JP2011523946A - 含フッ素ポリエーテルペルオキシド及びそれらの含フッ素単量体の乳化重合における応用 - Google Patents
含フッ素ポリエーテルペルオキシド及びそれらの含フッ素単量体の乳化重合における応用 Download PDFInfo
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- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 39
- 229920000570 polyether Polymers 0.000 title claims abstract description 39
- 239000000178 monomer Substances 0.000 title claims abstract description 37
- 150000002978 peroxides Chemical class 0.000 title claims abstract description 36
- 238000007720 emulsion polymerization reaction Methods 0.000 title description 6
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 67
- 239000011737 fluorine Substances 0.000 claims abstract description 67
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 66
- 239000004094 surface-active agent Substances 0.000 claims abstract description 40
- 239000006185 dispersion Substances 0.000 claims abstract description 34
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 claims description 23
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 150000001336 alkenes Chemical class 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 13
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 8
- 239000004815 dispersion polymer Substances 0.000 claims description 7
- BLTXWCKMNMYXEA-UHFFFAOYSA-N 1,1,2-trifluoro-2-(trifluoromethoxy)ethene Chemical compound FC(F)=C(F)OC(F)(F)F BLTXWCKMNMYXEA-UHFFFAOYSA-N 0.000 claims description 5
- YSYRISKCBOPJRG-UHFFFAOYSA-N 4,5-difluoro-2,2-bis(trifluoromethyl)-1,3-dioxole Chemical compound FC1=C(F)OC(C(F)(F)F)(C(F)(F)F)O1 YSYRISKCBOPJRG-UHFFFAOYSA-N 0.000 claims description 5
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 claims description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 4
- 239000005977 Ethylene Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 238000005502 peroxidation Methods 0.000 claims description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 150000002170 ethers Chemical class 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 26
- 238000000034 method Methods 0.000 abstract description 20
- 150000003839 salts Chemical class 0.000 abstract description 17
- 238000006116 polymerization reaction Methods 0.000 abstract description 15
- 239000003999 initiator Substances 0.000 abstract description 13
- 230000035484 reaction time Effects 0.000 abstract description 12
- SNGREZUHAYWORS-UHFFFAOYSA-N perfluorooctanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F SNGREZUHAYWORS-UHFFFAOYSA-N 0.000 abstract description 9
- 239000000654 additive Substances 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 230000000379 polymerizing effect Effects 0.000 abstract description 4
- 230000000996 additive effect Effects 0.000 abstract description 2
- 230000006698 induction Effects 0.000 abstract description 2
- 239000000126 substance Substances 0.000 description 12
- -1 peroxide carboxylic acid Chemical class 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 6
- 239000011164 primary particle Substances 0.000 description 6
- 229920001519 homopolymer Polymers 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 230000005484 gravity Effects 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000015271 coagulation Effects 0.000 description 3
- 238000005345 coagulation Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- SNGREZUHAYWORS-UHFFFAOYSA-M 2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctanoate Chemical compound [O-]C(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F SNGREZUHAYWORS-UHFFFAOYSA-M 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- YOALFLHFSFEMLP-UHFFFAOYSA-N azane;2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctanoic acid Chemical compound [NH4+].[O-]C(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YOALFLHFSFEMLP-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229920002313 fluoropolymer Polymers 0.000 description 2
- 239000004811 fluoropolymer Substances 0.000 description 2
- 238000005194 fractionation Methods 0.000 description 2
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 2
- 229920002493 poly(chlorotrifluoroethylene) Polymers 0.000 description 2
- 239000005023 polychlorotrifluoroethylene (PCTFE) polymer Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 description 1
- 208000032170 Congenital Abnormalities Diseases 0.000 description 1
- 230000005526 G1 to G0 transition Effects 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 210000003754 fetus Anatomy 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 210000003954 umbilical cord Anatomy 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
- C08G65/22—Cyclic ethers having at least one atom other than carbon and hydrogen outside the ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/002—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds
- C08G65/005—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens
- C08G65/007—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens containing fluorine
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/321—Polymers modified by chemical after-treatment with inorganic compounds
- C08G65/323—Polymers modified by chemical after-treatment with inorganic compounds containing halogens
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions 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; Compositions of derivatives of such polymers
- C08L27/02—Compositions 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; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions 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; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
A-O-(Gf-O)m(Gf-O-O)n-(CF2O)p-(CF2OO)q-(CF(CF3)O)r-B (I)
式中、Gfは-CF2CF(CF3)-又は-CF(CF3)CF2-を表し、
末端基のAは-CF3、-COOM又は-CF2COOMを、Bは-COOM又は-CF2COOMを表し、ここで、Mは-H、-NH4又はアルカリ金属元素を表し、
m、n、p、q、rは下記の条件を満たす:
(1)m、n、p、q、rのいずれも零以上の整数、
(2)n+q = 1、
(3)n+q = m+p+r、
(4)m = n+p+q+r、
(5)分子量の範囲要件を満たす。
酸価:20〜120mgNaOH/g、
過酸化価:0.5%〜10.0%(wt)。
CF3O(CF2CF(CF3)O)(CF2OO)(C(CF3)FO)COONH4
CF3O(CF2CF(CF3)O)(CF2OO)(C(CF3)FO)COOH
CF3O(CF2CF(CF3)O)(CF2OO)(C(CF3)FO)COOK
CF3O(CF2CF(CF3)O)3(CF2CF(CF3)OO)(CF2O)(C(CF3)FO)CF2COONH4
CF3O(CF2CF(CF3)O)3(CF2CF(CF3)OO)(CF2O)(C(CF3)FO)CF2COOH
CF3O(CF2CF(CF3)O)3(CF2CF(CF3)OO)(CF2O)(C(CF3)FO)CF2COOK
CF3O(CF2CF(CF3)O)4(CF2CF(CF3)OO)(CF2O)(CF2OO)(C(CF3)FO)CF2COONH4
CF3O(CF2CF(CF3)O)4(CF2CF(CF3)OO)(CF2O)(CF2OO)(C(CF3)FO)CF2COOH
CF3O(CF2CF(CF3)O)4(CF2CF(CF3)OO)(CF2O)(CF2OO)(C(CF3)FO)CF2COOK
NH4OOCO(CF2CF(CF3)O)3(CF2CF(CF3)OO)(C(CF3)FO)2CF2COONH4
HOOCO(CF2CF(CF3)O)3(CF2CF(CF3)OO)(C(CF3)FO)2CF2COOH
KOOCO(CF2CF(CF3)O)3(CF2CF(CF3)OO)(C(CF3)FO)2CF2COOK
CF3O(CF2CF(CF3)O)(CF2CF(CF3)OO)(C(CF3)FO)COONH4
CF3O(CF2CF(CF3)O)(CF2CF(CF3)OO)(C(CF3)FO)COOH
CF3O(CF2CF(CF3)O)(CF2CF(CF3)OO)(C(CF3)FO)COOK
(1)反応容器に反応溶媒(水又はその他の溶媒)を加え、酸素含量を=20ppmにするように、N2又は反応気体の置換によって反応容器内の酸素を除去する。
(2)含フッ素ポリエーテルペルオキシドを界面活性剤として加え、さらに含フッ素単量体を加え、反応システムの圧力を0.5MPa〜12MPaにコントロールする。
(3)反応システムに添加剤、開始剤を加え、含フッ素単量体の重合反応を発生させ、含フッ素単量体重合分散体を得る。反応の温度は10℃〜150℃で、反応の時間は一般に0.5h〜50hである。
1、ペルフルオロオレフィン類、例えば、テトラフルオロエチレン(TFE)、ヘキサフルオロプロピレン(HFP)など、
2、ハロゲン化オレフィン類、例えば、フッ化ビニリデン(VDF)、クロロトリフルオロエチレン(CTFE)、臭素又はヨウ素化オレフィンなど、
3、フルオロオレフィンエーテル類、例えば、パーフルオロメチルビニルエーテル(PMVE)など、
4、含フッ素複素環二重結合物、例えば、パーフルオロ-2, 2-ジメチル-1, 3-ジオキソール(PDD)など、
5、含フッ素オレフィンと共重合できる非フッ素化オレフィン又は二重結合類化合物、例えば、エチレン、プロピレンなど。
1、ペルフルオロオレフィン類、例えば、テトラフルオロエチレン(TFE)、ヘキサフルオロプロピレン(HFP)など、
2、ハロゲン化オレフィン類、例えば、フッ化ビニリデン(VDF)、クロロトリフルオロエチレン(CTFE)、臭素又はヨウ素化オレフィンなど、
3、フルオロオレフィンエーテル類、例えば、パーフルオロメチルビニルエーテル(PMVE)など、
4、フッ素複素環二重結合物、例えば、パーフルオロ-2, 2-ジメチル-1, 3-ジオキソール(PDD)など、
5、含フッ素オレフィンと共重合できる非フッ素化オレフィン又は二重結合類化合物、例えば、エチレン、プロピレンなど。
1、粒子の平均直径:光散乱法、
2、標準比重:ASTMD-1457方法、
3、固形物の濃度:乾燥条件:150℃、3h、
4、分子量分布:ゲルクロマトグラフィー、
5、ムーニー粘度:GB/T 1232(中国国家標準)、
6、密度:GB/T 533(中国国家標準)、
7、過酸化価:ヨウ素法。
特許GB 1,104,482(1968)の製造方法を参照して、容積が2000mlの、-70℃の還流装置付きの鋼製抗圧反応器に、出力が125Wである紫外ライト(波長が250nm〜400nm)照射装置を設け、反応器と原料を予冷した後、既に予冷した反応器の中に-45℃まで予冷したヘキサフルオロプロピレン(HFP)2000gを加える。反応器の底部に速度20L/hの酸素(O2, 標準状態で計量)及び速度2.5L/hのC2F3Cl(標準状態で計量)の混合気体を加え、反応温度は-45℃に維持し、8h反応させる。その後、紫外ライトの照射を止め、反応を止める。冷凍を止め、HFPを回収する。ケトルにある反応産物を取り出し、攪拌器を備えた容器にいれ、適量の90℃の水を加え加水分解を16h行い、攪拌を止め、静止分層した後油相を取り、加水分解産物665gを得る。前記加水分解産物に対し真空分留を行い、沸点の異なる留分(30℃〜180℃)を取り出し、特定の範囲の酸価及び/又は過酸化価の含フッ素ポリエーテルペルオキシドのカルボン酸604gを得る。ヨウ素法を通じて、各留分範囲の物質の過酸化価を分析し、19FNMRを通じて、製造し得た物質の構成単位と構造を確認する。
容積が50Lの、攪拌器を備えたステンレス鋼製抗圧容器に、脱イオン水32L、パラフィン2000g、界面活性剤のペルフルオロオクタン酸アンモニア50gを加える。まず、窒素で容器の中の酸素を置換する、その後、テトラフルオロエチレン(TFE)単量体で置換を行い、容器の中の酸素含有量を20ppm以下にする。72℃の条件下容器の中の内部圧力が2.0MPaになるようにTFE単量体を加える。さらに、0.05%(質量)の過硫酸アンモニウム(APS)水溶液500g、コハク酸8gを加え、反応を開始させる。反応の進行に伴い、容器の中の内部圧力が低くなり、分散液の固形物の濃度が約30%になるまでに、TFE単量体を継続的に追加し内部圧力を1.9〜2.0MPaに維持する。次に、攪拌を止め、圧力を解放し、反応を終え、TFEホモポリマー水性分散体を得る。反応時間は累計して3.0h、凝析、乾燥などの後続工程は公知のもので、特別な限定はない。
容積が50Lの、攪拌器を備えたステンレス鋼製抗圧容器に、脱イオン水30Lを加える。最初、窒素で容器の中の酸素を置換し、容器の中の酸素含有量を20ppm以下にする。次に、まずフッ化ビニリデン(VDF)とヘキサフルオロプロピレン(HFP)からなる初期混合単量体3Kgを加え、ここで、VDF:HFP=55:45(モル比)、その後、攪拌を行い、且温度の調節を行い、容器の中の温度が90℃の時に、容器の内部圧力が2.3MPaに達するまでVDF:HFP=75:25(モル比)のフッ化ビニリデン(VDF)とヘキサフルオロプロピレン(HFP)からなる混合単量体を補充追加し、界面活性剤のペルフルオロオクタン酸アンモニウム5g、過硫酸カリウム10g、ペルフルオロオクタン酸40ml、マロン酸ジエチル80ml、及びホウ砂30gを加え、反応を開始させる。反応の進行に伴い、容器の中の内部圧力が低くなり、フッ化ビニリデン(VDF)とヘキサフルオロプロピレン(HFP)からなる混合単量体(VDF:HFP=75:25(モル比))を継続的に追加し、内部圧力を2.2〜2.3MPaに維持する。分散液の固形物の濃度が約32%になるように混合単量体を加える。その後、攪拌を止め、圧力を釈放し、反応を終え、フッ化ビニリデン(VDF)とヘキサフルオロプロピレン(HFP)の共重合体水性分散体を得る。反応時間は累計して4h、凝析、乾燥などの後続工程は公知の工程なので、特別な限定はない。
Claims (8)
- 下記一般式で示される、平均分子量が300〜5000の含フッ素ポリエーテルペルオキシド:
A-O-(Gf-O)m(Gf-O-O)n-(CF2O)p-(CF2OO)q-(CF(CF3)O)r-B (I)
式中、Gfは-CF2CF(CF3)-又は-CF(CF3)CF2-を表し;
末端基Aは-CF3、-COOM又は-CF2COOMを表し、Bは-COOM又は-CF2COOMを表し、ここで、Mは-H、-NH4又はアルカリ金属元素を表し;
m、n、p、q、rは下記の条件を満たす:
(1)m、n、p、q、rのいずれも零以上の整数、
(2)n+q = 1、
(3)n+q = m+p+r、
(4)m = n+p+q+r、
(5)分子量の範囲要件を満たす。 - 酸価が20〜120mgNaOH/gであり、過酸化価が0.5wt%〜10.0wt%であることを特徴とする、請求項1に記載の含フッ素ポリエーテルペルオキシド。
- 請求項1または2に記載の含フッ素ポリエーテルペルオキシドを含むものを界面活性剤とすることを特徴とする、含フッ素単量体重合分散体。
- 固形分含有量が15wt%以上、分散体の中に粒子の平均直径が300nm以下であることを特徴とする、請求項3に記載の分散体。
- 界面活性剤の濃度が10wt%以下であることを特徴とする、請求項3に記載の分散体。
- 界面活性剤の用量が0.05wt%〜4wt%であることを特徴とする、請求項5に記載の分散体。
- 界面活性剤の用量が0.05wt%〜0.4wt%であることを特徴とする、請求項5に記載の分散体。
- 含フッ素単量体が下記のものを含むことを特徴とする、請求項5に記載の分散体:
1、テトラフルオロエチレン、ヘキサフルオロプロピレンを含むペルフルオロオレフィン類、
2、フッ化ビニリデン、クロロトリフルオロエチレン、臭素またはヨウ素化オレフィンを含むハロゲン化オレフィン類、
3、パーフルオロメチルビニルエーテルを含むフルオロオレフィンエーテル類、
4、パーフルオロ-2, 2-ジメチル-1, 3-ジオキソールを含む含フッ素複素環二重結合物、
5、エチレン、プロピレンを含む含フッ素オレフィンと共重合できる非フッ素化オレフィンまたは二重結合類化合物。
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