H, F, a fluoroalkyl group having 120 carbon atoms, or a fluoroalkyl group containing 1-20 carbon atoms, and Is the H, NH
- Rf represents a fluoroalkyl group having 1 to 20 carbon atoms or a fluoroalkyl group containing 1 to 20 carbon atoms, and Z represents —OM 1 or Y; M 1 represents H, NH
- the 2-alkynoleoxycarboxylic acid derivative is produced by esterifying the alkanoyloxycarboxylic acid derivative represented by the formula (1).
- the process for producing a fluoropolymer of the present invention comprises polymerizing a fluoropolymer using a carboxylic acid ester bond-containing carboxylic acid derivative as a surfactant in an aqueous medium.
- the "fluorinated polymer” is a polymer having a fluorine atom bonded to a carbon atom.
- the fluorine-containing polymer is obtained by polymerizing one or more fluorine-containing monomers, but is a non-fluorine-based monomer having no fluorine atom. It may be obtained by copolymerizing a body.
- the “fluorine-containing monomer” is a monomer having at least one fluorine atom bonded to a carbon atom. The fluorinated polymer will be described later.
- the carboxylic acid ester bond-containing carboxylic acid derivative is a carboxylic acid derivative having a carboxylic acid ester bond and —C ⁇ OM (M is as defined above).
- carboxylate bond means (1) _C—— or —OC ⁇ _,
- One or two or more hydrogen atoms may be substituted by a substituent such as a fluorine atom, or may be bonded to a hydrocarbon group which may have ether oxygen in the main chain.
- a substituent such as a fluorine atom
- Examples of the carboxylic acid ester bond include a structure represented by R—CO ⁇ _, a structure represented by R— ⁇ CO_ (R is an alkyl group which may have a substituent, or And the above-mentioned ether oxygen-containing fluoroalkyl group which may have a substituent.
- the carboxylic acid ester bond-containing carboxylic acid derivative easily undergoes ester hydrolysis by post-treatment such as coagulation performed after the polymerization, and the resulting hydrolyzate generally has volatility, It can be removed by heating.
- the carboxylate bond is an acyloxy group represented by RfCOO_ (Rf represents a fluoroalkyl group having 120 carbon atoms or a fluoroalkyl group containing ether oxygen having 112 carbon atoms), or
- the alkoxy group represented by RfOCO_ (Rf is the same as described above) is preferably a luponyl group.
- fluoroalkyl group means an alkyl group in which at least one H is substituted by F.
- ether oxygen-containing fluoroalkyl group refers to an alkyl group containing, in the main chain, an alkyleneoxy group having 13 to 13 carbon atoms as a repeating unit, and at least one H is F Means those substituted with
- Examples of the above ether oxygen-containing fluoroalkyl group include _ (CFO)-
- ether oxygen-containing fluoroalkyl group is different from the above-mentioned “fluoroalkyl group” in that it has an ether oxygen as described above.
- Rf is the fluoroalkyl group
- the lower limit of the number of carbon atoms is preferably 2, the more preferable lower limit is 3, the preferable upper limit is 9, and the more preferable upper limit is 4.
- Rf is the above ether oxygen-containing fluoroalkyl group
- the preferable lower limit of the number of carbon atoms is 2, the preferable upper limit is 8, and the more preferable upper limit is 4.
- the above-mentioned M in the above-mentioned carboxylic acid ester bond-containing carboxylic acid derivative is preferably a milk which is preferably NH because milk produced is easily removed by heat treatment.
- Li, Na, and K are preferred from the viewpoints of forming power and dispersing power.
- the carboxylic acid ester bond-containing carboxylic acid derivative in the method for producing a fluoropolymer of the present invention includes:
- Rf and M are as defined above. Same as what you did. Rf 2 and Rf may be the same or different.
- Rf 3 may include one substituent Rf 4 and / or one double bond.
- Rf 4 represents F, a fluoroalkyl group having 1 to 20 carbon atoms, or a fluoroalkylene group having 112 to 20 carbon atoms.
- Rf and M are the same as defined above.
- Rf 1 , Rf 2 and Rf in the above general formula (1) are used for polymerization in the method for producing a fluoropolymer of the present invention, which can be carried out by determining the number of carbon atoms and the value of d so as to exhibit surface activity.
- a and b represent an integer of 0-2, and d represents an integer of 1-3.
- the above d is preferably an integer of 1 to 2 in terms of ease of preparation, and more preferably 1.
- Rf 1 and Rf 2 are the same or different and are H, F, a fluoroalkyl group having 120 carbon atoms, or a fluoroalkyl group containing 112 carbon atoms containing ether oxygen. Represents
- the preferred upper limit of the number of carbon atoms in the fluoroalkyl group is 9, the more preferred upper limit is 5, the more preferred upper limit is 3, and the particularly preferred upper limit is 2.
- the preferred upper limit of the number of carbon atoms of the ether oxygen-containing fluoroalkyl group is 8, the more preferred upper limit is 5, and the still more preferred upper limit is 2.
- Rf 1 and Rf 2 are the same or different, general formula:
- A represents H or F
- j represents an integer of 1 to 6
- p represents an integer of 0 to 3.
- the preferable upper limit of j is 4, the more preferable upper limit is 3, and the further preferable upper limit is 2.
- the preferable upper limit of the above p is 1, and the above p is more preferably 0.
- Rf and Rf are the same or different and are CF-, CF-CF, CF-CF-CF, respectively.
- Rf is the same as defined above.
- acyl in the “2_acyloxycarboxylic acid derivative” is 1 C ⁇ Rf as is clear from the general formula (1), and the definition of the Rf As described above, the concept includes those having the ether oxygen-containing fluoroalkyl group.
- a preferred lower limit of the number of carbon atoms of the fluoroalkyl group is 2, a more preferred lower limit is 3, a preferred upper limit is 9, and a more preferred upper limit is 4.
- a preferred lower limit of the number of carbon atoms of the ether oxygen-containing fluoroalkyl group is 2, a preferred upper limit is 8, and a more preferred upper limit is 4.
- N represents an integer of 1-4
- m represents an integer of 0-3.
- A is the same as defined above. ), Preferably.
- the upper limit of the above n is more preferably 3 and the upper limit of the above q is more preferably 2.
- Rf is CF-, CF CF-, CF CF CF-, CF CF CF CF-, HCF-, HCF
- it is CF-, HCF CF CF- or HCF CF CF-.
- Rf 2 and Rf may be the same or different.
- d Rf when d is an integer of 2 to 3, d Rf may be the same or different, and when a is 2, a Rf 1 is may be different may be the same, if b is 2, b number of Rf 2 may be the different from one may be the same.
- Rf 1 and Rf 2 are the same or different
- M is the same as defined above.
- NH is preferred as M because it can be easily removed by heat treatment after use as a surfactant.
- the Rf 3 is -CH 1, _C H — or _ (CH) -T- (f 2f g 2g-2 2 h
- CH) _ [f represents an integer of 1 to 6
- g represents an integer of 2 to 6
- h and i are the same or different.
- Rf 4 is the same as defined above. Is preferred.
- Rf and M are the same as defined above.
- Rf 5 is —CH— or _C H f 2f g 2g-2
- the dicarboxylic acid half ester (A) is a compound in which Rf 3 in the general formula (2) is an unsubstituted alkylene having no substituent. those groups, the dicarboxylic acid half ester (B), said Rf 3 is one substituent R f 4 (Rf 4 is the same as defined above.) to have substituted alkylene having a Or a substituted phenolic group.
- the f and the g are each preferably 5 or less, more preferably 2 or less.
- the above f and the above g may be the same or different.
- CH CH_CH— is more preferred.
- the dicarboxylic acid half ester (A) includes, for example, RfOM (Rf is the same as defined above; M 2 represents H NH Li Na or K) and H ⁇ OCRf 5 C ⁇ OM (Rf 5 and ⁇
- Rf 4 is preferably F, a fluoroalkyl group having 8 or less carbon atoms, or an ether oxygen-containing fluoroalkylene group having 8 or less carbon atoms.
- F, a fluoroalkyl group having 4 or less carbon atoms and an ether oxygen-containing fluoroalkylene group having 4 or less carbon atoms are more preferable.
- the h and the i are preferably 0 or 1, and more preferably 0.
- the dicarboxylic acid half ester (B) has the following general formula
- Rf Rf 4 and M are the same as defined above.
- H and i are the same or different and represent an integer of 0-3.
- the dicarboxylic acid half ester (B) is, for example, M 3 MOC (CH 2) _T_ (CH 2) CO 2
- OM (M 3 represents H NH Li Na or K.
- TM h and i are as defined above.
- a part or all of the carboxylic acid ester bond-containing carboxylic acid derivative remains in the aqueous dispersion together with the fluorinated polymer obtained by polymerization in the method for producing a fluorinated polymer of the present invention. If there is no change under environmental conditions that do not cause hydrolysis, the aqueous dispersion will be mixed in the wet powder obtained by coagulation as required.
- the carboxylic acid ester bond-containing carboxylic acid derivative can be used, for example, as a surfactant, and then collected and reused.
- the carboxylic acid derivative containing a carboxylic acid ester bond usually produces a hydrolyzate by hydrolysis.
- the hydrolysis can be carried out mainly in the presence of an acid or alkali, for example, in the post-treatment such as aggregation after polymerization in the method for producing a fluoropolymer of the present invention.
- ° C preferably 100-200 ° C.
- the “hydrolyzate” refers to a compound having two or more molecules generated by hydrolysis, that is, a compound having the above-mentioned —C ⁇ OM (M is the same as defined above).
- RfC ⁇ OH (Rf is the same as defined above) or a salt thereof, or Rf ⁇ H (Rf is the same as defined above) or an alcoholate thereof.
- RfCOOH salt examples include RfCOOM (Rf and M are the same as defined above), and the like.
- examples of the alcoholates include Rf OM (Rf and M are as defined above. The same as the above).
- the carboxylic acid ester bond-containing carboxylic acid derivative is preferably one in which the hydrolyzate has volatility. If the hydrolyzate has volatility, it can be easily removed by heating.
- heating examples include drying and baking after applying a coating composition prepared from an aqueous dispersion of the fluoropolymer to a substrate, and aqueous dispersion of the fluoropolymer. Drying and pelletization of the wet powder obtained by coagulating the liquid, and heating in the forming process using the obtained dry powder and pellets are mentioned.
- the carboxylic acid ester-containing carboxylic acid derivative is subjected to ordinary post-treatments such as coagulation and heating, and then reduced to a concentration of 10 ppm or less, preferably 1 ppm or less, of the aqueous dispersion of the fluoropolymer. Can be. Further, during post-treatment such as coagulation, the cleaning efficiency can be increased by making the aqueous dispersion of the above-mentioned fluorine-containing polymer acidic or alkaline and increasing the temperature for washing.
- the carboxylic acid ester bond-containing carboxylic acid derivative exerts surface activity as an emulsifier when polymerizing the fluoropolymer, and is easily hydrolyzed and removed by post-treatment. Can be. Therefore, the method for producing a fluoropolymer of the present invention makes it possible to extremely reduce the residual amount of the carboxylic acid ester-containing carboxylic acid derivative which coexists with the obtained fluoropolymer. It can suppress foaming, improve physical properties, prevent coloration, and the like during processing of powders, pellets, molded articles, coating films, and the like made of a fluoropolymer.
- the hydrolyzate preferably has 6 or less carbon atoms bonded to a fluorine atom because it is easily removed by heating.
- the number of carbon atoms bonded to the fluorine atoms is preferably 2 or more, more preferably 4 or less, more preferably 3 or less, in terms of the above removal.
- the fluoropolymer in the method for producing a fluoropolymer of the present invention, if at least one carboxylic acid ester bond-containing carboxylic acid derivative is used as the surfactant, the fluoropolymer can be produced efficiently. is there.
- two or more of the above carboxylic acid ester-containing carboxylic acid derivatives may be used simultaneously as the surfactant, or those having a volatile property or a fluorine-containing polymer may be used.
- Compounds having a surface activity other than the above-mentioned carboxylic acid ester bond-containing carboxylic acid derivative may be used at the same time as long as they can remain on the molded article made of the union.
- the above-mentioned other compounds having a surfactant activity are not particularly limited.
- any of an anionic, cationic, nonionic or betaine surfactant may be used.
- These surfactants may be of a hide mouth carbon type.
- an additive for stabilizing each compound is added.
- the additives are not particularly limited, and may be, for example, those usually used for general surfactants such as stabilizers.
- an aqueous medium, the carboxylic acid ester-containing carboxylic acid derivative, a monomer, and other additives as necessary are charged into a polymerization reactor.
- the reaction is carried out by stirring the contents of the reactor and maintaining the reactor at a predetermined polymerization temperature, and then adding a predetermined amount of a polymerization initiator to start the polymerization reaction.
- a monomer, a polymerization initiator, a chain transfer agent, the above-mentioned carboxylic acid ester bond-containing carboxylic acid derivative and the like may be additionally added according to the purpose.
- the polymerization temperature is usually 5 to 120 ° C, and the polymerization pressure is 0.05 to 10 MPaG.
- the polymerization temperature and the polymerization pressure are appropriately determined depending on the type of the monomer used, the molecular weight of the target polymer, and the reaction rate.
- the carboxylic acid ester bond-containing carboxylic acid derivative is preferably added in an amount of 0.0001 to 15% by mass of the aqueous medium, and more preferably the lower limit is 0.001% by mass.
- the more preferred upper limit is 10% by mass, and the still more preferred upper limit is 1% by mass.
- the amount is less than 0.0001% by mass, the dispersing power becomes insufficient, and when the amount exceeds 15% by mass, the effect corresponding to the added amount cannot be obtained. On the contrary, the polymerization rate may be reduced or the reaction may be stopped. is there.
- the amount of the carboxylic acid ester-containing carboxylic acid derivative to be added is appropriately determined depending on the type of the monomer used, the molecular weight of the target polymer, and the like.
- the polymerization initiator is not particularly limited as long as it can generate radicals in the above-mentioned polymerization temperature range, and known oil-soluble and Z- or water-soluble polymerization initiators can be used.
- the polymerization can be started as redox in combination with a reducing agent or the like.
- concentration of the polymerization initiator is appropriately determined depending on the type of the monomer, the molecular weight of the target polymer, and the reaction rate.
- the "aqueous medium” is a reaction medium for causing polymerization, and means a liquid containing water.
- the aqueous medium is not particularly limited as long as it contains water, and water, for example, alcohol
- a fluorine-free organic solvent such as ether and ketone, and / or a fluorine-containing organic solvent having a boiling point of 40 ° C. or lower.
- a fluorine-containing organic solvent such as C318 can be used.
- a known chain transfer agent and a radical scavenger may be further added to adjust the polymerization rate and the molecular weight according to the purpose.
- the fluorine-containing polymer is obtained by polymerizing a fluorine-containing monomer, and a fluorine-free monomer can also be copolymerized according to the purpose.
- Y 2 CY ⁇ R 5 ⁇ R 6 (Y 2 is H or F, and R 4 and R 6 are each a part or all of a hydrogen atom having 18 to 18 carbon atoms substituted with a nitrogen atom.
- R 5 is an alkylene group having 18 carbon atoms in which part or all of the hydrogen atoms are substituted by fluorine atoms.), And the like.
- the above fluorinated fins preferably have 2 to 6 carbon atoms.
- the fluorofluorin having 2 to 6 carbon atoms include tetrafluoroethylene [TFE], hexafluoropropylene [HFP], chlorofluoroethylene [CTFE], and fluorofluorene [CTFE].
- vinylidene fluoride [VDF] trifluoroethylene, hexafluoroisobutylene and perfluorobutylethylene.
- the cyclic fluorinated monomer is preferably perfluoro-2,2-dimethyl-1,3-dioxole [P DD], perfluoro-2-methylene-4-methyl-1,3-dioxolane. [PMD] and the like.
- R 4 and R 6 preferably have 14 to 14 carbon atoms, and more preferably have all hydrogen atoms replaced by fluorine, It said R 5 is preferably those having 2 to 4 carbon atoms, more preferably, Ru der which all hydrogen atoms are replaced by fluorine atoms.
- Examples of the fluorine-free monomer include hydrocarbons having reactivity with the fluorine-containing monomer. Elementary monomers and the like.
- Examples of the hydrocarbon monomer include alkenes such as ethylene, propylene, butylene, and isobutylene; ethyl vinyl ether, propyl vinylinoleatenore, butinolevininoleatenole, isobutinolevininoleatenole, and the like.
- Alkyl vinyl ethers such as cyclohexyl butyl ether; vinyl acetate, vinyl propionate
- N-butyrate isobutyrate, valerate, bivalate, vinole, porinoate, puprilate, pulate, versatate, laurate, myristate, palmitate , Butyl stearate, butyl benzoate, butyl para-t_butyl benzoate, butyl cyclohexanecarboxylate, vinyl monochloroacetate, butyl adipate, butyl acrylate, butyl methacrylate, butyl crotonate, butyl sorbate, Buryl esters such as cinnamate vinyl, vinyl decilenate, hydroxyacetate butyl, hydroxypropioate butyl, hydroxybutyrate butyl, hydroxyvalerate, hydroxyisobutyrate butyl, hydroxycyclohexanecarboxylate butyl, etc .; ethylaryl ether , Alkylaryl ethers such as propylaryl ether, al
- alkylaryl esters such as steles and cyclohexylaryl esters.
- the fluorine-free monomer may also be a functional group-containing hydrocarbon monomer.
- the functional group-containing hydrocarbon monomer include hydroxyalkyl vinyl ethers such as hydroxyethyl vinyl ether, hydroxypropyl vinyl ether, hydroxybutyl vinyl ether, hydroxyisobutyl vinyl ether, and hydroxycyclohexyl vinyl ether; itaconic acid
- Non-fluorine-containing monomers having a carboxyl group such as succinic acid, succinic anhydride, fumaroleic acid, fumaric anhydride, crotonic acid, maleic acid, maleic anhydride, perfluorobutenoic acid; glycidyl butyl ether, glycidyl ralyl ether
- Non-fluorine-containing monomers having a glycidyl group such as, etc .
- non-fluorine-containing monomers having an amino group such as aminoalkyl vinyl ether, aminoalkyla
- a monomer having the largest molar fraction of a monomer in the polymer (hereinafter, "most common monomer”) ) Is TFE, the VDF polymer is the most monomeric SVDF, and the CTFE polymer is the most monomeric CTFE.
- the TFE polymer may suitably be a TFE homopolymer, or (1) TFE, (2) one or more than two or more TFE having 2 to 8 carbon atoms. It may be a copolymer of a fluorine-containing monomer, particularly HFP or CTFE, and (3) another monomer.
- examples of the above (3) other monomers include, for example, fluoro (alkyl vinyl ether) having an alkyl group having 115 carbon atoms, especially 113 carbon atoms; fluorodixole; perfluoroalkylethylene. ⁇ -hydroperfluoroolefin and the like.
- the TFE polymer may be a copolymer of TFE and one or more fluorine-free monomers.
- fluorine-free monomer examples include alkenes such as ethylene and propylene; bier esters; and bier ethers.
- TFE polymers also include copolymers of TFE, one or more fluorine-containing monomers having from 2 to 8 carbon atoms, and one or more fluorine-free monomers. It may be united.
- the VDF polymer may preferably be a VDF homopolymer [PVDF], or (1) VDF, (2) one or two or more carbon atoms having 2 to 8 carbon atoms.
- VDF VDF homopolymer
- the CTFE polymer may preferably be a CTFE homopolymer, or (1) CTFE, or (2) one or more than two or more CTFEs having 2 to 8 carbon atoms.
- the CTFE polymer may be a copolymer of CTFE and one or more fluorine-free monomers.
- the fluorine-free monomer may be ethylene, propylene, or the like. Alkenes; bier esters; vinyl ethers and the like.
- the fluoropolymer produced by the method for producing a fluoropolymer of the present invention may be glassy, plastic or elastomeric. These are amorphous or partially crystalline and can be subjected to compression firing, melt processing or non-melt processing.
- polytetrafluoroethylene polymer [PTFE polymer] is used as the non-melt-processable resin
- melt-processable resin is used as the (II) melt-processable resin
- Tylene / TFE copolymer [ETFE], TFEZHFP copolymer [FEP], and TFE / perfluoro (alkylbutyl ether) copolymer [PFA, MFA, etc.] are (III) TFEZ as elastomeric copolymers.
- Propylene copolymer, TFE / propylene copolymer Z Third monomer copolymer (the above-mentioned third monomer is VDF, HFP, CTFE, perfluoro (alkyl alkyl ether) s, etc.), TFE and perfluoro (alkyl butyl ether) HFP / ethylene copolymer, HFPZ ethylene ZTFE copolymer; PV DF; VDF / HFP copolymer, HFP / ethylene copolymer, VDF / TFE / HFP copolymer, etc. Thermoplastic elastomer; and JP-B-61-49327 And the like.
- Rf 6 represents a perfluoroalkyl group having 16 carbon atoms.
- K3, k4, and k5 are the same or different and are integers from 0 to 5.
- Q 5 , Q 6 And R 7 are the same or different and are F or CF.
- the process for producing a fluoropolymer of the present invention is for producing a fluoropolymer.
- the concentration of the above-mentioned fluoropolymer is usually 10 to 50% by mass of the aqueous dispersion obtained by carrying out the above-mentioned polymerization.
- a preferred lower limit of the concentration of the fluoropolymer is 10% by mass, a more preferred lower limit is 15% by mass, a preferred upper limit is 40% by mass, a more preferred upper limit is 35% by mass, and a further preferred upper limit is. 30% by mass.
- the aqueous dispersion obtained by carrying out the above polymerization may be concentrated or subjected to dispersion stabilization treatment to form a disposable sponge, or a powder obtained by subjecting to coagulation or coagulation to be recovered and dried. Other solids may be used.
- the method for producing the fluoropolymer of the present invention comprises a fluorine-containing polymer.
- the produced fluorinated polymer may be a fluorinated polymer dispersed in the aqueous dispersion or dispersed in the dispurgeon. It may be a fluorinated polymer or a fluorinated polymer as the above-mentioned powder or other solid substance.
- the polymerization of the PTFE polymer is usually carried out at a polymerization temperature of 10 to 100 ° C. and a polymerization pressure of 0.055 MPaG.
- pure water and the carboxylic acid ester-containing carboxylic acid derivative are charged into a pressure-resistant reaction vessel equipped with a stirrer, deoxygenated, charged with TFE, brought to a predetermined temperature, and a polymerization initiator is added to carry out the reaction. Start. As the pressure decreases as the reaction progresses, additional TFE is continuously or intermittently supplied so as to maintain the initial pressure. When a predetermined amount of TFE has been supplied, stop the supply, purge the TFE in the reaction vessel, return the temperature to room temperature, and terminate the reaction.
- the polytetrafluoroethylene polymer [PTFE polymer] is not only a TFE homopolymer but also a copolymer of TFE and a modified monomer, which is non-melting calorie ( Hereinafter, it is a concept including “modified PTFE”).
- modified monomer examples include perhaloolefins such as HFP and CTFE; fluoro (alkyl vinyl ether) having an alkyl group having 115 carbon atoms, particularly 113 carbon atoms; Cyclic fluorinated monomers such as sole; perhaloalkylethylene; ⁇ -hydroperhaloolefin.
- perhaloolefins such as HFP and CTFE
- Cyclic fluorinated monomers such as sole
- perhaloalkylethylene ⁇ -hydroperhaloolefin.
- the supply of the modified monomer can be carried out in an initial batch or in a continuous or intermittent manner.
- Modifier monomer content in the modified PTFE is usually in the range of, 0.5 001 2 mol 0/0.
- the carboxylic acid ester bond-containing carboxylic acid described above is used.
- the acid derivative can be used within the range of use in the above-mentioned method for producing a fluoropolymer of the present invention.
- an amount of 0.0001 to 5% by mass of the aqueous medium is added.
- the concentration of the carboxylic acid derivative containing a carboxylic acid ester bond is not particularly limited as long as it is within the above range, but is usually added at a critical micelle concentration (CMC) or less at the start of polymerization. If the addition amount is large, the aspect ratio becomes large and needle-like particles are formed, and the aqueous dispersion becomes gel-like and stability is impaired.
- CMC critical micelle concentration
- an organic peroxide such as persulfate (for example, ammonium persulfate), disuccinic acid peroxide, or diglutaric acid peroxide may be used alone or in combination. It can be used in the form of a mixture. Further, it may be used in combination with a reducing agent such as sodium sulfite to form a redox system. Further, during polymerization, a radical scavenger such as hydroquinone or catechol may be added, or a peroxide decomposer such as ammonium sulfite may be added to adjust the radical concentration in the system.
- persulfate for example, ammonium persulfate
- disuccinic acid peroxide for example, disuccinic acid peroxide
- diglutaric acid peroxide diglutaric acid peroxide
- a radical scavenger such as hydroquinone or catechol
- a peroxide decomposer such as ammonium sulfite
- chain transfer agents can be used.
- saturated hydrocarbons such as methane, ethane, propane, and butane
- halogenated compounds such as chloromethane, dichloromethane, and difluoroethane
- Hydrocarbons, methanol, alcohols such as ethanol, hydrogen and the like are mentioned, and those in a gaseous state at normal temperature and normal pressure are preferable.
- the amount of the chain transfer agent used is usually 110 ppm, preferably 500 ppm, based on the total amount of TFE supplied.
- a saturated hydrocarbon having 12 or more carbon atoms which is substantially inert and becomes liquid under the above reaction conditions may be further used as a dispersion stabilizer of the reaction system. It can be used in an amount of 2 to 10 parts by mass with respect to 100 parts by mass of the aqueous medium. Further, as a buffer for adjusting the pH during the reaction, ammonium carbonate, ammonium phosphate or the like may be added.
- the solid content concentration is 10 to 50% by mass
- the average particle size is 0.05 5,000 ⁇
- the carboxylic acid derivative containing a carboxylic acid ester bond is used.
- An aqueous dispersion having particles made of a PTFE polymer having a fine particle diameter of 0.3 ⁇ m or less can be obtained.
- the PTFE polymer has a number average molecular weight of 1,000, 10,000,000.
- the aqueous dispersion of the PTFE polymer can be used for various applications as a fine powder after coagulation and drying.
- the aqueous dispersion obtained by emulsion polymerization of a polymer latex or the like is usually diluted with water to a polymer concentration of 10 to 20% by mass.
- the reaction is carried out in a vessel equipped with a stirrer while stirring more vigorously than during the reaction.
- the coagulation may be carried out while adding a water-soluble organic compound such as methanol or acetone, an inorganic salt such as potassium nitrate or ammonium carbonate, or an inorganic acid such as hydrochloric acid, sulfuric acid or nitric acid as a coagulant. .
- the coagulation may be performed continuously using an in-line mixer or the like.
- Drying of the wet powder obtained by adhering to the aqueous dispersion of the PTFE polymer is usually carried out in a vacuum or high-frequency wave while keeping the wet powder in a state where it does not flow much, preferably in a stationary state. , Hot air or the like. Friction between powders, especially at high temperatures, generally has an undesirable effect on fine powder type PTFE polymers. This is because particles of this kind of PTFE polymer easily fibrillate even with a small shear force, and lose the original stable particle structure.
- the drying is performed at a drying temperature of 10 to 250 ° C, preferably 100 to 200 ° C.
- the carboxylic acid ester-containing carboxylic acid derivative is usually hydrolyzed to produce a hydrolyzate.
- the obtained PTFE polymer fine powder is preferably used for molding, for example, for hydraulic and fuel tubes for aircraft and automobiles, etc., flexible hoses for chemicals, steam, etc., and electric wires. Coating applications and the like.
- the aqueous dispersion of the PTFE polymer obtained by the above polymerization is further stabilized by condensing a nonionic surfactant, and further concentrated, and, depending on the purpose, an organic or inorganic filler is added. It is also preferable to use the composition as a heated composition for various uses.
- the above composition has a non-adhesive property and a low coefficient of friction by being coated on a substrate made of metal or cellamitas, It can provide a coating film surface with excellent smoothness, abrasion resistance, weather resistance and heat resistance, and is suitable for coating of jars and cooking utensils, impregnation of glass cloth, and the like.
- the polymerization of FEP is usually carried out at a polymerization temperature of 60-100.
- C polymerization pressure 0.7-4. Force to perform at 5MpaG S preferred level.
- FEP also be those modified with further within 0.5 2 mass 0/0 range of the third component and to Pafuruoro (alkyl Bulle ethers) of Yore , total monomers Is also good.
- the carboxylic acid ester bond-containing carboxylic acid derivative can be used in the range of use in the method for producing a fluoropolymer of the present invention, but is usually used in an amount of 0.0001 to 5% by mass of the aqueous medium. Add the amount of
- FEP polymerization of FEP
- a chain transfer agent cyclohexane, methanol, ethanol, carbon tetrachloride, chloroform, chloroform, methylene chloride, methyl chloride, etc.
- ammonium carbonate disodium hydrogen phosphate and the like.
- the polymerization of TFE / perfluoro (alkylbutyl ether) copolymer such as PFA and MFA is usually carried out at a polymerization temperature of 60-100 ° C. It is preferable to carry out at a pressure of 0.7-2.5 MpaG.
- TFE / Pafuruoro (alkyl Bulle ether) preferred monomer composition of the copolymer (Mo Honoré 0/0), TFE: Pafuruoro (alkyl vinyl ether) (95-99 7.): (0.5 3 5), More preferably, it is (98-99.5): (0.52).
- the carboxylic acid ester bond-containing carboxylic acid derivative described above can be used within the range of use in the method for producing a fluoropolymer of the present invention.
- the carboxylic acid ester bond-containing carboxylic acid derivative described above can be used within the range of use in the method for producing a fluoropolymer of the present invention.
- the carboxylic acid ester bond-containing carboxylic acid derivative described above can be used within the range of use in the method for producing a fluoropolymer of the present invention.
- the carboxylic acid ester bond-containing carboxylic acid derivative described above can be used within the range of use in the method for producing a fluoropolymer of the present invention.
- cyclohexane, methanol, ethanol, carbon tetrachloride, chloroform, methylene chloride, methyl chloride, methane, ethane, etc. are used as
- the polymerization of ETFE is usually carried out at a polymerization temperature of 20 to 100 ° C and a polymerization pressure of 0.5 to 0.8 MPaG.
- a third monomer may be further used, and the ETFE may be modified within a range of 0 to 20% by mass of all monomers.
- TFE: ethylene: third monomer (70 98) :( 302) :( 4-110).
- the carboxylic acid ester-containing carboxylic acid derivative described above can be used within the range of use in the method for producing a fluoropolymer of the present invention. — Add 2% by weight.
- ETFE polymerization of ETFE
- the polymerization of the elastomeric polymer is carried out by charging pure water and the carboxylic acid ester bond-containing carboxylic acid derivative into a pressure-resistant reaction vessel equipped with a stirrer, followed by deoxygenation. Thereafter, the monomers are charged, the temperature is adjusted to a predetermined value, and a polymerization initiator is added to start the reaction. As the pressure decreases as the reaction proceeds, additional monomer is continuously or intermittently supplied so as to maintain the initial pressure. When a predetermined amount of the monomer is supplied, the supply is stopped, the monomer in the reaction vessel is purged, and the temperature is returned to room temperature to terminate the reaction.
- the fluoropolymer fine particles are once synthesized at a high carboxylic acid ester bond-containing rubonic acid derivative concentration and then diluted. It is also possible to use a method in which the final polymerization rate can be increased by performing the polymerization as compared with the ordinary polymerization.
- the polymerization of the above-mentioned elastomeric polymer is appropriately selected from the viewpoints of the physical properties of the target polymer and the control of the polymerization rate, but the polymerization temperature is usually -20 to 200 ° C, preferably 5 to 150 ° C.
- the polymerization is carried out at a temperature of 0.5 ° C. and a polymerization pressure of usually 0.5 to 10 MPaG, preferably 17 to 17 MPaG.
- the pH in the polymerization medium is usually maintained at 2.5 to 9 by a known method using a pH adjuster described below.
- the monomers used for the polymerization of the elastomeric polymer include, in addition to vinylidene fluoride,
- fluorine-containing ethylenically unsaturated monomers having at least the same number of fluorine atoms as carbon atoms and copolymerizable with vinylidene fluoride.
- fluorine-containing ethylenically unsaturated monomer include trifluoropropene, pentafluoropropene, hexafluorobutene, and otafluorobutene. Hexafluoropropene is especially preferred because of the elastomeric properties obtained when it blocks the crystal growth of the polymer.
- fluorine-containing ethylenically unsaturated monomer examples include trifluoroethylene, TFE and CTFE, and a fluorine-containing monomer having one or more chlorine and / or bromine substituents. It is also possible to use a monomer. Perfluoro (alkyl biel ether), for example perfluoro (methyl vinyl ether), can also be used. TFE and HFP are preferred for producing elastomeric polymers.
- the above-mentioned carboxylic acid ester-containing rubric acid derivative is used within the range of use in the method for producing the fluoropolymer of the present invention. It is added in an amount of 0.0001% by weight to the medium.
- a known inorganic radical polymerization initiator can be used as the polymerization initiator.
- the inorganic radical polymerization initiator Particularly known water-soluble inorganic peroxides such as sodium, potassium and ammonium persulfates, perphosphates, perborates, percarbonates or permanganates are particularly useful.
- the radical polymerization initiator may further comprise a reducing agent, for example, sodium, potassium or ammonium sulfite, bisulfite, metabisulfite, hyposulfite, thiosulfate, phosphite or hypophosphite.
- a preferred inorganic radical polymerization initiator is ammonium persulfate, more preferably used in a redox system with ammonium persulfate and sodium bisulfite.
- the additive concentration of the polymerization initiator, the molecular weight and the polymer of interest, polymerization reaction rate by connexion forces total monomers are properly determined 0.5 0001- 10 mass 0/0, preferably 0.01 5 wt% Set to quantity.
- any known chain transfer agent can be used.
- hydrocarbons, esters, ethers, alcohols, ketones, chlorine compounds, Carbonates and the like can be used, and in the case of thermoplastic elastomers, hydrocarbons, esters, ethers, alcohols, chlorine compounds, iodine compounds and the like can be used.
- acetone and isopropyl alcohol are preferred.
- isopentane, getyl malonate and ethyl acetate are preferred from the viewpoint that the reaction rate is hardly reduced.
- Diiodine compounds such as I and ICH I can be iodinated at the polymer terminal
- the amount of the chain transfer agent with respect to the total amount of monomers fed usually 0. 5 X 10_ 3 - 5 X 10- 3 mole 0/0, preferably 1. 0 X 10- 3 one 3. 5 X 10- 3, which is a mole 0/0.
- paraffin wax or the like can be preferably used as an emulsion stabilizer in the polymerization of PVDF.
- phosphate or water is used as a pH adjuster.
- Sodium oxide, potassium hydroxide and the like can be preferably used.
- the elastomeric polymer obtained by the process for producing a fluoropolymer of the present invention has a solid content of 10 to 40% by mass and an average particle size of 0.03 lxm at the end of the polymerization.
- the elastomeric polymer obtained by the method for producing a fluoropolymer of the present invention may be obtained by adding a dispersion stabilizer such as a hydrocarbon surfactant, concentrating the dispersion, and the like, if necessary.
- a disposable material suitable for rubber molding can be obtained.
- the dispurgeon is treated by adjusting pH, coagulating, heating and the like. Each process is performed as follows.
- the pH is adjusted by adding a mineral acid such as nitric acid, sulfuric acid, hydrochloric acid, or phosphoric acid, and / or a carboxylic acid having 5 or less carbon atoms and a pK of 4.2 or less, and adjusting the pH to 2 or less. It consists of doing.
- a mineral acid such as nitric acid, sulfuric acid, hydrochloric acid, or phosphoric acid, and / or a carboxylic acid having 5 or less carbon atoms and a pK of 4.2 or less
- the coagulation is performed by adding an alkaline earth metal salt.
- alkaline earth metal salts include nitrates, chlorates and acetates of calcium or magnesium.
- Either the pH adjustment or the coagulation may be performed first, but it is preferable to perform the pH adjustment first.
- washing is performed with the same volume of water as the elastomer, a small amount of impurities such as buffer solution and salt present in the elastomer are removed, and drying is performed. Drying is usually carried out at about 70-200 ° C in a drying oven at high temperature with circulating air.
- the carboxylic acid ester-containing carboxylic acid derivative is usually hydrolyzed to produce a hydrolyzate.
- the carboxylic acid derivative containing a carboxylic acid ester bond can be suitably used also as a dispersant for dispersing a fluorine-containing polymer obtained by polymerization in an aqueous medium.
- the aqueous dispersion is an aqueous dispersion of a fluoropolymer comprising particles made of a fluoropolymer, a carboxylic acid ester bond-containing carboxylic acid derivative, and an aqueous medium.
- particles comprising the fluoropolymer are dispersed in an aqueous medium in the presence of the carboxylic acid ester bond-containing carboxylic acid derivative.
- the carboxylic acid ester bond-containing The carboxylic acid derivative is the same as the carboxylic acid ester-containing carboxylic acid derivative described above in the method for producing a fluoropolymer of the present invention.
- the carboxylic acid ester bond-containing carboxylic acid derivative is preferably one that produces a hydrolyzate by hydrolysis.
- the hydrolyzate generally has volatility and can be removed by heating.
- the hydrolyzate include those exemplified in the description of the method for producing the fluoropolymer of the present invention.
- the heating for example, a coating composition prepared from the fluoropolymer aqueous dispersion of the present invention is applied to a substrate, followed by drying or baking, and the fluoropolymer aqueous dispersion obtained by coagulation. And wet heating and drying in a wet process, pelletizing, and molding using the obtained dry powder and pellets.
- the heating is preferably performed at a temperature of about 10 250 ° C.
- the carboxylic acid ester bond-containing force in the fluoropolymer aqueous dispersion of the present invention is a 2-carboxylic acid derivative represented by the above general formula (1)
- the dicarboxylic acid half ester represented by the formula (2) is preferred because it is easily dispersible from powders, pellets, molded articles, coating films, etc. obtained from the above-mentioned fluoropolymer aqueous dispersion having good dispersibility.
- the carboxylic acid ester bond-containing carboxylic acid derivative is preferably 0.0001 to 15% by mass of the aqueous fluoropolymer dispersion of the present invention. If it is less than 0.0001% by mass, the dispersion stability may be poor. If it exceeds 15% by mass, there is no dispersion effect commensurate with the abundance and it is not practical.
- a more preferred lower limit of the carboxylic acid ester bond-containing carboxylic acid derivative is 0.001% by mass, a more preferred upper limit is 10% by mass, and a still more preferred upper limit is 2% by mass.
- the aqueous fluoropolymer dispersion of the present invention includes an aqueous dispersion obtained by carrying out the above-mentioned polymerization, a dispersion obtained by concentrating or dispersing the aqueous dispersion, and Any powder obtained by dispersing a powder of a fluoropolymer in an aqueous medium in the presence of the carboxylic acid ester bond-containing rubonic acid derivative may be used.
- a known method is employed as the above-mentioned concentration method, and the concentration of the fluoropolymer can be reduced to 4060% by mass depending on the use. Concentration increases stability of dispurgeon
- a dispersion stabilizer may be added. As the dispersion stabilizer, the carboxylic acid ester bond-containing carboxylic acid derivative and other various surfactants may be added.
- dispersion stabilizers examples include nonionic surfactants such as polyoxyalkyl ethers, in particular, polyoxyethylene alkyl phenyl ether (for example, Triton ⁇ ⁇ _ ⁇ (trade name) manufactured by Rohm & Haas Co.), Ability to include polyoxyethylene ethers such as oxyethylene isotridecinoleether (Dispanol TC (trade name) manufactured by NOF Corporation) and polyoxyethylene propyl tridecyl ether
- nonionic surfactants such as polyoxyalkyl ethers, in particular, polyoxyethylene alkyl phenyl ether (for example, Triton ⁇ ⁇ _ ⁇ (trade name) manufactured by Rohm & Haas Co.), Ability to include polyoxyethylene ethers such as oxyethylene isotridecinoleether (Dispanol TC (trade name) manufactured by NOF Corporation) and polyoxyethylene propyl tridecyl ether
- the present invention is not limited to this.
- the total amount of the dispersion stabilizer is 0.5 to 20% by mass based on the solid content of the dispurgeon. If the amount is less than 0.5% by mass, the dispersion stability may be poor. If the amount exceeds 20% by mass, there is no dispersion effect commensurate with the abundance, which is not practical.
- a more preferred lower limit of the dispersion stabilizer is 2% by mass, and a more preferred upper limit is 12% by mass.
- the aqueous dispersion obtained by carrying out the above polymerization may be subjected to a dispersion stabilization treatment without concentrating depending on the use to prepare a long-life fluoropolymer aqueous dispersion. .
- the same dispersion stabilizer as described above can be used.
- aqueous fluoropolymer dispersion of the present invention is not particularly limited, and is applied as it is to an aqueous dispersion, which is applied to a substrate, dried, and then fired as necessary. Coating; impregnating by impregnating and drying a porous support such as a nonwoven fabric or a resin molded product, and preferably baking; coating and drying on a substrate such as glass, and then immersing in water as necessary. And a cast film formed by peeling a substrate to obtain a thin film. Examples of these applications include an aqueous dispersion type paint, a binder for an electrode, and a water repellent for an electrode. .
- the aqueous fluoropolymer dispersion of the present invention may be prepared by compounding a compounding agent such as a known pigment, a thickener, a dispersant, an antifoaming agent, an antifreezing agent, and a film-forming auxiliary, or Further, another polymer compound can be compounded and used as an aqueous coating material for coating.
- a compounding agent such as a known pigment, a thickener, a dispersant, an antifoaming agent, an antifreezing agent, and a film-forming auxiliary
- aqueous fluoropolymer dispersion of the present invention is also obtained by subjecting the aqueous fluoropolymer dispersion to coagulation or aggregation, collecting, drying, and granulating as desired. Applications that use powders are mentioned. For the coagulation or aggregation, a conventionally known method is directly employed. S power
- Rf and M are as defined above. Same as what you did. Rf 2 and Rf may be the same or different.
- the 2_acyloxycarboxylic acid derivative represented by the formula is also one of the present invention.
- the 2-hydroxylcarboxylic acid derivative of the present invention can exhibit surface activity.
- a fluorine-containing polymer is produced by polymerization in an aqueous medium, it is present in the aqueous medium.
- It is suitable as an emulsifier to be used, and also as a dispersant in a fluoropolymer aqueous dispersion in which particles made of a fluoropolymer are dispersed in an aqueous medium.
- the 2-acinoleoxycarboxylic acid derivative of the present invention can be used, for example, as the above-mentioned emulsifier, dispersant, etc., and then recovered and reused.
- the 2-aminocarboxylic acid derivative of the present invention easily undergoes ester hydrolysis by post-treatment such as coagulation performed after the above-mentioned polymerization, and the resulting hydrolyzate usually has a volatile property. And can be removed by heating.
- the heating for example, an aqueous dispersion of the fluoropolymer is dried and fired after applying the prepared coating composition to a substrate, and the aqueous dispersion of the fluoropolymer is obtained by praying. Drying and pelletization of the wet powder obtained, and heating in the forming process using the obtained dry powder and pellets.
- the 2-hydroxylcarboxylic acid derivative of the present invention is obtained by polymerizing a fluorinated polymer.
- the emulsifier at the time of carrying out, while exhibiting surface activity as a dispersant or the like in a fluoropolymer aqueous dispersion can be easily hydrolyzed and removed by a post-treatment, and a powder comprising the obtained fluoropolymer, Since it does not remain in pellets, molded articles, coating films, etc., it is possible to suppress foaming, improve physical properties, prevent coloration, and the like during processing of these molded articles, coating films, and the like.
- the method for producing the 2-acyloxycarboxylic acid derivative of the present invention is not particularly limited, and for example, the following general formula (5)
- Examples of the 2-hydroxycarboxylic acid derivative include (CF) C ( ⁇ H) COOM, (C
- the 2-hydroxycarboxylic acid derivative can be prepared, for example, by the following method.
- a method of producing a 2-hydroxycarboxylic acid ester from fluoroalkenyl ether, and hydrolyzing the ester using a known method to obtain 2-hydroxycarboxylic acid or a salt thereof is obtained, for example, by converting octafluoroisobutene by-produced in the production of hexafluoropropene into an alcohol adduct as a raw material, followed by dehydrofluorination in the next step.
- the resulting heptafluoroisobutenylalkyl ether is [(CF) diene. ! ⁇ ,! ⁇ Represents an alkyl group having 1 to 12 carbon atoms] and the like.
- oxidation reaction for example, an oxidation reaction using RuO in an amount determined from stoichiometry is used.
- the method for esterifying the above 2-hydroxycarboxylic acid derivative is not particularly limited, and for example, the following method can be adopted.
- the method (I) or (II) is preferred from the viewpoint of operability, yield, and the like. Adopted well.
- any of RfCOF, RfC ⁇ Cl, RfCOBr or RfC ⁇ I may be used.
- RfCOCl is preferred.
- a method of producing a 2-acyloxycarboxylic acid derivative by esterification with the alkanol compound represented by the formula (1) is preferable. This method is also one of the present invention.
- This method is the method of the above (I) wherein the halogen force of the halogenated acyl is SF or C1, and the method of the above (II).
- the auxiliaries are preferably used in a range of 0.1 to 2 equivalents to the 2-hydroxycarboxylic acid derivative.
- the dehydrating agent is preferably used in an amount of 0.75 equivalent to the above 2-hydroxycarboxylic acid derivative.
- the dropping amount of RfCOOM 1 to the above 2-hydroxycarboxylic acid derivative is preferably 0.72 equivalent. preferable.
- the above as R 2 in the above RfCOOR 2 for use in the method of (III) is, for example, methyl group, Echiru group, forces methyl group and a propyl group are preferred.
- the 2-hydroxycarboxylic acid derivative of the present invention can be suitably used as a surfactant.
- a surfactant comprising the 2_acinoleoxycarboxylic acid derivative is also included in the present invention.
- the surfactant of the present invention can be used satisfactorily as a surfactant as long as it contains at least one type of 2-hydroxycarboxylic acid derivative represented by the general formula (1). Force It may contain two or more kinds of the above-mentioned 2-hydroxylcarboxylic acid derivatives.
- the surfactant of the present invention may contain one or more compounds having other surfactant properties in addition to the 2_acinoleoxycarboxylic acid derivative.
- the above-mentioned other compounds having a surfactant property are not particularly limited.
- any of anionic, cationic, nonionic and betaine-based surfactants may be used.
- the activator may be a hide mouth carbon type.
- the surfactant of the present invention may contain an additive in addition to the above-mentioned 2-acyloxycarboxylic acid derivative and other optionally used compounds having a surfactant property.
- the additives are not particularly limited, and may be, for example, those usually used for general surfactants such as stabilizers.
- the surfactant of the present invention is composed of the above-mentioned 2-acinoleoxycarboxylic acid derivative, it can exhibit appropriate surface activity in various uses.
- the surfactant of the present invention has an effect of lowering the surface tension by being mixed with various liquids such as water, and the addition amount and the set surface tension can be appropriately determined depending on the purpose. The invention's effect
- the method for producing a fluoropolymer of the present invention has the above-described constitution, the amount of the surfactant remaining in the resin is extremely small, and the fluoropolymer having little coloring and good physical properties is efficiently produced. That can be S. Further, since the aqueous fluoropolymer dispersion of the present invention has the above-described configuration, the fluoropolymer can be stably present, and the coloration is low and the physical properties are low. It is possible to provide a fluoropolymer molded article, a coating film, and the like, which have good properties.
- the 2-acinoleoxycarboxylic acid derivative of the present invention has the above-mentioned constitution, it can be suitably used as a surfactant or the like. Further, since the surfactant of the present invention is composed of the above-mentioned 2-acyloxycarboxylic acid derivative, it has a suitable surface activity.
- This compound is neutralized with aqueous ammonia, and (CF) C (OCOCF CF CF H) COON
- the concentration of (CF) C ( ⁇ C ⁇ CF CF CF CF ⁇ 1) ⁇ 0 ⁇ ⁇ 1 in the obtained aqueous solution was 0.1.
- the surface tension was measured at 25 ° C. by the Wilm-Hermi method in terms of mass%, and was 62 N m / m.
- the mixture was neutralized with aqueous ammonia.
- TFE fluoroethylene
- the internal temperature was set to 70 ° C, TFE was injected so that the internal pressure became 0.78 MPa, and 5 g of a 0.6% by weight aqueous solution of ammonium persulfate [APS] was charged to start the reaction. Since the pressure in the polymerization system decreased as the polymerization proceeded, TFE was continuously added to keep the internal pressure at 0.78 MPa, and the reaction was continued. Stirring was stopped when TFE was added until the resin solid content in the aqueous dispersion became about 5% by mass, and the residual pressure in the tank was returned to normal pressure to terminate the reaction. The following items were measured for this aqueous dispersion. The results are shown in Table 1.
- Solid concentration determined from the weight loss when the obtained aqueous dispersion was dried at 150 ° C. for 1 hour.
- Residual surfactant concentration lg nitric acid was added to 100 g of the obtained aqueous dispersion, and the mixture was stirred at 25 ° C for 15 minutes. The obtained resin powder was washed again with 100 g of water, and then washed at 180 ° C. After drying for 6 hours, a PTFE powder was obtained. This powder lg was dispersed in 20 ml of methanol, extracted under stirring at 50 ° C for 24 hours, and the concentration of the surfactant extracted in methanol was measured by liquid chromatography using Quattro LC (manufactured by Mic romass). / Tandem mass spectrometry (LC / MSZMS) and converted to resin concentration.
- Quattro LC manufactured by Mic romass
- MSZMS Tandem mass spectrometry
- the method for producing a fluoropolymer of the present invention has the above-described constitution, the amount of the surfactant remaining in the resin is extremely small, and the fluoropolymer having little coloring and good physical properties is efficiently produced. That can be S. Further, since the aqueous fluoropolymer dispersion of the present invention has the above-described constitution, the fluoropolymer can be stably present, and the molded product of the fluoropolymer having little coloring and good physical properties can be obtained. And a coating film or the like. Since the 2-acinoleoxycarboxylic acid derivative of the present invention has the above-mentioned constitution, it is suitable as a surfactant or the like. Can be used for Further, since the surfactant of the present invention is composed of the above-mentioned 2-acyloxycarboxylic acid derivative, it has a suitable surface activity.
Abstract
Description
Claims
Priority Applications (4)
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EP04747679A EP1661916A4 (en) | 2003-07-16 | 2004-07-16 | PROCESS FOR PREPARING FLUOROUS POLYMER, AQUEOUS DISPERSION OF FLUOROUS POLYMER, 2-ACYLOXYCARBOXYLENE DERIVATIVE AND TENSID |
US10/564,642 US7569631B2 (en) | 2003-07-16 | 2004-07-16 | Method for producing fluorine-containing polymer, aqueous dispersion of fluorine-containing polymer,2-acyloxycarboxylic acid derivative, and surface active agent |
US12/494,208 US7754796B2 (en) | 2003-07-16 | 2009-06-29 | Method for producing fluorine-containing polymer, aqueous dispersion of fluorine-containing polymer, 2-acyloxycarboxylic acid derivative, and surface active agent. |
US12/788,214 US8067528B2 (en) | 2003-07-16 | 2010-05-26 | Method for producing fluorine-containing polymer, aqueous dispersion of fluorine-containing polymer, 2-acyloxycarboxylic acid derivative, and surface active agent |
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US12/494,208 Division US7754796B2 (en) | 2003-07-16 | 2009-06-29 | Method for producing fluorine-containing polymer, aqueous dispersion of fluorine-containing polymer, 2-acyloxycarboxylic acid derivative, and surface active agent. |
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2004
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- 2004-07-16 WO PCT/JP2004/010214 patent/WO2005007707A1/ja active Application Filing
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2009
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2010
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Also Published As
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US8067528B2 (en) | 2011-11-29 |
EP1661916A4 (en) | 2008-10-01 |
US20100234635A1 (en) | 2010-09-16 |
US7569631B2 (en) | 2009-08-04 |
US7754796B2 (en) | 2010-07-13 |
EP1661916A1 (en) | 2006-05-31 |
US20090264568A1 (en) | 2009-10-22 |
US20060223924A1 (en) | 2006-10-05 |
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