CN112752778B - Polyacetal copolymer and process for producing the same - Google Patents
Polyacetal copolymer and process for producing the same Download PDFInfo
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- CN112752778B CN112752778B CN201980062380.2A CN201980062380A CN112752778B CN 112752778 B CN112752778 B CN 112752778B CN 201980062380 A CN201980062380 A CN 201980062380A CN 112752778 B CN112752778 B CN 112752778B
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- 229930182556 Polyacetal Natural products 0.000 title claims abstract description 43
- 229920006324 polyoxymethylene Polymers 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims description 16
- -1 siloxane compound Chemical class 0.000 claims abstract description 26
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 21
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 20
- 125000000962 organic group Chemical group 0.000 claims abstract description 18
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 9
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims description 14
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims description 5
- 125000005702 oxyalkylene group Chemical group 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 12
- 238000006116 polymerization reaction Methods 0.000 description 23
- 239000002253 acid Substances 0.000 description 21
- 239000002685 polymerization catalyst Substances 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 9
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 238000010538 cationic polymerization reaction Methods 0.000 description 5
- 229910015900 BF3 Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000011964 heteropoly acid Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 3
- 239000002841 Lewis acid Substances 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical group [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 3
- 150000007517 lewis acids Chemical class 0.000 description 3
- 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 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- WQEVDHBJGNOKKO-UHFFFAOYSA-K vanadic acid Chemical compound O[V](O)(O)=O WQEVDHBJGNOKKO-UHFFFAOYSA-K 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
- 150000007513 acids Chemical class 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000007334 copolymerization reaction Methods 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
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 239000008188 pellet Substances 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
- 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 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- OYGQVDSRYXATEL-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5,6,6,7,7,7-pentadecafluoroheptane-1-sulfonic acid Chemical compound OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F OYGQVDSRYXATEL-UHFFFAOYSA-N 0.000 description 1
- FQERLIOIVXPZKH-UHFFFAOYSA-N 1,2,4-trioxane Chemical compound C1COOCO1 FQERLIOIVXPZKH-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
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 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
- XKTYXVDYIKIYJP-UHFFFAOYSA-N 3h-dioxole Chemical compound C1OOC=C1 XKTYXVDYIKIYJP-UHFFFAOYSA-N 0.000 description 1
- 229910021630 Antimony pentafluoride Inorganic materials 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 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
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-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
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 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
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 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
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-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
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 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
- 150000004820 halides Chemical class 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 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
- ALTWGIIQPLQAAM-UHFFFAOYSA-N metavanadate Chemical compound [O-][V](=O)=O ALTWGIIQPLQAAM-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 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
- 150000002926 oxygen Chemical class 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
- 150000002989 phenols Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 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
- 239000000047 product Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 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
- AHJWSRRHTXRLAQ-UHFFFAOYSA-N tetramethoxymethane Chemical compound COC(OC)(OC)OC AHJWSRRHTXRLAQ-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
- 238000012546 transfer Methods 0.000 description 1
- GTSMGKYOGFOSAR-UHFFFAOYSA-N tridecane-1-sulfonic acid Chemical compound CCCCCCCCCCCCCS(O)(=O)=O GTSMGKYOGFOSAR-UHFFFAOYSA-N 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- 239000013638 trimer Substances 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
- SJEYEFOHSMBQIX-UHFFFAOYSA-N undecane-1-sulfonic acid Chemical compound CCCCCCCCCCCS(O)(=O)=O SJEYEFOHSMBQIX-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 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
- C08G2/22—Copolymerisation of aldehydes or ketones with epoxy compounds
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
The present invention provides a novel polyacetal copolymer having excellent productivity and mechanical properties by introducing a group having a novel structure, and a method for producing the same. The object of the present invention is achieved by the following polyacetal copolymers: which is obtained by copolymerizing at least trioxane and a siloxane compound represented by the formula (1). (in the formula (1), R is respectively 1 Represents a monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms, X represents R 1 Or an organic group having an epoxy group. Wherein more than 2 of X are organic groups having epoxy groups, and R are plural 1 X are optionally the same or different respectively. )
Description
Technical Field
The present invention relates to a novel polyacetal copolymer excellent in productivity and mechanical properties, and a method for producing the same.
Background
Polyacetal resins have excellent properties in terms of mechanical properties, thermal properties, electrical properties, slidability, moldability and the like, and are widely used mainly as structural materials, mechanical parts and the like in electric devices, automobile parts, precision mechanical parts and the like. However, as the application field of polyacetal resins expands, the required properties tend to be increasingly high, complex and specialized. As such a desirable characteristic, further improvement in mechanical strength is demanded while maintaining excellent slidability, appearance, and the like inherent in polyacetal resins.
In contrast, for the purpose of improving rigidity only, a method of filling a fibrous filler or the like into a polyacetal resin is generally used, but this method has problems such as poor appearance and reduced sliding characteristics of a molded article due to the filling of the fibrous filler or the like, and further has a problem of reduced toughness.
In addition, although it is known that the polyacetal copolymer is improved in rigidity without substantially impairing slidability or appearance by reducing the amount of the comonomer, the method of reducing the comonomer has problems such as a decrease in toughness and a decrease in thermal stability of the polymer, and is not necessarily satisfactory.
It has also been attempted to improve rigidity by introducing a branched structure, but when a cationic polymerization catalyst, particularly a protonic acid, is used as a polymerization catalyst, initiation of polymerization may be delayed and polymerization may occur suddenly and explosively depending on the kind of a comonomer, and there is a problem in terms of production stability.
For example, as a polyacetal copolymer, a copolymer obtained by copolymerizing trioxane with a compound having 2 or more glycidyl ether groups in 1 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 groups is used for polymerization, there remains a problem in terms of polymerization stability. In particular, when a protonic acid is used as a polymerization catalyst, polymerization does not occur at a low catalyst amount, and if the catalyst amount is increased, a phenomenon occurs in which a severe polymerization reaction suddenly occurs after an irregular induction period, and it is difficult to control the polymerization.
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open No. 2001-163944
Disclosure of Invention
Problems to be solved by the invention
The present invention provides a novel polyacetal copolymer having excellent productivity and mechanical properties by introducing a group having a novel structure, and a method for producing the same.
Solution for solving the problem
The object of the present invention is achieved as follows.
1. A polyacetal copolymer obtained by copolymerizing at least trioxane and a siloxane compound represented by the formula (1).
(in the formula (1), R is respectively 1 Represents a monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms, X represents R 1 Or an organic group having an epoxy group. Wherein more than 2 of X are organic groups having epoxy groups, and R are plural 1 X are optionally the same or different respectively. )
2. The polyacetal copolymer according to the item 1, which is obtained by copolymerizing (B) a cyclic acetal compound having an oxyalkylene group of 2 or more carbon atoms in the ring.
3. The polyacetal copolymer according to the item 1 or 2, wherein the organic group having an epoxy group is a 2- (3, 4-cyclohexyl) ethyl group.
4. The polyacetal copolymer according to any one of 1 to 3, wherein the siloxane compound represented by the formula (1) as defined in the formula (A) is the following compound (A-1). In the formula (A-1), me represents a methyl group.
5. A process for producing a polyacetal copolymer, wherein at least trioxane and a siloxane compound represented by the formula (1) are copolymerized.
(in the formula (1), R is respectively 1 Represents a monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms, X represents R 1 Or an organic group having an epoxy group. Wherein more than 2 of X's present in the plurality are those having an epoxy groupA plurality of R groups 1 X are optionally the same or different respectively. )
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, there may be provided: a novel polyacetal copolymer excellent in productivity and mechanical properties and a process for producing the same.
Detailed Description
The following describes specific embodiments of the present invention in detail, but the present invention is not limited to the following embodiments at all, and can be implemented with modifications as appropriate within the scope of the object of the present invention.
< polyacetal copolymer >)
The polyacetal copolymer of the present invention is characterized by being obtained by copolymerizing at least trioxane and (A) a siloxane compound represented by the formula (1).
The polyacetal copolymer of the present invention has a siloxane structure having a plurality of epoxy groups after reaction, and thus, is excellent in mechanical properties.
Trioxane
The trioxane 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.
Siloxane Compound represented by the formula (A) formula (1)
The component (A) used in the present invention is a silicone compound represented by the formula (1).
(in the formula (1), R is respectively 1 Represents a monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms, X represents R 1 Or an organic group having an epoxy group. Wherein more than 2 of X are organic groups having epoxy groups, and R are plural 1 X are optionally the same or different respectively. )
R 1 Specific examples of the monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms or the aromatic hydrocarbon group having 6 to 10 carbon atoms include saturated monovalent aliphatic hydrocarbon groups such as alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl and heptyl, unsaturated monovalent aliphatic hydrocarbon groups such as alkenyl groups such as vinyl, allyl, isopropenyl and butenyl, phenyl, naphthyl and the like, preferably methyl, ethyl, n-propyl, isopropyl, n-butyl and t-butyl, and more preferably methyl.
The organic group in X is a compound having C, H, N, O atoms, and specific examples of the epoxy group-containing organic group include 2- (3, 4-cyclohexyl) ethyl and 3-glycidoxypropyl, and 2- (3, 4-cyclohexyl) ethyl is preferable from the viewpoint of stability of polymerization. The number of carbon atoms in the organic group is preferably 1 to 20, more preferably 3 to 15. In addition, from the viewpoints of polymerization stability and mechanical strength, 2- (3, 4-cyclohexyl) ethyl group which is an alkylene group having 1 to 5 carbon atoms is preferable.
The silicone compound of formula (1) can be produced by a method described in known documents, for example, JP-A2010-229324 and JP-A2016-204288. When these production methods are applied, a 6-membered ring, 10-membered ring or 12-membered ring cyclic siloxane in which 3,5 or 6 units of a siloxane unit as a by-product are bonded may be produced, but the presence thereof has little influence on the production of the polyacetal copolymer of the present invention, so long as it contains 80 mass% or more of the 8-membered ring cyclic siloxane of the present invention.
The reason why the polymerization control is easy in the case of copolymerizing the siloxane compound of formula (1) in the present invention is presumably that the epoxy group as a copolymerization reaction site is fixedly disposed on the outer side of the molecule by the siloxane ring structure of formula (1), and thus the reaction probability is improved.
Particularly preferred silicone compounds are the following compound (A-1). In the formula (A-1), me represents a methyl group.
In the present invention, the component (a) is preferably used in an amount of 0.01 to 5 parts by mass, more preferably 0.03 to 1 part by mass, based on 100 parts by mass of trioxane.
(B) a cyclic acetal compound having an oxyalkylene group of 2 or more carbon atoms in the ring
In the present invention, (B) a cyclic acetal compound having an oxyalkylene group of 2 or more carbon atoms in the ring can be used as a comonomer.
The cyclic acetal compound having an oxyalkylene group of 2 or more carbon atoms in the ring of the present invention means: examples of the compound usually used as a comonomer in the production of the polyacetal copolymer include 1, 3-dioxolane, 1,3, 6-trioxane, and 1, 4-butanediol formal.
In the present invention, the component (B) is preferably used in an amount of 0.01 to 20 parts by mass, more preferably 0.05 to 5 parts by mass, based on 100 parts by mass of trioxane.
Process for producing polyacetal copolymer
The method for producing a polyacetal copolymer of the present invention is characterized by copolymerizing trioxane and (A) a specific cyclic siloxane compound having 2 or more epoxy groups in the molecule represented by the formula (1) above, in the presence of a cationic polymerization catalyst.
Cationic polymerization catalyst
As the cationic polymerization catalyst, a polymerization catalyst known in cationic copolymerization using trioxane as a main monomer can be used. Typically, a protic acid or a Lewis acid is used.
Proton acid
Examples of the protonic acid include perfluoroalkanesulfonic acid, heteropolyacid, and isopolyacid.
Specific examples of perfluoroalkanesulfonic acids include trifluoromethanesulfonic acid, pentafluoroethanesulfonic acid, heptafluoropropanesulfonic acid, nonafluorobutanesulfonic acid, undecane sulfonic acid, tridecane sulfonic acid, pentadecafluoroheptanesulfonic acid, and heptadecafluorooctanesulfonic acid.
The heteropolyacid is a polyacid produced by dehydration condensation of various kinds of oxygen acids, and has a single-core or polynuclear complex ion in which a specific heterogeneous element exists in the center and which shares an oxygen atom and enables condensation of a condensed acid group. Isopoly acid is also called isopoly acid, and refers to inorganic oxy acid having a high molecular weight formed from a condensate of inorganic oxy acid of a single kind of metal having a valence of V or VI.
Specific examples of the heteropoly acid include phosphomolybdic acid, phosphotungstic acid, phosphomolybdic vanadic acid, phosphotungstic vanadic acid, silicotungstic acid, silicomolybdic vanadic acid, and the like. In particular, from the viewpoint of polymerization activity, the heteropoly acid is preferably selected from the group consisting of silicomolybdic acid, silicotungstic acid, phosphomolybdic acid, and phosphotungstic acid.
Specific examples of the isopoly acid include tungsten isopoly acid exemplified by paratungstic acid, metatungstic acid, and the like; molybdenum isopoly acids exemplified by paramolybdic acid, etc.; metavanadate, vanadium isopoly-acid, and the like. Among them, from the viewpoint of polymerization activity, a tungstic isopoly acid is preferable.
Lewis acid
Examples of the lewis acid include halides of boron, tin, titanium, phosphorus, arsenic and antimony, and specifically boron trifluoride (and ether complexes thereof), tin tetrachloride, titanium tetrachloride, phosphorus pentafluoride, phosphorus pentachloride, antimony pentafluoride and complexes or salts thereof.
The amount of the polymerization catalyst is not particularly limited, but is preferably 0.1ppm to 50ppm, more preferably 0.1ppm to 30ppm, based on the total amount of all the monomers.
In the production of the polyacetal copolymer of the present invention, the components for adjusting the molecular weight may be used in combination with the above-mentioned components to adjust the amount of the terminal groups. Examples of the component for adjusting the molecular weight include chain transfer agents that do not form unstable terminals, i.e., compounds having an alkoxy group such as methylal, monomethoxy methylal, dimethoxy methylal, and the like.
The method for producing the polyacetal copolymer of the present invention is not particularly limited. The polymerization apparatus is not particularly limited in production, and any known apparatus, batch-type, continuous-type, or the like may be used. Further, the polymerization temperature is preferably kept to 65℃or more and 135℃or less.
The cationic polymerization catalyst is preferably used by dilution with an inert solvent which does not adversely affect the polymerization.
Deactivation of the polymerization catalyst after polymerization can be carried out by a conventionally known method. For example, the polymerization reaction may be carried out by adding an alkaline compound or an aqueous solution thereof to a product of the polymerization reaction discharged from the polymerization apparatus or a reaction product in the polymerization apparatus.
The basic compound used for neutralizing the polymerization catalyst to deactivate it is not particularly limited. After polymerization and deactivation, further washing, separation and recovery of unreacted monomers, drying, and the like are carried out by conventionally known methods as needed.
The polyacetal copolymer obtained as described above preferably has a weight average molecular weight of 10000 to 500000, particularly preferably 20000 to 150000, as determined by size exclusion chromatography, corresponding to methyl methacrylate. In addition, for the terminal groups, the reaction mixture is composed of 1 The amount of the hemiformal terminal groups detected by H-NMR (for example, based on the method described in Japanese patent application laid-open No. 2001-11143) is preferably 0 to 4mmol/kg, particularly preferably 0 to 2mmol/kg.
In order to control the terminal amount of the hemiformal within the above range, the total amount of the monomers and comonomers to be polymerized is preferably 20ppm or less, particularly preferably 10ppm or less, of impurities, particularly moisture.
The polyacetal copolymer of the present invention is preferably blended with various known stabilizers, which are selected as needed. The stabilizer used herein may be any one of 1 or 2 or more of hindered phenol compounds, nitrogen-containing compounds, hydroxides of alkali metals or alkaline earth metals, inorganic salts, carboxylates, and the like.
Further, if necessary, additives commonly used for thermoplastic resins, for example, 1 or 2 or more of colorants such as dyes and pigments, lubricants, nucleating agents, mold release agents, antistatic agents, surfactants, organic polymer materials, inorganic or organic fibrous, powdery and plate-like fillers, and the like may be added to the polyacetal copolymer of the present invention.
Examples
The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
< polymerization >)
300g of trioxane was charged into a closed autoclave having a jacket through which a heat medium was allowed to flow and stirring vanes, and the compound described in Table 1 as component (A) and optionally 1, 3-Dioxolane (DO) as component (B) were further added so that the proportions of the components were each represented by the mass parts shown in Table 1. The contents were stirred, hot water at 80℃was circulated through the jacket, and after maintaining the internal temperature at about 80℃a catalyst solution (solution of methyl formate of phosphotungstic acid (PWA), boron trifluoride dibutyl ether complex (BF) 3 OBu 2 ) Dibutyl ether solution) was brought to the catalyst concentration (relative to the total monomer) shown in table 1 to initiate polymerization. When boron trifluoride dibutyl ether complex is used, the catalyst concentration indicates the concentration of boron trifluoride.
The component (A) used in the examples was the following (A-1).
After 5 minutes, 300g of water containing 0.1% of triethylamine was added to the autoclave, the reaction was stopped, the content was taken out, crushed to 200 mesh or less, washed with acetone and dried, and the polyacetal copolymer yield (ratio (%) of the copolymer obtained by adding the whole monomer) was calculated. The results are shown in Table 1.
As a comparison, the following diglycidyl compounds (X-1 and X-2) were used for polymerization instead of the component (A-1) of the present invention to give comparative polyacetal copolymers.
X-1: butanediol diglycidyl ether
X-2: trimethylol propane triglycidyl ether
To 100 parts by mass of the polyacetal copolymer obtained by the above-mentioned method, 0.35 parts by mass of pentaerythritol tetrakis [ 3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ] and 0.15 parts by mass of melamine were added as stabilizers, and melt-kneaded at 210℃in a small twin-screw extruder to obtain a polyacetal resin composition in the form of pellets.
The following evaluation was performed using the pellets. The results are shown in Table 2.
< tensile Strength >
The tensile strength of ISOType1A test pieces was measured according to ISO527-1, 2. The measuring chamber was kept at 23℃under 50% RH.
< flexural Strength and flexural modulus >)
The determination of the flexural strength and flexural modulus was carried out in accordance with ISO 178. The measuring chamber was kept at 23℃under 50% RH.
TABLE 1
TABLE 2
Examples 1 to 8 show that polyacetal copolymers having excellent mechanical properties were obtained in a low catalyst amount and a high yield. In comparative examples 5 and 6, no polymerization reaction was observed at the same catalyst amount. In comparative examples 5 and 6, when the catalyst amount was 20ppm, abrupt reaction was caused, but the final yield was as low as about 50%.
As shown in the results of tables 1 and 2, the present invention provides a novel polyacetal copolymer excellent in production stability and mechanical properties, and a method of producing the same.
Claims (5)
1. A polyacetal copolymer obtained by copolymerizing at least trioxane and (A) a siloxane compound represented by the formula (1),
in the formula (1), R is respectively 1 Represents a monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms, X represents R 1 Or an organic group having an epoxy group, wherein 2 or more of X's present in the plurality are the organic groups having an epoxy group, and R's present in the plurality are the organic groups having an epoxy group 1 X are optionally the same or different respectively,
the amount of (A) is 0.01 to 5 parts by mass per 100 parts by mass of the trioxane.
2. The polyacetal copolymer according to claim 1, wherein the polyacetal (B) is obtained by copolymerizing a cyclic acetal compound having an oxyalkylene group having 2 or more carbon atoms in its ring, and the amount of the polyacetal (B) is 0.01 to 20 parts by mass based on 100 parts by mass of the trioxane.
3. Polyacetal copolymer according to claim 1 or 2, wherein the organic group having an epoxy group is a 2- (3, 4-epoxycyclohexyl) ethyl group.
4. The polyacetal copolymer according to claim 1 or 2, wherein the siloxane compound represented by the formula (1) is a compound (A-1) wherein Me represents a methyl group,
。
5. a process for producing a polyacetal copolymer, which comprises copolymerizing at least trioxane and a siloxane compound represented by the formula (1),
in the formula (1), R is respectively 1 Represents a monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms, X represents R 1 Or an organic group having an epoxy group, wherein 2 or more of X's present in the plurality are the organic groups having an epoxy group, and R's present in the plurality are the organic groups having an epoxy group 1 X are optionally the same or different respectively,
the siloxane compound represented by the formula (1) is 0.01 to 5 parts by mass per 100 parts by mass of the trioxane.
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| PCT/JP2019/047574 WO2020137413A1 (en) | 2018-12-26 | 2019-12-05 | Polyacetal copolymer and method for producing same |
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| WO2016170850A1 (en) * | 2015-04-20 | 2016-10-27 | 信越化学工業株式会社 | Epoxy group-containing cyclic organosiloxane |
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| JPH01146958A (en) * | 1987-12-04 | 1989-06-08 | Polyplastics Co | Thermoplastic resin composition |
| JP4387619B2 (en) | 2001-09-27 | 2009-12-16 | 旭化成ケミカルズ株式会社 | Branched polyoxymethylene copolymer and resin composition thereof |
| JP2005232404A (en) | 2004-02-23 | 2005-09-02 | Mitsubishi Gas Chem Co Inc | Polyacetal resin composition |
| JP5428252B2 (en) * | 2008-09-05 | 2014-02-26 | 三菱瓦斯化学株式会社 | Branched / crosslinked polyacetal copolymer |
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| CN1030430A (en) * | 1987-07-02 | 1989-01-18 | 聚塑料株式会社 | Siliceous Copolyacetal and preparation method thereof |
| JP2002234923A (en) * | 2001-02-09 | 2002-08-23 | Polyplastics Co | Polyacetal copolymer and resin composition |
| JP2009275094A (en) * | 2008-05-14 | 2009-11-26 | Mitsubishi Gas Chem Co Inc | Polyacetal resin composition excellent in sliding property |
| JP2011084702A (en) * | 2009-10-19 | 2011-04-28 | Mitsubishi Gas Chemical Co Inc | Polyacetal copolymer |
| CN103483372A (en) * | 2013-09-02 | 2014-01-01 | 上海硅普化学品有限公司 | 3,4-epoxy cyclohexylethylmethyl cyclosiloxane and preparation method for same |
| WO2016170850A1 (en) * | 2015-04-20 | 2016-10-27 | 信越化学工業株式会社 | Epoxy group-containing cyclic organosiloxane |
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