JP2021001264A - Polyacetal copolymer and method for producing the same - Google Patents
Polyacetal copolymer and method for producing the same Download PDFInfo
- Publication number
- JP2021001264A JP2021001264A JP2019115382A JP2019115382A JP2021001264A JP 2021001264 A JP2021001264 A JP 2021001264A JP 2019115382 A JP2019115382 A JP 2019115382A JP 2019115382 A JP2019115382 A JP 2019115382A JP 2021001264 A JP2021001264 A JP 2021001264A
- Authority
- JP
- Japan
- Prior art keywords
- group
- polyacetal copolymer
- acid
- organopolysiloxane
- formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229930182556 Polyacetal Natural products 0.000 title claims abstract description 46
- 229920006324 polyoxymethylene Polymers 0.000 title claims abstract description 46
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 20
- 150000001875 compounds Chemical class 0.000 claims abstract description 18
- -1 cyclic acetal compound Chemical class 0.000 claims abstract description 16
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 14
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims abstract description 10
- 125000005702 oxyalkylene group Chemical group 0.000 claims abstract description 10
- 150000004756 silanes Chemical class 0.000 claims abstract description 10
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract description 9
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 12
- 239000002685 polymerization catalyst Substances 0.000 claims description 12
- 238000010538 cationic polymerization reaction Methods 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- 230000000379 polymerizing effect Effects 0.000 claims description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 238000004581 coalescence Methods 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 abstract description 24
- 239000002253 acid Substances 0.000 description 25
- 238000000034 method Methods 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 4
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 4
- 239000002841 Lewis acid Substances 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000011964 heteropoly acid Substances 0.000 description 3
- 150000007517 lewis acids Chemical class 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 150000007514 bases Chemical class 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000012986 chain transfer agent Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical group C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 2
- 239000012765 fibrous filler Substances 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical class COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 2
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 description 2
- 230000037048 polymerization activity Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- GKNWQHIXXANPTN-UHFFFAOYSA-N 1,1,2,2,2-pentafluoroethanesulfonic acid Chemical compound OS(=O)(=O)C(F)(F)C(F)(F)F GKNWQHIXXANPTN-UHFFFAOYSA-N 0.000 description 1
- XBWQFDNGNOOMDZ-UHFFFAOYSA-N 1,1,2,2,3,3,3-heptafluoropropane-1-sulfonic acid Chemical compound OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)F XBWQFDNGNOOMDZ-UHFFFAOYSA-N 0.000 description 1
- AUAGGMPIKOZAJZ-UHFFFAOYSA-N 1,3,6-trioxocane Chemical compound C1COCOCCO1 AUAGGMPIKOZAJZ-UHFFFAOYSA-N 0.000 description 1
- MFXWQGHKLXJIIP-UHFFFAOYSA-N 1-bromo-3,5-difluoro-2-methoxybenzene Chemical compound COC1=C(F)C=C(F)C=C1Br MFXWQGHKLXJIIP-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- HPILSDOMLLYBQF-UHFFFAOYSA-N 2-[1-(oxiran-2-ylmethoxy)butoxymethyl]oxirane Chemical compound C1OC1COC(CCC)OCC1CO1 HPILSDOMLLYBQF-UHFFFAOYSA-N 0.000 description 1
- WPMYUUITDBHVQZ-UHFFFAOYSA-M 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=CC(CCC([O-])=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-M 0.000 description 1
- MECNWXGGNCJFQJ-UHFFFAOYSA-N 3-piperidin-1-ylpropane-1,2-diol Chemical compound OCC(O)CN1CCCCC1 MECNWXGGNCJFQJ-UHFFFAOYSA-N 0.000 description 1
- 229910021630 Antimony pentafluoride Inorganic materials 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 230000000735 allogeneic effect Effects 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- VBVBHWZYQGJZLR-UHFFFAOYSA-I antimony pentafluoride Chemical compound F[Sb](F)(F)(F)F VBVBHWZYQGJZLR-UHFFFAOYSA-I 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical class [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- ZZNQQQWFKKTOSD-UHFFFAOYSA-N diethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OCC)(OCC)C1=CC=CC=C1 ZZNQQQWFKKTOSD-UHFFFAOYSA-N 0.000 description 1
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 1
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 description 1
- CVQVSVBUMVSJES-UHFFFAOYSA-N dimethoxy-methyl-phenylsilane Chemical compound CO[Si](C)(OC)C1=CC=CC=C1 CVQVSVBUMVSJES-UHFFFAOYSA-N 0.000 description 1
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 description 1
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- RSIHJDGMBDPTIM-UHFFFAOYSA-N ethoxy(trimethyl)silane Chemical compound CCO[Si](C)(C)C RSIHJDGMBDPTIM-UHFFFAOYSA-N 0.000 description 1
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- AKRQHOWXVSDJEF-UHFFFAOYSA-N heptane-1-sulfonic acid Chemical compound CCCCCCCS(O)(=O)=O AKRQHOWXVSDJEF-UHFFFAOYSA-N 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000000415 inactivating effect Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 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
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- POPACFLNWGUDSR-UHFFFAOYSA-N methoxy(trimethyl)silane Chemical compound CO[Si](C)(C)C POPACFLNWGUDSR-UHFFFAOYSA-N 0.000 description 1
- RJMRIDVWCWSWFR-UHFFFAOYSA-N methyl(tripropoxy)silane Chemical compound CCCO[Si](C)(OCCC)OCCC RJMRIDVWCWSWFR-UHFFFAOYSA-N 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 125000005375 organosiloxane group Chemical group 0.000 description 1
- 150000002926 oxygen Chemical class 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- JGTNAGYHADQMCM-UHFFFAOYSA-N perfluorobutanesulfonic acid Chemical compound OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F JGTNAGYHADQMCM-UHFFFAOYSA-N 0.000 description 1
- QZHDEAJFRJCDMF-UHFFFAOYSA-N perfluorohexanesulfonic acid Chemical compound OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F QZHDEAJFRJCDMF-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 1
- OBCUTHMOOONNBS-UHFFFAOYSA-N phosphorus pentafluoride Chemical compound FP(F)(F)(F)F OBCUTHMOOONNBS-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 description 1
- 238000001542 size-exclusion chromatography Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 description 1
- AHJWSRRHTXRLAQ-UHFFFAOYSA-N tetramethoxymethane Chemical compound COC(OC)(OC)OC AHJWSRRHTXRLAQ-UHFFFAOYSA-N 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- GYZQBXUDWTVJDF-UHFFFAOYSA-N tributoxy(methyl)silane Chemical compound CCCCO[Si](C)(OCCCC)OCCCC GYZQBXUDWTVJDF-UHFFFAOYSA-N 0.000 description 1
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- PYOKUURKVVELLB-UHFFFAOYSA-N trimethyl orthoformate Chemical compound COC(OC)OC PYOKUURKVVELLB-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- WQEVDHBJGNOKKO-UHFFFAOYSA-K vanadic acid Chemical compound O[V](O)(O)=O WQEVDHBJGNOKKO-UHFFFAOYSA-K 0.000 description 1
- 238000005406 washing Methods 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
- C08G2/00—Addition polymers of aldehydes or cyclic oligomers thereof or of ketones; Addition copolymers thereof with less than 50 molar percent of other substances
- C08G2/18—Copolymerisation of aldehydes or ketones
- C08G2/24—Copolymerisation of aldehydes or ketones with acetals
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
Description
本発明は、生産性、機械的特性に優れた新規なポリアセタール共重合体およびその製造方法に関する。 The present invention relates to a novel polyacetal copolymer having excellent productivity and mechanical properties, and a method for producing the same.
ポリアセタール樹脂は、機械的特性、熱的特性、電気的特性、摺動性、成形性等において、優れた特性を持っており、主に構造材料や機構部品等として電気機器、自動車部品、精密機械部品等に広く使用されている。しかし、ポリアセタール樹脂が利用される分野の拡大に伴い、要求特性は益々高度化、複合化、特殊化する傾向にある。そのような要求特性として、ポリアセタール樹脂が本来有する優れた摺動性、外観等を維持したまま、機械的強度に対し一層の向上が要求される。 Polyacetal resin has excellent properties in mechanical properties, thermal properties, electrical properties, slidability, moldability, etc., and is mainly used as structural materials and mechanical parts for electrical equipment, automobile parts, precision machinery, etc. Widely used for parts, etc. However, as the fields in which polyacetal resins are used expand, the required characteristics tend to become more sophisticated, composite, and specialized. As such required characteristics, further improvement in mechanical strength is required while maintaining the excellent slidability, appearance, etc. inherent in the polyacetal resin.
これに対し、単に剛性を向上させるだけの目的であれば、ポリアセタール樹脂に繊維状フィラー等を充填する方法が一般的であるが、この方法では、繊維状フィラー等の充填による成形品の外観不良や摺動特性の低下等の問題、更には靱性低下の問題がある。 On the other hand, for the purpose of simply improving the rigidity, a method of filling the polyacetal resin with a fibrous filler or the like is common, but in this method, the appearance of the molded product is poor due to the filling of the fibrous filler or the like. There are problems such as deterioration of sliding characteristics and toughness.
また、ポリアセタール共重合体では、コモノマー量を減少させることにより、摺動性や外観を実質的に損なうことなく剛性を向上させることが知られているが、コモノマー減量の手法においては、靱性が低下するのみならずポリマーの熱安定性も低下する等の問題が生じ、必ずしも要求に応え得るものではなかった。 Further, it is known that the polyacetal copolymer improves the rigidity without substantially impairing the slidability and appearance by reducing the amount of comonomer, but the toughness is lowered in the method of reducing the amount of comonomer. Not only that, but also the thermal stability of the polymer is lowered, which causes problems, and it is not always possible to meet the demand.
分岐構造導入による剛性向上も試みられているが、コモノマーの種類によっては、カチオン重合触媒、特にプロトン酸を重合触媒とする場合に、重合開始が遅れ、突然爆発的に重合が起こってしまうことがあり、生産安定性の面からも課題があった。 Attempts have been made to improve the rigidity by introducing a branched structure, but depending on the type of comonomer, when a cationic polymerization catalyst, especially a protonic acid, is used as the polymerization catalyst, the start of polymerization may be delayed and polymerization may suddenly occur explosively. There was also a problem in terms of production stability.
例えば、ポリアセタール共重合体に関して、トリオキサンと、１分子中にグリシジルエーテル基を２個以上有する化合物とを共重合させた共重合体が提案されている（特許文献１）。しかし、グリシジルエーテル基に代表されるエポキシ基とエーテル酸素を官能基として複数個有する化合物を重合に使用する場合、重合安定性に課題が残っている。特にプロトン酸を重合触媒に使用した場合、低触媒量では重合が起こらず、触媒量を上げると、不定期な誘導期ののち、突然激しい重合反応が起こる現象が発生し、重合制御を難しくしている。 For example, with respect to a polyacetal copolymer, a copolymer obtained by copolymerizing a trioxane with a compound having two or more glycidyl ether groups in one molecule has been proposed (Patent Document 1). However, when a compound having a plurality of epoxy groups represented by glycidyl ether groups and ether oxygen as functional groups is used for polymerization, there remains a problem in polymerization stability. In particular, when protonic acid is used as a polymerization catalyst, polymerization does not occur at a low catalytic amount, and when the amount of catalyst is increased, a phenomenon occurs in which a violent polymerization reaction suddenly occurs after an irregular induction period, making polymerization control difficult. ing.
本発明の目的は、生産性、機械的特性に優れた新規なポリアセタール共重合体の製造方法を提供することにある。 An object of the present invention is to provide a novel method for producing a polyacetal copolymer having excellent productivity and mechanical properties.
本発明の目的は、下記によって達成された。
１． 少なくとも、トリオキサン（Ａ）、炭素数２以上のオキシアルキレン基を環内に有する環状アセタール化合物（Ｂ）およびオルガノポリシロキサン（Ｃ）、とを重合反応させたポリアセタール共重合体であって、該オルガノポリシロキサン（Ｃ）が、下記式（１）で表される化合物から選ばれる一種以上のシラン化合物の縮合物であって、アルコキシ基を有する化合物である、ポリアセタール共重合体。
Ｒ１ ｎＳｉ（ＯＲ２）４−ｎ （１）
式（１）においてＲ１は一価炭化水素基を表し、Ｒ２は炭素数４以下のアルキル基を表す。ｎは０〜３の整数である。
２． 前記式（１）におけるＲ２がメチル基およびエチル基から選ばれる少なくとも一種である前記１に記載のポリアセタール共重合体。
３． 前記式（１）におけるＲ１がメチル基またはフェニル基から選ばれる少なくとも一種である前記１または２記載のポリアセタール共重合体。
４． 少なくとも、トリオキサン（Ａ）、炭素数２以上のオキシアルキレン基を環内に有する環状アセタール化合物（Ｂ）およびオルガノポリシロキサン（Ｃ）、とを、カチオン重合触媒の存在下重合反応させたポリアセタール共重合体の製造方法であって、該オルガノポリシロキサン（Ｃ）が、下記式（１）で表される化合物から選ばれる一種以上のシラン化合物の縮合物であって、アルコキシ基を有する化合物である、ポリアセタール共重合体の製造方法。
Ｒ１ ｎＳｉ（ＯＲ２）４−ｎ （１）
式（１）においてＲ１は一価炭化水素基を表し、Ｒ２は炭素数４以下のアルキル基を表す。ｎは０〜３の整数である。
An object of the present invention has been achieved by:
1. 1. A polyacetal copolymer obtained by polymerizing at least trioxane (A), a cyclic acetal compound (B) having an oxyalkylene group having 2 or more carbon atoms in a ring, and an organopolysiloxane (C), and the organoxane. A polyacetal copolymer in which polysiloxane (C) is a condensate of one or more silane compounds selected from the compounds represented by the following formula (1) and is a compound having an alkoxy group.
R 1 n Si (OR 2 ) 4-n (1)
In the formula (1), R 1 represents a monovalent hydrocarbon group, and R 2 represents an alkyl group having 4 or less carbon atoms. n is an integer from 0 to 3.
2. 2. The polyacetal copolymer according to 1 above, wherein R 2 in the formula (1) is at least one selected from a methyl group and an ethyl group.
3. 3. The polyacetal copolymer according to 1 or 2 above, wherein R 1 in the formula (1) is at least one selected from a methyl group or a phenyl group.
4. A polyacetal co-weight obtained by polymerizing at least trioxane (A), a cyclic acetal compound (B) having an oxyalkylene group having 2 or more carbon atoms in a ring, and an organopolysiloxane (C) in the presence of a cationic polymerization catalyst. A method for producing a coalescence, wherein the organopolysiloxane (C) is a condensate of one or more silane compounds selected from the compounds represented by the following formula (1), and is a compound having an alkoxy group. A method for producing a polyacetal copolymer.
R 1 n Si (OR 2 ) 4-n (1)
In the formula (1), R 1 represents a monovalent hydrocarbon group, and R 2 represents an alkyl group having 4 or less carbon atoms. n is an integer from 0 to 3.
本発明によると、生産性、機械的特性に優れた新規なポリアセタール共重合体およびそのポリアセタール共重合体の製造方法を提供することができる。 According to the present invention, it is possible to provide a novel polyacetal copolymer having excellent productivity and mechanical properties and a method for producing the polyacetal copolymer thereof.
以下、本発明の具体的な実施形態について、詳細に説明するが、本発明は、以下の実施形態に何ら限定されるものではなく、本発明の目的の範囲内において、適宜変更を加えて実施することができる。 Hereinafter, specific embodiments of the present invention will be described in detail, but the present invention is not limited to the following embodiments, and the present invention is carried out with appropriate modifications within the scope of the object of the present invention. can do.
＜ポリアセタール共重合体＞
本発明のポリアセタール共重合体は、トリオキサン（Ａ）、炭素数２以上のオキシアルキレン基を環内に有する環状アセタール化合物（Ｂ）および特定の一種以上のシラン化合物の縮合物であって、アルコキシ基を有するオルガノポリシロキサン（Ｃ）とを重合反応させた共重合体であることを特徴とする。
<Polyacetal copolymer>
The polyacetal copolymer of the present invention is a condensate of trioxane (A), a cyclic acetal compound (B) having an oxyalkylene group having 2 or more carbon atoms in a ring, and a specific one or more silane compounds, and has an alkoxy group. It is a copolymer obtained by polymerizing and reacting with an organopolysiloxane (C) having.
本発明のポリアセタール共重合体は、複数のポリアセタール分子の末端がオルガノポリシロキサンと結合した構造を含んでいるため、それにより機械的特性に優れるもの考えられる。 Since the polyacetal copolymer of the present invention contains a structure in which the ends of a plurality of polyacetal molecules are bonded to organopolysiloxane, it is considered that the polyacetal copolymer is excellent in mechanical properties.
≪トリオキサン（Ａ）≫
本発明において用いられるトリオキサン（Ａ）とは、ホルムアルデヒドの環状三量体であり、一般的には酸性触媒の存在下でホルムアルデヒド水溶液を反応させることによって得られ、これを蒸留等の方法で精製して用いられる。
≪Trioxan (A) ≫
The trioxane (A) used in the present invention is a cyclic trimer of formaldehyde, which is generally obtained by reacting an aqueous formaldehyde solution in the presence of an acidic catalyst, and is purified by a method such as distillation. Is used.
≪炭素数２以上のオキシアルキレン基を環内に有する環状アセタール化合物（Ｂ）≫
本発明において、炭素数２以上のオキシアルキレン基を環内に有する環状アセタール化合物（Ｂ）をコモノマーとして用いることが可能である。
<< Cyclic acetal compound (B) having an oxyalkylene group having 2 or more carbon atoms in the ring >>
In the present invention, the cyclic acetal compound (B) having an oxyalkylene group having 2 or more carbon atoms in the ring can be used as a comonomer.
本発明の炭素数２以上のオキシアルキレン基を環内に有する環状アセタール化合物とは、ポリアセタール共重合体の製造においてコモノマーとして一般に使用される化合物である、具体的には、１，３−ジオキソラン、１，３，６−トリオキソカン、１，４−ブタンジオールホルマール等が挙げられる。 The cyclic acetal compound having an oxyalkylene group having 2 or more carbon atoms in the ring of the present invention is a compound generally used as a comonomer in the production of a polyacetal copolymer, specifically 1,3-dioxolane. Examples thereof include 1,3,6-trioxocan and 1,4-butanediol formal.
本発明において、（Ｂ）成分は、トリオキサン１００質量部に対して０．０１〜２０質量部の範囲となるように使用するのが好ましく、さらに好ましくは０．０５〜５質量部の範囲である。 In the present invention, the component (B) is preferably used in the range of 0.01 to 20 parts by mass with respect to 100 parts by mass of trioxane, and more preferably in the range of 0.05 to 5 parts by mass. ..
≪式（１）で表されるシラン化合物から選ばれる一種以上のシラン化合物を縮合させることで得られ、アルコキシ基を有するオルガノポリシロキサン（Ｃ）≫
Ｒ１ ｎＳｉ（ＯＲ２）４−ｎ （１）
式（１）においてＲ１は一価炭化水素基を表し、Ｒ２は炭素数４以下のアルキル基を表す。ｎは０〜３の整数である。
<< Organopolysiloxane (C) obtained by condensing one or more silane compounds selected from the silane compounds represented by the formula (1) and having an alkoxy group >>
R 1 n Si (OR 2 ) 4-n (1)
In the formula (1), R 1 represents a monovalent hydrocarbon group, and R 2 represents an alkyl group having 4 or less carbon atoms. n is an integer from 0 to 3.
式（１）で表されるシラン化合物としては、例えば、フェニルトリメトキシシラン、メチルトリメトキシシラン、メチルトリエトキシシラン、メチルトリプロポキシシラン、メチルトリブトキシシラン、エチルトリメトキシシラン、エチルトリエトキシシラン、テトラメトキシシラン、テトラエトキシシラン、テトラプロポキシシラン、テトラブトキシシラン、メチルフェニルジメトキシシラン、トリメチルメトキシシラン、トリメチルエトキシシラン、ジメチルジメトキシシラン、ジメチルジエトキシシラン、ジフェニルジメトキシシラン、ジフェニルジエトキシシランなどが挙げられる。 Examples of the silane compound represented by the formula (1) include phenyltrimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, and ethyltriethoxysilane. Examples thereof include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methylphenyldimethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, and diphenyldiethoxysilane. ..
本発明のオルガノポリシロキサン（Ｃ）は、式（１）で表されるシラン化合物から選ばれる一種以上のシラン化合物を公知の縮合反応触媒、具体的には酸触媒、塩基触媒、有機金属化合物触媒などを用いて、縮合させることにより得られる。 The organopolysiloxane (C) of the present invention is a known condensation reaction catalyst, specifically, an acid catalyst, a base catalyst, or an organic metal compound catalyst, in which one or more silane compounds selected from the silane compounds represented by the formula (1) are known. It is obtained by condensing with or the like.
具体的には、例えば、特許２９０４３１７号公報や同３３８９３３８号公報等に記載の方法で（アルコキシ）シラン化合物を部分加水分解縮合し、本発明の効果を生ずる程度のアルコキシ基を含有するものである。 Specifically, for example, the (alkoxy) silane compound is partially hydrolyzed and condensed by the method described in Japanese Patent No. 2904317, Japanese Patent No. 3389338, etc., and contains an alkoxy group to the extent that the effect of the present invention is obtained. ..
本発明のオルガノポリシロキサン（Ｃ）がアルコキシ基を有することは、オルガノポリシロキサン中のアルコキシ基を定量することによって知ることができる。例えば、２９Ｓｉ−ＮＭＲ測定やＫＯＨを加えて熱分解した際に生成するアルコール量で定量することができる。 The fact that the organopolysiloxane (C) of the present invention has an alkoxy group can be known by quantifying the alkoxy group in the organopolysiloxane. For example, it can be quantified by 29 Si-NMR measurement or the amount of alcohol produced when KOH is added and thermally decomposed.
本発明のオルガノポリシロキサン（Ｃ）は、アルコキシ基と場合により炭化水素基を含有しかつシロキサン骨格を有する化合物である。アルコキシ基の具体例としては、例えば、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基が挙げられる。 The organopolysiloxane (C) of the present invention is a compound containing an alkoxy group and optionally a hydrocarbon group and having a siloxane skeleton. Specific examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.
上記炭化水素基の具体例としてはメチル基、エチル基、プロピル基等の飽和炭化水素基やフェニル基、ナフチル基等の芳香族炭化水素基が挙げられる。
本発明のオルガノポリシロキサン（Ｃ）にかかわる前記式（１）におけるＲ２は得られるポリアセタール共重合体の機械物性の観点からメチル基およびエチル基から選ばれる少なくとも１種であることが好ましい。
Specific examples of the above-mentioned hydrocarbon group include saturated hydrocarbon groups such as methyl group, ethyl group and propyl group, and aromatic hydrocarbon groups such as phenyl group and naphthyl group.
R 2 in the above formula (1) relating to the organopolysiloxane (C) of the present invention is preferably at least one selected from a methyl group and an ethyl group from the viewpoint of the mechanical properties of the obtained polyacetal copolymer.
また、前記オルガノポリシロキサン（Ｃ）にかかわる前記式（１）におけるＲ１は得られるポリアセタール共重合体の機械物性の観点からメチル基もしくはフェニル基から選ばれる少なくとも一つであることが好ましい。 Further, R 1 in the formula (1) relating to the organopolysiloxane (C) is preferably at least one selected from a methyl group or a phenyl group from the viewpoint of mechanical properties of the obtained polyacetal copolymer.
本発明のオルガノポリシロキサン（Ｃ）の市販品としては、例えば、「ＳＲ２４０２Ｒｅｓｉｎ」、「ＡＹ４２−１６３」、「ＤＣ−３０７４ｉｎｔｅｒｍｅｄｉａｔｅ」及び「ＤＣ−３０３７ｉｎｔｅｒｍｅｄｉａｔｅ」（以上、ダウ・東レ株式会社製）、「ＫＣ−８９Ｓ」、「ＫＲ−５００」、「Ｘ−４０−９２２５」、「Ｘ−４０−９２４６」、「Ｘ−４０−９２５０」、「ＫＲ−９２１８」、「ＫＲ−２１３」、「ＫＲ−５１０」、「Ｘ−４０−９２２７」、「Ｘ−４０−９２４７」、「ＫＲ−４０１Ｎ」（以上、信越化学工業株式会社製）等が挙げられる。 Examples of commercially available products of the organopolysiloxane (C) of the present invention include "SR2402Resin", "AY42-163", "DC-3074intermediate" and "DC-3037intermediate" (all manufactured by Dow Toray Co., Ltd.). KC-89S "," KR-500 "," X-40-9225 "," X-40-9246 "," X-40-9250 "," KR-9218 "," KR-213 "," KR- "510", "X-40-9227", "X-40-9247", "KR-401N" (all manufactured by Shin-Etsu Chemical Co., Ltd.) and the like can be mentioned.
本発明において、（Ｃ）成分は重合反応において連鎖移動剤として機能していると考えられる。その結果、トリオキサン（Ａ）、炭素数２以上のオキシアルキレン基を環内に有する環状アセタール化合物（Ｂ）および前記オルガノシロキサン（Ｃ）との重合反応を行う際に重合の制御が容易となり、生産性が向上すると考えられる。 In the present invention, the component (C) is considered to function as a chain transfer agent in the polymerization reaction. As a result, the polymerization can be easily controlled when the polymerization reaction is carried out with the trioxane (A), the cyclic acetal compound (B) having an oxyalkylene group having 2 or more carbon atoms in the ring, and the organosiloxane (C), and the production becomes easy. It is thought that the sex will improve.
本発明において、（Ｃ）成分は、トリオキサン（Ａ）１００質量部に対して０．０１〜５質量部の範囲となるように使用するのが好ましく、さらに好ましくは０．０３〜１質量部の範囲である。 In the present invention, the component (C) is preferably used so as to be in the range of 0.01 to 5 parts by mass with respect to 100 parts by mass of trioxane (A), and more preferably 0.03 to 1 part by mass. The range.
＜カチオン重合触媒＞
カチオン重合触媒としては、トリオキサン（Ａ）を主モノマーとするカチオン共重合において公知の重合触媒が使用できる。代表的には、プロトン酸、ルイス酸、が挙げられる。特にプロトン酸であることが好ましい。
<Cationic polymerization catalyst>
As the cationic polymerization catalyst, a polymerization catalyst known for cationic copolymerization using trioxane (A) as a main monomer can be used. Typical examples include protonic acid and Lewis acid. Particularly, it is preferably a protonic acid.
≪プロトン酸≫
プロトン酸としては、パーフルオロアルカンスルホン酸、ヘテロポリ酸、イソポリ酸等が挙げられる。パーフルオロアルカンスルホン酸の具体例として、トリフルオロメタンスルホン酸、ペンタフルオロエタンスルホン酸、ヘプタフルオロプロパンスルホン酸、ノナフルオロブタンスルホン酸、ウンデカフルオロペンタンスルホン酸、トリデカフルオロヘキサンスルホン酸、ペンタデカフルオロへプタンスルホン酸、ヘプタデカフルオロオクタンスルホン酸が挙げられる。
≪Protonic acid≫
Examples of the protonic acid include perfluoroalkanesulfonic acid, heteropolyacid, isopolyacid and the like. Specific examples of perfluoroalcan sulfonic acid include trifluoromethanesulfonic acid, pentafluoroethanesulfonic acid, heptafluoropropanesulfonic acid, nonafluorobutanesulfonic acid, undecafluoropentanesulfonic acid, tridecafluorohexanesulfonic acid, and pentadecafluoro. Examples thereof include heptane sulfonic acid and heptadecafluorooctane sulfonic acid.
ヘテロポリ酸とは、異種の酸素酸が脱水縮合して生成するポリ酸をいい、中心に特定の異種元素が存在し、酸素原子を共有して縮合酸基が縮合してできる単核又は複核の錯イオンを有する。イソポリ酸とは、イソ多重酸、同核縮合酸、同種多重酸とも称され、Ｖ価又はＶＩ価の単一種類の金属を有する無機酸素酸の縮合体から成る高分子量の無機酸素酸をいう。 Heteropolyacid refers to a polyacid produced by dehydration condensation of different types of oxygen acids, which is mononuclear or dinuclear formed by the presence of a specific different element in the center and the condensation of condensed acid groups sharing oxygen atoms. Has complex ions. The isopolyacid is also referred to as an isopolyxic acid, a homonuclear condensate acid, or an allogeneic multiplex acid, and refers to a high molecular weight inorganic oxygen acid composed of a condensate of an inorganic oxygen acid having a single type of metal having a V valence or a VI valence. ..
ヘテロポリ酸の具体例として、リンモリブデン酸、リンタングステン酸、リンモリブドタングステン酸、リンモリブドバナジン酸、リンモリブドタングストバナジン酸、リンタングストバナジン酸、ケイタングステン酸、ケイモリブデン酸、ケイモリブドタングステン酸、ケイモリブドタングステントバナジン酸等が挙げられる。特に、重合活性の観点から、ヘテロポリ酸は、ケイモリブデン酸、ケイタングステン酸、リンモリブデン酸、リンタングステン酸から選択されることが好ましい。 Specific examples of heteropolyacids include phosphomolybdic acid, phosphotungstic acid, phosphomolybdate tungstic acid, phosphomolybd vanadic acid, phosphomolybd tongue tungstic acid, phosphotungstic acid, phytotungstic acid, silicate molybdate, and phymolybd. Examples thereof include tungstic acid and molybdate tungsten tungstic acid. In particular, from the viewpoint of polymerization activity, the heteropolyacid is preferably selected from silicolybdic acid, silicotungstic acid, phosphomolybdic acid, and phosphotungstic acid.
イソポリ酸の具体例として、パラタングステン酸、メタタングステン酸等に例示されるイソポリタングステン酸、パラモリブデン酸、メタモリブデン酸等に例示されるイソポリモリブデン酸、メタポリバナジウム酸、イソポリバナジウム酸等が挙げられる。中でも、重合活性の観点から、イソポリタングステン酸であることが好ましい。 Specific examples of isopolyacids include isopolytungstic acid such as paratungstic acid and metatungstic acid, paramolybdic acid, isopolymolybdic acid such as metamolybdic acid, metapolyvanadium acid, and isopolyvanadium acid. And so on. Of these, isopolytungstic acid is preferable from the viewpoint of polymerization activity.
≪ルイス酸≫
ルイス酸としては、例えば、ホウ素、スズ、チタン、リン、ヒ素及びアンチモンのハロゲン化物が挙げられ、具体的には三フッ化ホウ素（およびそのエーテル錯体）、四塩化スズ、四塩化チタン、五フッ化リン、五塩化リン、五フッ化アンチモン及びその錯化合物又は塩が挙げられる。
≪Lewis acid≫
Examples of the Lewis acid include halides of boron, tin, titanium, phosphorus, arsenic and antimony, and specifically, boron trifluoride (and its ether complex), tin tetrachloride, titanium tetrachloride, and pentafluoride. Phosphorus pentafluoride, phosphorus pentachloride, antimony pentafluoride and complex compounds or salts thereof can be mentioned.
重合触媒の量は特に限定されるものでないが、全モノマーの合計に対して０．１ｐｐｍ以上５０ｐｐｍ以下であることが好ましく、０．１ｐｐｍ以上３０ｐｐｍ以下であることがより好ましい。 The amount of the polymerization catalyst is not particularly limited, but is preferably 0.1 ppm or more and 50 ppm or less, and more preferably 0.1 ppm or more and 30 ppm or less with respect to the total of all the monomers.
本発明においては、上記成分の他に分子量を調整する成分を併用し、末端基量を調整することができる。分子量を調整する成分としては、不安定末端を形成することのない連鎖移動剤、即ち、メチラール、モノメトキシメチラール、ジメトキシメチラール等のアルコキシ基を有する化合物が例示される。 In the present invention, in addition to the above components, a component for adjusting the molecular weight can be used in combination to adjust the amount of terminal groups. Examples of the component for adjusting the molecular weight include a chain transfer agent that does not form an unstable end, that is, a compound having an alkoxy group such as methylal, monomethoxymethylal, and dimethoxymethylal.
本発明で使用する重合装置も特に限定されるものではなく、公知の装置が使用され、バッチ式、連続式等、いずれの方法も可能である。また、重合温度は６５℃以上１３５℃以下に保つことが好ましい。 The polymerization apparatus used in the present invention is not particularly limited, and known apparatus is used, and any method such as batch type or continuous type is possible. Moreover, it is preferable to keep the polymerization temperature at 65 ° C. or higher and 135 ° C. or lower.
カチオン重合触媒は、重合に悪影響のない不活性な溶剤で希釈して使用することが好ましい。 The cationic polymerization catalyst is preferably diluted with an inert solvent that does not adversely affect the polymerization.
重合後の重合触媒の失活は従来公知の方法で行うことができる。例えば、重合反応後、重合機より排出される生成反応物、重合機中の反応生成物に塩基性化合物又はその水溶液等を加えて行うこともできる。 The deactivation of the polymerization catalyst after the polymerization can be carried out by a conventionally known method. For example, after the polymerization reaction, a basic compound or an aqueous solution thereof may be added to the product reaction product discharged from the polymerization machine or the reaction product in the polymerization machine.
重合触媒を中和し失活するための塩基性化合物は、特に限定されるものでない。重合及び失活の後、必要に応じて更に、洗浄、未反応モノマーの分離回収、乾燥等を従来公知の方法にて行う。 The basic compound for neutralizing and inactivating the polymerization catalyst is not particularly limited. After polymerization and deactivation, if necessary, further washing, separation and recovery of unreacted monomers, drying and the like are carried out by conventionally known methods.
上記のようにして得られるポリアセタール共重合体は、サイズ排除クロマトグラフィにて決定されたポリメタクリル酸メチル相当の重量平均分子量が１００００〜５０００００であることが好ましく、特に好ましくは２００００〜１５００００である。また、末端基については、１Ｈ−ＮＭＲにより検出されるヘミホルマール末端基量（例えば、特開２００１−１１１４３公報記載の方法による）が０〜４ｍｍｏｌ／ｋｇであることが好ましく、特に好ましくは０〜２ｍｍｏｌ／ｋｇである。 The polyacetal copolymer obtained as described above preferably has a weight average molecular weight equivalent to methyl polymethacrylate determined by size exclusion chromatography of 1000 to 500,000, and particularly preferably 2000 to 150,000. Regarding the terminal group, the amount of hemiformal terminal group detected by 1 H-NMR (for example, by the method described in JP-A-2001-11143) is preferably 0 to 4 mmol / kg, and particularly preferably 0 to 0. It is 2 mmol / kg.
ヘミホルマール末端基量を上記範囲に制御するためには、重合に供するモノマー、コモノマー総量中の不純物、特に水分を２０ｐｐｍ以下にするのが好ましく、特に好ましくは１０ｐｐｍ以下である。
＜その他成分＞
In order to control the amount of hemiformal terminal groups within the above range, the amount of impurities in the total amount of monomers and comonomer to be polymerized, particularly water content, is preferably 20 ppm or less, particularly preferably 10 ppm or less.
<Other ingredients>
本発明で製造されるポリアセタール共重合体には、必要に応じて選択される公知の各種安定剤を配合するのが好ましい。ここで用いられる安定剤としては、ヒンダードフェノール化合物、窒素含有化合物、アルカリ或いはアルカリ土類金属の水酸化物、無機塩、カルボン酸塩等のいずれか１種または２種以上を挙げることができる。 It is preferable that the polyacetal copolymer produced by the present invention contains various known stabilizers selected as necessary. Examples of the stabilizer used here include any one or more of hindered phenol compounds, nitrogen-containing compounds, hydroxides of alkaline or alkaline earth metals, inorganic salts, carboxylates and the like. ..
更に、本発明で製造されるポリアセタール共重合体には、必要に応じて、熱可塑性樹脂に対する一般的な添加剤、例えば染料、顔料等の着色剤、滑剤、核剤、離型剤、帯電防止剤、界面活性剤、或いは、有機高分子材料、無機または有機の繊維状、粉体状、板状の充填剤等を１種または２種以上添加することができる。 Further, the polyacetal copolymer produced by the present invention contains, if necessary, general additives for thermoplastic resins such as colorants such as dyes and pigments, lubricants, nucleating agents, mold release agents, and antistatic agents. One or more kinds of agents, surfactants, organic polymer materials, inorganic or organic fibrous, powdery, plate-like fillers and the like can be added.
以下、実施例によって本発明を具体的に説明するが、本発明はこれら実施例に限定されるものではない。 Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples.
＜重合反応＞
熱媒を通すことのできるジャケットと撹拌羽根を有する密閉オートクレーブ中に３００ｇのトリオキサン（Ａ）を入れ、さらに（Ｃ）成分として表１に記載の化合物と（Ｂ）成分として１，３−ジオキソラン（ＤＯ）を、それぞれ表１に示した質量部の割合になるように添加した。これら内容物を撹拌し、ジャケットに８０℃の温水を通して内部温度を約８０℃に保った後、触媒として、リンタングステン酸（ＰＷＡ）をギ酸メチル溶液の形で（Ａ）と（Ｂ）の質量の和に対して４．５ｐｐｍまたはトリフルオロメタンスルホン酸（ＴｆＯＨ）をシクロヘキサン溶液の形で（Ａ）と（Ｂ）の質量の和に対して１．０ｐｐｍ添加し、重合反応を行った。実施例６はＴｆＯＨ、それ以外は、ＰＷＡを使用した。
実施例で用いた（Ｃ）成分は（Ｃ−１）ＫＲ−５００（Ｒ１：メチル基、Ｒ２：メチル基）、（Ｃ−２）ＫＲ−４０１Ｎ（Ｒ１：メチル基／フェニル基、Ｒ２：メチル基）（ともに信越化学工業社製）である。実施例、比較例の各成分は、表１に示した。
<Polymerization reaction>
300 g of trioxane (A) was placed in a closed autoclave having a jacket through which a heat medium could pass and a stirring blade, and the compound shown in Table 1 as the component (C) and 1,3-dioxolane as the component (B) ( DO) was added in proportions of parts by mass shown in Table 1. These contents are stirred, and after keeping the internal temperature at about 80 ° C. by passing hot water at 80 ° C. through the jacket, phosphotungstic acid (PWA) is used as a catalyst in the form of a methyl formate solution by the masses of (A) and (B). 4.5 ppm or trifluoromethanesulfonic acid (TfOH) was added in the form of a cyclohexane solution to the sum of the masses of (A) and (B) at 1.0 ppm, and the polymerization reaction was carried out. TfOH was used in Example 6, and PWA was used otherwise.
The components (C) used in the examples were (C-1) KR-500 (R 1 : methyl group, R 2 : methyl group), (C-2) KR-401N (R 1 : methyl group / phenyl group), R 2: is a methyl group) (both manufactured by Shin-Etsu Chemical Co., Ltd.). The components of Examples and Comparative Examples are shown in Table 1.
５分後にこのオートクレーブへトリエチルアミン０．１％を含む水３００ｇを加えて反応を停止し、内容物を取り出して２００メッシュ以下に粉砕し、アセトン洗浄及び乾燥後、ポリアセタール共重合体収率（重合に使用した（Ａ）と（Ｂ）と（Ｃ）の質量の和に対して得られた共重合体質量の割合（質量％））を算出した。この結果を表２に示した。 After 5 minutes, 300 g of water containing 0.1% triethylamine was added to this autoclave to stop the reaction, the contents were taken out, pulverized to 200 mesh or less, washed with acetone and dried, and then the polyacetal copolymer yield (for polymerization). The ratio (% by mass) of the obtained copolymer mass to the sum of the masses of (A), (B) and (C) used) was calculated. The results are shown in Table 2.
比較として下記ジグリシジル化合物（Ｘ−１およびＸ−２）を本発明の（Ｃ）成分に替えて重合に用い、比較のポリアセタール共重合体を得た。 For comparison, the following diglycidyl compounds (X-1 and X-2) were used in the polymerization in place of the component (C) of the present invention to obtain a comparative polyacetal copolymer.
Ｘ−１: ブタンジオールジグリシジルエーテル
Ｘ−２：トリメチロールプロパントリグリシジルエーテル
上記の方法で得たポリアセタール共重合体１００質量部に、安定剤としてペンタエリスリチル−テトラキス〔３−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオネート〕（商品名：Ｉｒｇａｎｏｘ１０１０ ＢＡＳＦ社製）を０．３５質量部、およびメラミン０．１５質量部を添加し、小型２軸押出機にて２１０℃で溶融混練し、ペレット状のポリアセタール樹脂組成物を得た。
これらのペレットを使用し下記の評価を行った。結果を表２に示す。
Pentaerythrityl-tetrax [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (trade name: Irganox1010 BASF) as a stabilizer in 100 parts by mass of the polyacetal copolymer obtained by the above method. 0.35 parts by mass and 0.15 parts by mass of melamine were added and melt-kneaded at 210 ° C. with a small twin-screw extruder to obtain a pellet-shaped polyacetal resin composition.
The following evaluation was performed using these pellets. The results are shown in Table 2.
＜引張強度＞
ＩＳＯ５２７−１、２に準拠し、ＩＳＯＴｙｐｅ１Ａ試験片の引張強度の測定を行った。測定室は、２３℃５０％ＲＨの雰囲気を保持した。
＜曲げ強度および曲げ弾性率＞
ＩＳＯ１７８に準拠し、曲げ強度、及び曲げ弾性率の測定を行った。測定室は、２３℃５０％ＲＨの雰囲気を保持した。
<Tensile strength>
The tensile strength of the ISOType1A test piece was measured according to ISO527-1,2. The measurement room maintained an atmosphere of 23 ° C. and 50% RH.
<Bending strength and flexural modulus>
Bending strength and flexural modulus were measured in accordance with ISO178. The measurement room maintained an atmosphere of 23 ° C. and 50% RH.
実施例１〜７において、低触媒量で、高収率でポリアセタール共重合体が得られ、機械的特性に優れたポリアセタール共重合体であることが明らかになった。比較例２および３では、実施例と同じ触媒量では、重合反応は観測されなかった。比較例２および３において、触媒量を２０ｐｐｍとした場合、突然激しい反応が起こったが、最終的な収率は５０質量％程度と低いものであった。 In Examples 1 to 7, a polyacetal copolymer was obtained in a high yield with a low catalyst amount, and it was clarified that the polyacetal copolymer was excellent in mechanical properties. In Comparative Examples 2 and 3, no polymerization reaction was observed at the same amount of catalyst as in Examples. In Comparative Examples 2 and 3, when the amount of catalyst was 20 ppm, a violent reaction suddenly occurred, but the final yield was as low as about 50% by mass.
表２の結果から明らかなように、本発明によると、生産安定性、機械的特性に優れた新規なポリアセタール共重合体およびそのポリアセタール共重合体の製造方法を提供することができる。
As is clear from the results in Table 2, according to the present invention, it is possible to provide a novel polyacetal copolymer having excellent production stability and mechanical properties, and a method for producing the polyacetal copolymer thereof.
Claims (4)
Ｒ１ ｎＳｉ（ＯＲ２）４−ｎ （１）
式（１）においてＲ１は一価炭化水素基を表し、Ｒ２は炭素数４以下のアルキル基を表す。ｎは０〜３の整数である。 A polyacetal copolymer obtained by polymerizing at least trioxane (A), a cyclic acetal compound (B) having an oxyalkylene group having 2 or more carbon atoms in a ring, and an organopolysiloxane (C), and the organoxane. A polyacetal copolymer in which polysiloxane (C) is a condensate of one or more silane compounds selected from the compounds represented by the following formula (1) and is a compound having an alkoxy group.
R 1 n Si (OR 2 ) 4-n (1)
In the formula (1), R 1 represents a monovalent hydrocarbon group, and R 2 represents an alkyl group having 4 or less carbon atoms. n is an integer from 0 to 3.
Ｒ１ ｎＳｉ（ＯＲ２）４−ｎ （１）
式（１）においてＲ１は一価炭化水素基を表し、Ｒ２は炭素数４以下のアルキル基を表す。ｎは０〜３の整数である。
At least a polyacetal copolymer weight obtained by polymerizing trioxane (A), a cyclic acetal compound (B) having an oxyalkylene group having 2 or more carbon atoms in a ring, and an organopolysiloxane (C) in the presence of a cationic polymerization catalyst. A method for producing a coalescence, wherein the organopolysiloxane (C) is a condensate of one or more silane compounds selected from the compounds represented by the following formula (1), and is a compound having an alkoxy group. A method for producing a polyacetal copolymer.
R 1 n Si (OR 2 ) 4-n (1)
In the formula (1), R 1 represents a monovalent hydrocarbon group, and R 2 represents an alkyl group having 4 or less carbon atoms. n is an integer from 0 to 3.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2019115382A JP2021001264A (en) | 2019-06-21 | 2019-06-21 | Polyacetal copolymer and method for producing the same |
| CN202080028031.1A CN113677725B (en) | 2019-06-21 | 2020-04-10 | Polyacetal copolymer and process for producing the same |
| PCT/JP2020/016075 WO2020255543A1 (en) | 2019-06-21 | 2020-04-10 | Polyacetal copolymer and production method therefor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2019115382A JP2021001264A (en) | 2019-06-21 | 2019-06-21 | Polyacetal copolymer and method for producing the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2021001264A true JP2021001264A (en) | 2021-01-07 |
Family
ID=73995336
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2019115382A Pending JP2021001264A (en) | 2019-06-21 | 2019-06-21 | Polyacetal copolymer and method for producing the same |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP2021001264A (en) |
| CN (1) | CN113677725B (en) |
| WO (1) | WO2020255543A1 (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5145199A (en) * | 1974-10-16 | 1976-04-17 | Shinetsu Chemical Co | NETSUANTEISEIHORIOKISHIMECHIRENNO SEIZOHOHO |
| JPS58174412A (en) * | 1982-04-08 | 1983-10-13 | Asahi Chem Ind Co Ltd | Novel acetal polymer and its preparation |
| JPS6411117A (en) * | 1987-07-02 | 1989-01-13 | Polyplastics Co | Silicon-containing polyacetal copolymer and production thereof |
| JPH09235446A (en) * | 1996-02-28 | 1997-09-09 | Polyplastics Co | Polyoxymethylene composition and molded product thereof |
| WO2000047646A1 (en) * | 1999-02-10 | 2000-08-17 | Polyplastics Co., Ltd. | Process for continuously producing polyacetal resin |
| JP2002234924A (en) * | 2001-02-09 | 2002-08-23 | Polyplastics Co | Polyacetal copolymer and its composition |
| JP2011084702A (en) * | 2009-10-19 | 2011-04-28 | Mitsubishi Gas Chemical Co Inc | Polyacetal copolymer |
| JP2013001710A (en) * | 2011-06-10 | 2013-01-07 | Asahi Kasei Chemicals Corp | Polyacetal block copolymer |
| JP2015193700A (en) * | 2014-03-31 | 2015-11-05 | ポリプラスチックス株式会社 | Method for producing polyacetal copolymer |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102604017B (en) * | 2012-02-28 | 2013-12-04 | 中国科学院化学研究所 | Preparation method of cross-linkable acetal copolymer |
-
2019
- 2019-06-21 JP JP2019115382A patent/JP2021001264A/en active Pending
-
2020
- 2020-04-10 WO PCT/JP2020/016075 patent/WO2020255543A1/en active Application Filing
- 2020-04-10 CN CN202080028031.1A patent/CN113677725B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5145199A (en) * | 1974-10-16 | 1976-04-17 | Shinetsu Chemical Co | NETSUANTEISEIHORIOKISHIMECHIRENNO SEIZOHOHO |
| JPS58174412A (en) * | 1982-04-08 | 1983-10-13 | Asahi Chem Ind Co Ltd | Novel acetal polymer and its preparation |
| JPS6411117A (en) * | 1987-07-02 | 1989-01-13 | Polyplastics Co | Silicon-containing polyacetal copolymer and production thereof |
| JPH09235446A (en) * | 1996-02-28 | 1997-09-09 | Polyplastics Co | Polyoxymethylene composition and molded product thereof |
| WO2000047646A1 (en) * | 1999-02-10 | 2000-08-17 | Polyplastics Co., Ltd. | Process for continuously producing polyacetal resin |
| JP2002234924A (en) * | 2001-02-09 | 2002-08-23 | Polyplastics Co | Polyacetal copolymer and its composition |
| JP2011084702A (en) * | 2009-10-19 | 2011-04-28 | Mitsubishi Gas Chemical Co Inc | Polyacetal copolymer |
| JP2013001710A (en) * | 2011-06-10 | 2013-01-07 | Asahi Kasei Chemicals Corp | Polyacetal block copolymer |
| JP2015193700A (en) * | 2014-03-31 | 2015-11-05 | ポリプラスチックス株式会社 | Method for producing polyacetal copolymer |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113677725B (en) | 2023-12-29 |
| WO2020255543A1 (en) | 2020-12-24 |
| CN113677725A (en) | 2021-11-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPWO2017159602A1 (en) | Method for producing oxymethylene copolymer | |
| WO2020255543A1 (en) | Polyacetal copolymer and production method therefor | |
| JP7222678B2 (en) | Polyacetal resin composition and method for producing polyacetal resin composition | |
| JP7141330B2 (en) | Polyacetal resin composition and method for producing polyacetal resin composition | |
| JP7356828B2 (en) | Polyacetal resin composition and method for producing polyacetal resin composition | |
| JP2016145278A (en) | Polyacetal resin composition | |
| JP7141329B2 (en) | Polyacetal copolymer and method for producing the same | |
| JP7129284B2 (en) | Polyacetal copolymer and method for producing the same | |
| JP7061479B2 (en) | Polyacetal copolymer and its polymerization method | |
| JP7210194B2 (en) | Polyacetal resin composition | |
| JP7339812B2 (en) | Polyacetal resin composition and method for producing the same | |
| JP7179046B2 (en) | Polyacetal copolymer and method for producing the same | |
| WO2023171316A1 (en) | Polyacetal copolymer and method for polymerizing same | |
| JP3933925B2 (en) | Modified polyacetal resin and method for producing the same | |
| JP2004359757A (en) | Polyacetal copolymer | |
| JP2002356603A (en) | Polyacetal resin composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20220516 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20230207 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20230509 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20230731 |
|
| A911 | Transfer to examiner for re-examination before appeal (zenchi) |
Free format text: JAPANESE INTERMEDIATE CODE: A911 Effective date: 20230807 |
|
| A912 | Re-examination (zenchi) completed and case transferred to appeal board |
Free format text: JAPANESE INTERMEDIATE CODE: A912 Effective date: 20231006 |