CN117751149A - Process for producing modified polyacetal resin - Google Patents
Process for producing modified polyacetal resin Download PDFInfo
- Publication number
- CN117751149A CN117751149A CN202280054086.9A CN202280054086A CN117751149A CN 117751149 A CN117751149 A CN 117751149A CN 202280054086 A CN202280054086 A CN 202280054086A CN 117751149 A CN117751149 A CN 117751149A
- Authority
- CN
- China
- Prior art keywords
- polymer
- polyacetal resin
- hydroxyl group
- acid
- organic compound
- 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 101
- 229920006324 polyoxymethylene Polymers 0.000 title claims abstract description 101
- 239000011347 resin Substances 0.000 title claims abstract description 50
- 229920005989 resin Polymers 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims description 22
- 229920000642 polymer Polymers 0.000 claims abstract description 61
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 45
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 40
- 239000003377 acid catalyst Substances 0.000 claims abstract description 32
- 239000000178 monomer Substances 0.000 claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 claims abstract description 15
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 7
- 230000000415 inactivating effect Effects 0.000 claims description 21
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- 239000011964 heteropoly acid Substances 0.000 claims description 13
- 150000003839 salts Chemical class 0.000 claims description 13
- -1 amine compound Chemical class 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 9
- 229910052783 alkali metal Inorganic materials 0.000 claims description 7
- 150000001340 alkali metals Chemical class 0.000 claims description 6
- 150000003856 quaternary ammonium compounds Chemical class 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 10
- 238000006116 polymerization reaction Methods 0.000 description 24
- 239000000243 solution Substances 0.000 description 13
- 239000002253 acid Substances 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000000843 powder Substances 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 11
- 230000004048 modification Effects 0.000 description 11
- 238000012986 modification Methods 0.000 description 11
- 238000004898 kneading Methods 0.000 description 10
- 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 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 8
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 8
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 description 7
- 230000009849 deactivation Effects 0.000 description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 6
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 5
- 239000002685 polymerization catalyst Substances 0.000 description 5
- WQEVDHBJGNOKKO-UHFFFAOYSA-K vanadic acid Chemical compound O[V](O)(O)=O WQEVDHBJGNOKKO-UHFFFAOYSA-K 0.000 description 5
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 229910015900 BF3 Inorganic materials 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 description 3
- 229960001231 choline Drugs 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 description 2
- QLCJOAMJPCOIDI-UHFFFAOYSA-N 1-(butoxymethoxy)butane Chemical compound CCCCOCOCCCC QLCJOAMJPCOIDI-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 239000004381 Choline salt Substances 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 2
- 150000001241 acetals Chemical class 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000007942 carboxylates Chemical class 0.000 description 2
- 238000010538 cationic polymerization reaction Methods 0.000 description 2
- 239000012986 chain transfer agent Substances 0.000 description 2
- 235000019417 choline salt Nutrition 0.000 description 2
- 239000002826 coolant Substances 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 description 2
- 239000012442 inert solvent Substances 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 2
- VJHGSLHHMIELQD-UHFFFAOYSA-N nona-1,8-diene Chemical compound C=CCCCCCC=C VJHGSLHHMIELQD-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
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
- 150000003248 quinolines Chemical class 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-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
- LFKLPJRVSHJZPL-UHFFFAOYSA-N 1,2:7,8-diepoxyoctane Chemical compound C1OC1CCCCC1CO1 LFKLPJRVSHJZPL-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
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 1
- SYEWHONLFGZGLK-UHFFFAOYSA-N 2-[1,3-bis(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COCC(OCC1OC1)COCC1CO1 SYEWHONLFGZGLK-UHFFFAOYSA-N 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
- HTJFSXYVAKSPNF-UHFFFAOYSA-N 2-[2-(oxiran-2-yl)ethyl]oxirane Chemical compound C1OC1CCC1CO1 HTJFSXYVAKSPNF-UHFFFAOYSA-N 0.000 description 1
- PLDLPVSQYMQDBL-UHFFFAOYSA-N 2-[[3-(oxiran-2-ylmethoxy)-2,2-bis(oxiran-2-ylmethoxymethyl)propoxy]methyl]oxirane Chemical compound C1OC1COCC(COCC1OC1)(COCC1OC1)COCC1CO1 PLDLPVSQYMQDBL-UHFFFAOYSA-N 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
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- ZFIVKAOQEXOYFY-UHFFFAOYSA-N Diepoxybutane Chemical compound C1OC1C1OC1 ZFIVKAOQEXOYFY-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 229920002556 Polyethylene Glycol 300 Polymers 0.000 description 1
- 229920002582 Polyethylene Glycol 600 Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 239000004280 Sodium formate Substances 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 229940078456 calcium stearate Drugs 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 229940043279 diisopropylamine Drugs 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- GEAWFZNTIFJMHR-UHFFFAOYSA-N hepta-1,6-diene Chemical compound C=CCCCC=C GEAWFZNTIFJMHR-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 125000006353 oxyethylene group Chemical group 0.000 description 1
- 125000005704 oxymethylene group Chemical group [H]C([H])([*:2])O[*:1] 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- JLFNLZLINWHATN-UHFFFAOYSA-N pentaethylene glycol Chemical compound OCCOCCOCCOCCOCCO JLFNLZLINWHATN-UHFFFAOYSA-N 0.000 description 1
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 1
- GLOBUAZSRIOKLN-UHFFFAOYSA-N pentane-1,4-diol Chemical compound CC(O)CCCO GLOBUAZSRIOKLN-UHFFFAOYSA-N 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
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
- 229940068918 polyethylene glycol 400 Drugs 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 235000011181 potassium carbonates Nutrition 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
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- BTURAGWYSMTVOW-UHFFFAOYSA-M sodium dodecanoate Chemical compound [Na+].CCCCCCCCCCCC([O-])=O BTURAGWYSMTVOW-UHFFFAOYSA-M 0.000 description 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 1
- 235000019254 sodium formate Nutrition 0.000 description 1
- 229940082004 sodium laurate Drugs 0.000 description 1
- 229940045870 sodium palmitate Drugs 0.000 description 1
- 229940080350 sodium stearate Drugs 0.000 description 1
- ZDQYSKICYIVCPN-UHFFFAOYSA-L sodium succinate (anhydrous) Chemical compound [Na+].[Na+].[O-]C(=O)CCC([O-])=O ZDQYSKICYIVCPN-UHFFFAOYSA-L 0.000 description 1
- GGXKEBACDBNFAF-UHFFFAOYSA-M sodium;hexadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCC([O-])=O GGXKEBACDBNFAF-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- RKBCYCFRFCNLTO-UHFFFAOYSA-N triisopropylamine Chemical compound CC(C)N(C(C)C)C(C)C RKBCYCFRFCNLTO-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-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
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
The purpose of the present invention is to provide: the polyacetal resin can be easily modified, and a novel method for producing a polyacetal resin can be provided with various modified polyacetal resins. The object of the present invention is achieved by a method for producing a modified polyacetal resin, which comprises at least the steps of: a step (1) of polymerizing a monomer with a protonic acid catalyst to produce a crude polyacetal polymer; and (2) reacting the crude polyacetal polymer with an organic compound having a hydroxyl group while deactivating the proton catalyst.
Description
Technical Field
The present invention relates to a method for producing a modified polyacetal resin.
Background
Conventionally, as a modification method for introducing a specific structural unit or functional group into the main chain or terminal of a polyacetal resin, a method of cationic copolymerization with a comonomer copolymerizable therewith using trioxane as a main monomer has been generally known. For example, there are known: before the deactivation treatment of the cationic polymerization catalyst, a polyacetal resin and a polymer having an active hydrogen atom or a glycidyl group in the molecule are melt kneaded (patent document 1).
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open No. 2005-105103
Disclosure of Invention
Problems to be solved by the invention
In recent years, the versatility of polyacetal resins has been expanding, and polyacetal resins modified according to the application requirements have been demanded. However, there are limitations on the comonomer to be copolymerized and the compound to react with the terminal, and it is difficult to perform desired modification in the present situation.
The purpose of the present invention is to provide: the polyacetal resin can be easily modified, and a method for producing a polyacetal resin can be provided with various modified polyacetal resins.
Solution for solving the problem
The present invention is achieved as follows.
1. A method for producing a modified polyacetal resin, comprising at least the steps of:
a step (1) of polymerizing a monomer with a protonic acid catalyst to produce a crude polyacetal polymer; and, a step of, in the first embodiment,
and (2) reacting the crude polyacetal polymer with an organic compound having a hydroxyl group while deactivating the protonic acid catalyst.
2. The process for producing a modified polyacetal resin according to the item (1), wherein the protonic acid catalyst is selected from the group consisting of heteropoly acids and mixtures of heteropoly acids and salts thereof.
3. The process for producing a modified polyacetal resin according to the item (1) or (2), wherein the inactivating agent for inactivating the protonic acid catalyst is an amine compound, a quaternary ammonium compound or a salt of an alkali metal.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, there may be provided: the polyacetal resin can be easily modified, and a method for producing a polyacetal resin can be provided with various modified polyacetal resins.
Drawings
Fig. 1 is a schematic view showing a manufacturing process according to one embodiment of the present invention.
Detailed Description
Hereinafter, specific embodiments of the present invention will be described in detail. The present invention is not limited to the following embodiments, and may be implemented with appropriate modifications within the scope of the object of the present invention.
The method for producing a modified polyacetal resin of the present invention comprises the steps of: a step (1) of polymerizing a monomer with a protonic acid catalyst to produce a crude polyacetal polymer; and (2) reacting the crude polyacetal polymer with an organic compound having a hydroxyl group while deactivating the protonic acid catalyst.
< procedure (1): process for producing crude polyacetal Polymer
The step (1) is a step of polymerizing a monomer with a protonic acid catalyst to produce a crude polyacetal polymer. The "crude polyacetal polymer" of the present invention means: the polymer in a state where the monomer is polymerized and the catalyst is not deactivated means a polymer having a polymerization rate of 60% or more. Polymers having a polymerization rate of 65% or more are preferred. Here, "polymerization rate" means: the value of the amount of the polymer obtained after the polymerization reaction is expressed in terms of 100 fractions relative to the amount of the monomer used.
Monomer(s)
In the present invention, the monomer that can be used for producing the modified polyacetal resin is not particularly limited, and trioxane is preferably used as the main monomer. Examples of the comonomer include cyclic formals having at least one carbon-carbon bond among 1, 3-dioxolane, 1,3, 6-trioxane, 1, 4-butanediol formal, and the like. Among these, 1, 3-dioxolane is preferable from the viewpoint of production.
Further, as the comonomer, it is also possible to use: a compound having 2 or more epoxy groups in the molecule such as butanediol diglycidyl ether, a compound having an epoxy group such as glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether and the like, a compound having an alicyclic epoxy group such as 1, 3-butadiene diepoxide, 1, 4-pentanediol diepoxide, 1, 5-hexadiene diepoxide, 1, 6-heptadiene diepoxide, 1, 7-octadiene diepoxide, 1, 8-nonadiene diepoxide, 1, 9-decane diepoxide, 1, 10-undecane diepoxide, 1, 11-dodecane diepoxide and 2- (3, 4-epoxycyclohexyl) ethyl ester. Thus, a polyacetal copolymer having a branched structure and a crosslinked structure can be obtained.
In the present invention, the content of the comonomer is preferably in the range of 0.01 to 20 parts by mass, more preferably in the range of 0.05 to 5 parts by mass, relative to 100 parts by mass of trioxane. If the content of the comonomer is 0.01 parts by mass or more relative to 100 parts by mass of trioxane, polymerization can be stably performed. In addition, if the content of the comonomer is 20 parts by mass or less relative to 100 parts by mass of trioxane, a decrease in the crystallization rate and a decrease in the crystallinity of the polymer chain can be suppressed.
Proton acid catalyst
Examples of the protonic acid catalyst which can be used in the present invention include heteropoly acid, a mixture of heteropoly acid and its salt, isopoly acid, perfluoroalkanesulfonic acid, and the like.
Examples of the heteropoly acid include phosphomolybdic acid, phosphotungstic acid, phosphomolybdic vanadic acid, phosphomolybdic tungsten vanadic acid, phosphotungstic acid, silicomolybdic tungstic vanadic acid, and the like. The heteropolyacid is preferably any one or more of silicomolybdic acid, silicotungstic acid, phosphomolybdic acid and phosphotungstic acid. By using a heteropoly acid, good polymerization stability is obtained.
As the salt of the heteropolyacid, a salt of an alkali metal is preferable. Examples of the alkali metal salt of the heteropolyacid include sodium phosphotungstate, lithium phosphotungstate, and potassium phosphotungstate. Among the alkali metals, sodium is preferred. By using sodium phosphotungstate, good polymerization stability is obtained.
The mixing ratio by mass of the heteropolyacid to its salt (heteropolyacid salt/heteropolyacid) is preferably 10 or less, more preferably 5 or less. If the mixing ratio exceeds 10 by mass, the amount of the catalyst increases, and therefore, hydroxyl ends which become formaldehyde generation sources are excessively formed, and the quality of the polymer is lowered, which is not preferable.
Examples of the isopoly acid include isopoly tungstic acid exemplified by paratungstic acid, metatungstic acid, etc., isopoly molybdic acid exemplified by paramoly molybdic acid, metapoly vanadic acid, isopoly vanadic acid, etc. Among these, homopolytungstic acid is preferred. Good polymerization stability is obtained by using isopolytungstic acid.
Examples of perfluoroalkanesulfonic acids include trifluoromethanesulfonic acid, pentafluoroethanesulfonic acid, heptafluoropropanesulfonic acid, nonafluorobutanesulfonic acid, undecapentasulfonic acid, tridecane-fluorohexanesulfonic acid, pentadecafluoroheptanesulfonic acid, heptadecafluorooctanesulfonic acid. Of these, trifluoromethanesulfonic acid is preferred. By using trifluoromethanesulfonic acid, good polymerization stability is obtained.
In the present invention, the amount of the above-mentioned protonic acid catalyst may be appropriately adjusted according to the kind thereof to adjust the polymerization reaction. In general, the amount of the protonic acid catalyst to be used is preferably in the range of 0.05 to 100ppm (hereinafter, mass/mass ppm) with respect to the total amount of the monomers, more preferably in the range of 0.1 to 50 ppm. If the amount of the protonic acid catalyst is 0.05 to 100ppm based on the total amount of the monomers, the polymerization can be sufficiently carried out, and thus a desired degree of polymerization can be easily obtained. On the other hand, if the amount of the protonic acid catalyst exceeds 100ppm based on the total amount of the monomers, hydroxyl ends which are formaldehyde generating sources are excessively formed, and the quality of the polymer is lowered, which is not preferable.
In order to uniformly perform the reaction, the protonic acid catalyst is desirably diluted with an inert solvent which does not adversely affect the polymerization, and added to the main monomer and/or the comonomer for use. Examples of the inert solvent include methyl formate, ethyl formate, methyl acetate, ethyl acetate, butyl acetate, acetone, 2-butanone, methyl isobutyl ketone, and the like.
The protonic acid catalyst is suitably dissolved in the above-mentioned inactive solvent at a concentration of 1 to 30 mass/mass%, but is not limited thereto. In addition, the following method is preferable: the above-mentioned predetermined amount of the protonic acid catalyst is mixed in advance in a part or the total amount of any one or more of the above-mentioned main monomer, comonomer, molecular weight regulator, etc., and the solution is added to a polymerization system to perform polymerization.
Molecular weight regulator
In the production of the crude polyacetal copolymer of the present invention, a molecular weight regulator is preferably used in addition to the above-mentioned components to regulate the molecular weight. As the molecular weight regulator, a chain transfer agent known in cationic polymerization can be used.
Examples of the chain transfer agent include linear formals such as methylal, acetal and dibutoxymethane, alcohols such as methanol, ethanol and ethylene glycol, water and the like. Among these, methylal, acetal, and dibutoxymethane which do not form unstable ends are preferable. The amount to be added is preferably 50 to 2000ppm based on the whole monomer.
Process for producing crude polyacetal polymer
The crude polyacetal polymer of the present invention is obtained as follows: the polymerization reaction apparatus (continuous twin screw propeller type screw extruder) having a jacket for passing a heating or cooling medium outside the main body was obtained by continuously supplying a mixed solution containing the above trioxane, 1, 3-dioxolane, a molecular weight regulator, and a protonic acid catalyst, and polymerizing the mixed solution for a predetermined period of time.
< procedure (2): process for reacting a crude polyacetal polymer with an organic compound having a hydroxyl group while deactivating the protonic acid catalyst
The step (2) is as follows: the method comprises the steps of adding a deactivator to the crude polyacetal polymer obtained in the step (1) to deactivate the residual protonic acid catalyst, stabilizing the unstable terminal of the crude polyacetal polymer, and simultaneously reacting the crude polyacetal polymer with an organic compound having a hydroxyl group. By this step, the residue of the organic compound having a hydroxyl group can be introduced into the crude polyacetal polymer and modified, and the amount of deactivation of the protonic acid catalyst can be adjusted by changing the condition of addition of the deactivator, thereby adjusting the degree of modification.
Here, "the reaction of the crude polyacetal polymer with the organic compound having a hydroxyl group while the protonic acid catalyst is deactivated" refers not only to the case where the deactivator is added to the reaction system simultaneously with the organic compound having a hydroxyl group and reacts with the crude polyacetal polymer, but also to the case where the reaction of the deactivator with the crude polyacetal polymer and the reaction of the organic compound having a hydroxyl group with the crude polyacetal polymer are carried out simultaneously in the reaction system, if not simultaneously. For example, it also includes: firstly, an organic compound having a hydroxyl group is added and reacted with a crude polyacetal polymer, and an inactivating agent is added to the reaction system during the reaction; and the case of adding in reverse order thereof.
The method of adding the organic compound having a hydroxyl group and the inactivating agent to the crude polyacetal polymer obtained in the step (1) may be appropriately selected from known methods such as batch type and continuous type.
Deactivator (inactivating agent)
The deactivator which can be used in the present invention is not particularly limited. From the viewpoint of the deactivation of the protonic acid catalyst and the stabilization of the unstable terminal of the crude polyacetal polymer, which can be achieved by directly adding the crude polyacetal polymer and melt-kneading the crude polyacetal polymer under heating, the deactivator preferably comprises at least one selected from the group consisting of an amine compound, a compound having a quaternary ammonium group, a carbonate, a bicarbonate, and a carboxylate of an alkali metal element or an alkaline earth metal element, or a hydrate thereof. In addition, two or more of them may be used in combination.
Examples of the amine compound include primary amine compounds such as methylamine, ethylamine, propylamine, isopropylamine, and butylamine, secondary amine compounds such as dimethylamine, diethylamine, dipropylamine, diisopropylamine, and dibutylamine, and tertiary amine compounds such as trimethylamine, triethylamine, tripropylamine, triisopropylamine, and tributylamine. Examples of the compound having a quaternary ammonium group include choline and choline salts. Among these, choline or choline salts are preferred.
Examples of the carbonate, bicarbonate or carboxylate of an alkali metal element or an alkaline earth metal element or a hydrate thereof include sodium formate, sodium acetate, potassium carbonate, sodium bicarbonate, disodium succinate, sodium laurate, sodium palmitate, sodium stearate, calcium stearate, and the like. Among these, sodium carbonate, sodium hydrogencarbonate and sodium stearate are preferable. They may be used alone or in combination of two or more.
The amount of the deactivator to be added is not particularly limited, but is preferably 0.002 to 1.0 milliequivalents relative to 1kg of the crude polyacetal copolymer. If the amount is in the range of 0.002 to 1.0 milliequivalent, discoloration of the resulting polymer can be suppressed.
Organic Compounds having hydroxyl groups
Examples of the organic compound having a hydroxyl group (hereinafter, also referred to as a hydroxyl group-containing organic compound) which can be used in the present invention include organic compounds having an alcoholic hydroxyl group. The hydroxyl group may be present in plural in one compound. Examples thereof include: an alcohol having 1 to 34 carbon atoms, a polyalkylene oxide having a hydroxyl end and a number average molecular weight of 1000 or less (for example, ethylene oxide, propylene oxide, etc.), and a polyethylene glycol (PEG) having an average molecular weight of 600 or less (for example, PEG600, PEG400, PEG300, etc.)
The organic compound having a hydroxyl group may be appropriately selected depending on the use of the polyacetal resin, and the degree of modification may be appropriately selected.
Process for producing modified polyacetal resin
An outline of the method for producing a modified polyacetal resin of the present invention will be described with reference to FIG. 1. A shown in fig. 1 is "step (1): in the step of producing a crude polyacetal polymer, "the polymerization apparatus for polymerizing the monomer(s)" is used as B, and B is an extruder for the step of inactivating the protonic acid catalyst in the step of (2) and simultaneously reacting the crude polyacetal polymer with the organic compound having a hydroxyl group, "and for the step of simultaneously inactivating the polymerization catalyst by reacting the crude polyacetal polymer with the organic compound having a hydroxyl group. In addition, X and Y in fig. 1 show the locations where the deactivators were added. Specifically, X is a position where the deactivator is added before entering the extruder (before melt kneading), and Y is a position where the deactivator is added in the middle of the extruder.
Next, a treatment method for "inactivating the protonic acid catalyst" (hereinafter, also referred to as an inactivation treatment of the catalyst) and a step of modifying the crude polyacetal polymer will be described. Specifically, the deactivation treatment of the catalyst is as follows: from the position X shown in fig. 1, as shown in the following (1) to (4), an inactivating agent or a inactivating agent solution is added to the crude polyacetal polymer, and both are subjected to melt kneading treatment in an extruder B.
(1) The deactivator is added directly to the crude polyacetal polymer.
(2) A solution containing an inactivating agent is added to the crude polyacetal polymer.
(3) The solution containing the deactivator is mixed with a powder of polyacetal resin prepared in advance and then added to the crude polyacetal polymer.
(4) The deactivator is directly mixed with a powder of a polyacetal resin prepared in advance and then added to the crude polyacetal polymer.
Further, as shown in the following (5) to (8), from the position Y shown in fig. 1, the crude polyacetal polymer may be added in a state where melt-kneading has been performed in the extruder B.
(5) From the middle of the extruder B, a solution containing an inactivating agent was added by injection or the like to the part in a melt-kneaded state.
(6) The deactivator was directly added from the middle of the extruder B to the part in the melt-kneaded state.
(7) After mixing a solution containing an inactivating agent with a polyacetal resin powder prepared in advance, the dispersed powder was added from the middle of the extruder B to a part in a melt-kneaded state.
(8) The deactivator was directly mixed with the polyacetal resin powder prepared in advance, and then the dispersed powder was added from the middle of the extruder B to the melt-kneaded part.
(1) The powder of the crude polyacetal polymer or polyacetal resin shown in (8) and the deactivator may be mixed by a usual mixer such as a horizontal cylinder type, V type, ribbon type, paddle type or high-speed flow type. The molten resin discharged from a discharge die (not shown) provided in the discharge portion of the extruder B is cooled and then cut into pellets to obtain a modified polyacetal resin.
The hydroxyl group-containing organic compound of the present invention may be added simultaneously with the deactivator or separately from the deactivator at the timing of adding the deactivator in the deactivation treatment of the catalysts of (1) to (8).
When the hydroxyl group-containing organic compound and the deactivator are added simultaneously, the hydroxyl group-containing organic compound and the deactivator may be added directly at the same position (X or Y), or may be added after being mixed with a polyacetal resin powder prepared in advance.
When the hydroxyl group-containing organic compound and the inactivating agent are separately added, the inactivating agent may be added to the melt kneading section (not shown) by the method described in the above (5) to (8) when the hydroxyl group-containing organic compound is fed into the extruder B together with the crude polyacetal polymer and melt-kneaded, either directly or after being mixed with the powder of the polyacetal resin prepared in advance. Alternatively, the deactivator may be added to the crude polyacetal polymer before melt-kneading the same as described in the above (1) to (4) from X, and then melt-kneaded in the extruder B, and the hydroxyl-containing organic compound may be added to the melt-kneading part (not shown) from Y either directly or by mixing with a powder of the polyacetal resin prepared in advance. When the hydroxyl group-containing organic compound and the inactivating agent are separately added and mixed, it is preferable to add the hydroxyl group-containing organic compound before melt kneading.
The modification of the present invention is specifically caused in a crude polyacetal polymer polymerized by using a protonic acid catalyst, and the efficiency of the modification is extremely low when a Lewis acid, such as boron trifluoride, is used as a catalyst. The modification of the present invention can be specifically performed in the case of using a protonic acid catalyst.
In the present invention, the reaction with the organic compound having a hydroxyl group and the deactivation reaction of the catalyst are competing reactions, and therefore, the progress of the reaction between the crude polyacetal polymer and the organic compound having a hydroxyl group can be regulated by the deactivation treatment, and the degree of modification can also be regulated.
< other procedures >
The present invention may also include other steps. For example, the method may include a step of adding various additives from the middle of the extruder and melt-kneading the mixture, or a step of adding various additives to a pellet-shaped polyacetal resin and then melt-kneading the mixture again.
Examples
Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.
< procedure (1) >)
In the step (1), a crude polyacetal polymer is produced by polymerization as follows. As polymerization apparatus A, a continuous twin-screw paddle screw extruder type was used. The polymerization apparatus a includes a jacket (not shown) for passing a heating or cooling medium outside the main body. The main body has a vertically divided structure, and an upper portion thereof is openable. Inside the polymerization apparatus a, 2 rotating shafts each having a plurality of blades for stirring and pushing are provided in the longitudinal direction.
In the main body heated by the jacket temperature-adjusted by the medium of 80 ℃, a mixed solution containing 100 parts by mass of trioxane as a main monomer, 4.3 parts by mass of 1, 3-dioxolane as a comonomer, and 1000ppm of a molecular weight regulator was continuously supplied per unit time, and a polymerization catalyst was supplied thereto.
The content of the polymerization catalyst was 4ppm in the case of the combination of phosphotungstic acid and trifluoromethanesulfonic acid, and it was phosphotungstic acid and its salt, H 5 PV 2 W 10 O 40 The combination of (HPA) and the salt of phosphotungstic acid was set to 6ppm, and boron trifluoride diethyl ether was set to 30ppm (unit: mass ppm with respect to the whole monomer), and these resulting solutions were continuously added and copolymerized. Boron trifluoride diethyl etherate as polymerization catalystThe ether concentration is calculated as boron trifluoride.
< procedure (2) >)
In the step (2), the scaly crude polyacetal polymer discharged from the polymerization unit A was added with the organic compound having a hydroxyl group and the deactivator shown in tables 1 and 2, and melt-kneaded in a twin-screw extruder having a barrel temperature of 210℃and equipped with a vent, to obtain a pellet-shaped modified polyacetal resin. The addition of the organic compound having a hydroxyl group and the inactivating agent is performed as follows.
The addition position of the inactivating agent is X: the organic compound having a hydroxyl group and the deactivator shown in tables 1 and 2 were added to 2 parts by mass of the polyacetal resin powder per 100 parts by mass of the crude polyacetal polymer, and the obtained mixture was mixed, and the resultant was added together with the crude polyacetal polymer from the position X.
The addition position of the inactivating agent is Y: the organic compounds having hydroxyl groups shown in tables 1 and 2 were added to 2 parts by mass of polyacetal resin powder relative to 100 parts by mass of the crude polyacetal polymer, and mixed, and the obtained substance was added together with the crude polyacetal polymer from the X position, and then the deactivators shown in tables 1 and 2 were added from the Y position.
Compounds described in tables 1 and 2
[ organic Compound having hydroxyl group ]
OH1: eicosdiol (carbon number 22)
OH2: pentanediol (carbon number 5)
OH3: polyethylene glycol 400 (PEG 400)
[ catalyst ]
The catalysts described below were added as solutions in brackets, respectively.
PWA: phosphotungstic acid (0.2 wt% methyl formate solution)
Pwa+ salt: equal mass mixture of phosphotungstic acid and Na phosphotungstic acid (0.2 wt% methyl formate solution)
HPA + salt: h 5 PV 2 W 10 O 40 Equal mass mixture with Na phosphotungstic acid (0.2 wt% methyl formate solution)
TFMSA: trifluoromethanesulfonic acid (0.2 wt% cyclohexane solution)
·BF 3 : boron trifluoride diethyl etherate (boron trifluoride 1.5wt% in cyclohexane)
[ deactivator ]
The total amount added was 10ppm. The solid was directly added as a solid at ordinary temperature, and the solid called "aq." in tables 1 and 2 was added as an aqueous solution (concentration: 0.5 mg/mL).
StNa: sodium stearate
·Na 2 CO 3 : sodium carbonate,
·K 2 CO 3 : potassium carbonate
Choline
TEA: triethylamine
< modification evaluation >
0.2g of the pellet-shaped modified polyacetal resin obtained in the step (1) and the step (2) was dissolved in 4ml of 1, 3-Hexafluoroisopropanol (HFIP), and the mixture was reprecipitated by adding 8ml of methanol thereto with stirring. The reprecipitated resin was filtered and recovered, and dried. The above treatment was again performed on the dried polyacetal resin, and the obtained resin was used as a sample. 30mg of the obtained sample was dissolved in deuterated HFIP (0.6 ml), and 1H-NMR (nuclear magnetic resonance) was measured at a temperature of 318K under 128 times of accumulation using AVANCEIII (Bruker Biospin Co.) equipped with a Cryo probe. The amount of the introduced hydroxyl group-containing organic compound was determined from the peak areas of the oxymethylene group and the oxyethylene group of the polyacetal polymer and the peak areas of the hydroxyl group-adjacent methylene groups of the hydroxyl group-containing organic compound in the obtained NMR spectrum.
The amount of the hydroxyl group-containing organic compound introduced into each material having 5000ppm of the hydroxyl group-containing organic compound and the crude polyacetal polymer melt-kneaded was measured, and the modification efficiency was confirmed. The results are shown in tables 1 and 2. The modification efficiency was determined based on the introduction rate. The introduction rate was calculated by the following equation.
The rate of introduction (%) = (amount of introduction)/(amount of addition) ×100
TABLE 1
TABLE 2
As is clear from the results shown in tables 1 and 2, the use of a Lewis acid (BF 3 ) In the case of the polymerization catalyst, the amount of the hydroxyl group-containing organic compound introduced becomes small, but the amount of the hydroxyl group-containing organic compound introduced into the protonic acid catalyst (heteropoly acid or the like) used in the present invention becomes large. From this, it is found that the polyacetal resin can be easily modified to obtain various modified polyacetal resins by using the production method of the present invention.
Industrial applicability
Consider that: according to the production method of the present invention, not only the low-molecular compound but also the polymer compound which is not compatible with the polyacetal resin can be introduced, and the functional manifestation due to the change in compatibility of the modified polyacetal obtained thereby with various polymer compounds can be expected.
Description of the reference numerals
A polymerization apparatus
B extruder
X into the extruder
Midway position of Y extruder
Z-modified polyacetal resin
Claims (3)
1. A method for producing a modified polyacetal resin, comprising at least the steps of:
a step (1) of polymerizing a monomer with a protonic acid catalyst to produce a crude polyacetal polymer; and, a step of, in the first embodiment,
and (2) reacting the crude polyacetal polymer with an organic compound having a hydroxyl group while deactivating the protonic acid catalyst.
2. The process for producing a modified polyacetal resin according to claim 1, wherein the protonic acid catalyst is selected from a heteropoly acid or a mixture of a heteropoly acid and a salt thereof.
3. The method for producing a modified polyacetal resin according to claim 1 or 2, wherein the inactivating agent for inactivating the protonic acid catalyst is an amine compound, a quaternary ammonium compound or a salt of an alkali metal.
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- 2022-07-28 CN CN202280054086.9A patent/CN117751149A/en active Pending
- 2022-07-28 WO PCT/JP2022/029146 patent/WO2023017741A1/en active Application Filing
- 2022-07-28 JP JP2023520332A patent/JP7365531B2/en active Active
- 2022-08-04 TW TW111129324A patent/TW202313745A/en unknown
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Also Published As
| Publication number | Publication date |
|---|---|
| JP7365531B2 (en) | 2023-10-19 |
| JPWO2023017741A1 (en) | 2023-02-16 |
| WO2023017741A1 (en) | 2023-02-16 |
| TW202313745A (en) | 2023-04-01 |
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