JP2010159357A - Method for producing hydroxy group-containing olefin copolymer - Google Patents
Method for producing hydroxy group-containing olefin copolymer Download PDFInfo
- Publication number
- JP2010159357A JP2010159357A JP2009003101A JP2009003101A JP2010159357A JP 2010159357 A JP2010159357 A JP 2010159357A JP 2009003101 A JP2009003101 A JP 2009003101A JP 2009003101 A JP2009003101 A JP 2009003101A JP 2010159357 A JP2010159357 A JP 2010159357A
- Authority
- JP
- Japan
- Prior art keywords
- group
- compound
- olefin copolymer
- aluminoxy
- double bond
- 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.)
- Granted
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 title claims abstract description 63
- 229920000089 Cyclic olefin copolymer Polymers 0.000 title claims abstract description 32
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- -1 alkyl aluminum compound Chemical class 0.000 claims abstract description 58
- 150000001875 compounds Chemical class 0.000 claims abstract description 52
- 238000000034 method Methods 0.000 claims abstract description 30
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229920001577 copolymer Polymers 0.000 claims abstract description 19
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 18
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 18
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 14
- 125000003118 aryl group Chemical group 0.000 claims abstract description 14
- 125000003710 aryl alkyl group Chemical group 0.000 claims abstract description 12
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 9
- 125000000732 arylene group Chemical group 0.000 claims abstract description 7
- 150000003624 transition metals Chemical class 0.000 claims abstract description 7
- 229910052751 metal Inorganic materials 0.000 claims abstract description 6
- 239000002184 metal Chemical group 0.000 claims abstract description 6
- 125000004429 atom Chemical group 0.000 claims abstract description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 26
- 150000001336 alkenes Chemical class 0.000 claims description 25
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 8
- 239000007858 starting material Substances 0.000 abstract description 3
- 239000001257 hydrogen Substances 0.000 abstract description 2
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 27
- 229920000642 polymer Polymers 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 23
- 238000006116 polymerization reaction Methods 0.000 description 17
- 239000000178 monomer Substances 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 239000000243 solution Substances 0.000 description 14
- 150000003623 transition metal compounds Chemical class 0.000 description 14
- 238000005481 NMR spectroscopy Methods 0.000 description 13
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 13
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 13
- 229910052782 aluminium Inorganic materials 0.000 description 11
- 150000008040 ionic compounds Chemical class 0.000 description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- KHAVLLBUVKBTBG-UHFFFAOYSA-N dec-9-enoic acid Chemical compound OC(=O)CCCCCCCC=C KHAVLLBUVKBTBG-UHFFFAOYSA-N 0.000 description 8
- KISVAASFGZJBCY-UHFFFAOYSA-N methyl undecenate Chemical compound COC(=O)CCCCCCCCC=C KISVAASFGZJBCY-UHFFFAOYSA-N 0.000 description 8
- 239000002685 polymerization catalyst Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 229920002554 vinyl polymer Polymers 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 230000037048 polymerization activity Effects 0.000 description 7
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 7
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical group CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 6
- FRPZMMHWLSIFAZ-UHFFFAOYSA-N 10-undecenoic acid Chemical compound OC(=O)CCCCCCCCC=C FRPZMMHWLSIFAZ-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 239000002841 Lewis acid Substances 0.000 description 6
- 238000007334 copolymerization reaction Methods 0.000 description 6
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 6
- 150000007517 lewis acids Chemical class 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 6
- 229960002703 undecylenic acid Drugs 0.000 description 6
- AQZWEFBJYQSQEH-UHFFFAOYSA-N 2-methyloxaluminane Chemical compound C[Al]1CCCCO1 AQZWEFBJYQSQEH-UHFFFAOYSA-N 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- 231100000572 poisoning Toxicity 0.000 description 5
- 230000000607 poisoning effect Effects 0.000 description 5
- 229920000098 polyolefin Polymers 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical group CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 4
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical group CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 4
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 4
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 4
- 125000005234 alkyl aluminium group Chemical group 0.000 description 4
- 239000008346 aqueous phase Substances 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- DKAGJZJALZXOOV-UHFFFAOYSA-N hydrate;hydrochloride Chemical compound O.Cl DKAGJZJALZXOOV-UHFFFAOYSA-N 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 125000004430 oxygen atom Chemical group O* 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 150000008065 acid anhydrides Chemical class 0.000 description 3
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- OBDUMNZXAIUUTH-HWKANZROSA-N (e)-tetradec-2-ene Chemical group CCCCCCCCCCC\C=C\C OBDUMNZXAIUUTH-HWKANZROSA-N 0.000 description 2
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- FXNFFCMITPHEIT-UHFFFAOYSA-N Ethyl 10-undecenoate Chemical compound CCOC(=O)CCCCCCCCC=C FXNFFCMITPHEIT-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 150000001450 anions Chemical group 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 125000002843 carboxylic acid group Chemical group 0.000 description 2
- 238000012718 coordination polymerization Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 229920001038 ethylene copolymer Polymers 0.000 description 2
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 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 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004464 hydroxyphenyl group Chemical group 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012968 metallocene catalyst Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- VAMFXQBUQXONLZ-UHFFFAOYSA-N n-alpha-eicosene Natural products CCCCCCCCCCCCCCCCCCC=C VAMFXQBUQXONLZ-UHFFFAOYSA-N 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 125000004957 naphthylene group Chemical group 0.000 description 2
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 125000006502 nitrobenzyl group Chemical group 0.000 description 2
- 125000006501 nitrophenyl group Chemical group 0.000 description 2
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 2
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadec-1-ene Chemical compound CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 2
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- QROGIFZRVHSFLM-UHFFFAOYSA-N prop-1-enylbenzene Chemical group CC=CC1=CC=CC=C1 QROGIFZRVHSFLM-UHFFFAOYSA-N 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XBFJAVXCNXDMBH-UHFFFAOYSA-N tetracyclo[6.2.1.1(3,6).0(2,7)]dodec-4-ene Chemical compound C1C(C23)C=CC1C3C1CC2CC1 XBFJAVXCNXDMBH-UHFFFAOYSA-N 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- 125000005628 tolylene group Chemical group 0.000 description 2
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 description 2
- FQMMZTDQJFUYSA-UHFFFAOYSA-N triheptylalumane Chemical compound CCCCCCC[Al](CCCCCCC)CCCCCCC FQMMZTDQJFUYSA-UHFFFAOYSA-N 0.000 description 2
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 description 2
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 2
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 description 2
- USJZIJNMRRNDPO-UHFFFAOYSA-N tris-decylalumane Chemical compound CCCCCCCCCC[Al](CCCCCCCCCC)CCCCCCCCCC USJZIJNMRRNDPO-UHFFFAOYSA-N 0.000 description 2
- 125000005023 xylyl group Chemical group 0.000 description 2
- 125000006839 xylylene group Chemical group 0.000 description 2
- RFFLAFLAYFXFSW-RHQRLBAQSA-N 1,2-dichloro-3,4,5,6-tetradeuteriobenzene Chemical compound [2H]C1=C([2H])C([2H])=C(Cl)C(Cl)=C1[2H] RFFLAFLAYFXFSW-RHQRLBAQSA-N 0.000 description 1
- HOROZASJKPUNET-UHFFFAOYSA-N 1-chlorodec-5-yne Chemical compound CCCCC#CCCCCCl HOROZASJKPUNET-UHFFFAOYSA-N 0.000 description 1
- 229940106006 1-eicosene Drugs 0.000 description 1
- FIKTURVKRGQNQD-UHFFFAOYSA-N 1-eicosene Natural products CCCCCCCCCCCCCCCCCC=CC(O)=O FIKTURVKRGQNQD-UHFFFAOYSA-N 0.000 description 1
- GIEMHYCMBGELGY-UHFFFAOYSA-N 10-undecen-1-ol Chemical compound OCCCCCCCCCC=C GIEMHYCMBGELGY-UHFFFAOYSA-N 0.000 description 1
- WAGPVSSOAYEKJK-UHFFFAOYSA-N 2,2-dimethylundec-10-enoic acid Chemical compound OC(=O)C(C)(C)CCCCCCCC=C WAGPVSSOAYEKJK-UHFFFAOYSA-N 0.000 description 1
- GKIOPTBQHQARRY-UHFFFAOYSA-N 2-(2-methylpropyl)hex-5-enoic acid Chemical compound CC(C)CC(C(O)=O)CCC=C GKIOPTBQHQARRY-UHFFFAOYSA-N 0.000 description 1
- FLYIRERUSAMCDQ-UHFFFAOYSA-N 2-azaniumyl-2-(2-methylphenyl)acetate Chemical compound CC1=CC=CC=C1C(N)C(O)=O FLYIRERUSAMCDQ-UHFFFAOYSA-N 0.000 description 1
- ALIMAYNTTUQDMH-UHFFFAOYSA-N 2-butyldec-9-enoic acid Chemical compound CCCCC(C(O)=O)CCCCCCC=C ALIMAYNTTUQDMH-UHFFFAOYSA-N 0.000 description 1
- NHPSPSLXKDAPOJ-UHFFFAOYSA-N 2-butylhept-6-enoic acid Chemical compound CCCCC(C(O)=O)CCCC=C NHPSPSLXKDAPOJ-UHFFFAOYSA-N 0.000 description 1
- ORZDPVUOADWXKM-UHFFFAOYSA-N 2-butylhex-5-enoic acid Chemical compound CCCCC(C(O)=O)CCC=C ORZDPVUOADWXKM-UHFFFAOYSA-N 0.000 description 1
- RKDPFWCZHAHPPG-UHFFFAOYSA-N 2-butyloct-7-enoic acid Chemical compound CCCCC(C(O)=O)CCCCC=C RKDPFWCZHAHPPG-UHFFFAOYSA-N 0.000 description 1
- SQYLHGLUYQYVQN-UHFFFAOYSA-N 2-butylundec-10-enoic acid Chemical compound CCCCC(C(O)=O)CCCCCCCC=C SQYLHGLUYQYVQN-UHFFFAOYSA-N 0.000 description 1
- OHWFOMYHPLMVHI-UHFFFAOYSA-N 2-ethyldec-9-enoic acid Chemical compound CCC(C(O)=O)CCCCCCC=C OHWFOMYHPLMVHI-UHFFFAOYSA-N 0.000 description 1
- ARFIBEWONQFJSI-UHFFFAOYSA-N 2-ethylhept-6-enoic acid Chemical compound CCC(C(O)=O)CCCC=C ARFIBEWONQFJSI-UHFFFAOYSA-N 0.000 description 1
- FWUSTFBMWUQKDP-UHFFFAOYSA-N 2-ethylhex-5-enoic acid Chemical compound CCC(C(O)=O)CCC=C FWUSTFBMWUQKDP-UHFFFAOYSA-N 0.000 description 1
- HVBSEJKZBLYPJE-UHFFFAOYSA-N 2-ethylnon-8-enoic acid Chemical compound CCC(C(O)=O)CCCCCC=C HVBSEJKZBLYPJE-UHFFFAOYSA-N 0.000 description 1
- UPZLONXRGINPEN-UHFFFAOYSA-N 2-ethyloct-7-enoic acid Chemical compound CCC(C(O)=O)CCCCC=C UPZLONXRGINPEN-UHFFFAOYSA-N 0.000 description 1
- MSHFOZDISJNXON-UHFFFAOYSA-N 2-ethylundec-10-enoic acid Chemical compound CCC(C(O)=O)CCCCCCCC=C MSHFOZDISJNXON-UHFFFAOYSA-N 0.000 description 1
- CMAOLVNGLTWICC-UHFFFAOYSA-N 2-fluoro-5-methylbenzonitrile Chemical compound CC1=CC=C(F)C(C#N)=C1 CMAOLVNGLTWICC-UHFFFAOYSA-N 0.000 description 1
- WKEQSOPXSYEBNY-UHFFFAOYSA-N 2-methyl-3-propan-2-ylnon-8-enoic acid Chemical compound OC(=O)C(C)C(C(C)C)CCCCC=C WKEQSOPXSYEBNY-UHFFFAOYSA-N 0.000 description 1
- HWYNXJFFASVMKZ-UHFFFAOYSA-N 2-methyldec-9-enoic acid Chemical compound OC(=O)C(C)CCCCCCC=C HWYNXJFFASVMKZ-UHFFFAOYSA-N 0.000 description 1
- RIALMAVWQPXZHP-UHFFFAOYSA-N 2-methyldodec-11-enoic acid Chemical compound OC(=O)C(C)CCCCCCCCC=C RIALMAVWQPXZHP-UHFFFAOYSA-N 0.000 description 1
- IVIKGKAWCGPRBQ-UHFFFAOYSA-N 2-methylhept-6-enoic acid Chemical compound OC(=O)C(C)CCCC=C IVIKGKAWCGPRBQ-UHFFFAOYSA-N 0.000 description 1
- SXUXAXVRKXYXQZ-UHFFFAOYSA-N 2-methylhex-5-enoic acid Chemical compound OC(=O)C(C)CCC=C SXUXAXVRKXYXQZ-UHFFFAOYSA-N 0.000 description 1
- RKURGFBZYQOIIK-UHFFFAOYSA-N 2-methylnon-8-enoic acid Chemical compound OC(=O)C(C)CCCCCC=C RKURGFBZYQOIIK-UHFFFAOYSA-N 0.000 description 1
- CSUTZKBVCZFCJR-UHFFFAOYSA-N 2-methyloct-7-enoic acid Chemical compound OC(=O)C(C)CCCCC=C CSUTZKBVCZFCJR-UHFFFAOYSA-N 0.000 description 1
- XTWJVMPEOYBUME-UHFFFAOYSA-N 2-methylundec-10-enoic acid Chemical compound OC(=O)C(C)CCCCCCCC=C XTWJVMPEOYBUME-UHFFFAOYSA-N 0.000 description 1
- CORHVFQILXPQQO-UHFFFAOYSA-N 2-propan-2-yldec-9-enoic acid Chemical compound CC(C)C(C(O)=O)CCCCCCC=C CORHVFQILXPQQO-UHFFFAOYSA-N 0.000 description 1
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- FCODNCDARJDEKB-UHFFFAOYSA-N propan-2-yl hept-6-enoate Chemical compound CC(C)OC(=O)CCCCC=C FCODNCDARJDEKB-UHFFFAOYSA-N 0.000 description 1
- PUMURRNWNHHUFS-UHFFFAOYSA-N propan-2-yl hex-5-enoate Chemical compound CC(C)OC(=O)CCCC=C PUMURRNWNHHUFS-UHFFFAOYSA-N 0.000 description 1
- ZGTMOVNINHSRRK-UHFFFAOYSA-N propan-2-yl non-8-enoate Chemical compound CC(C)OC(=O)CCCCCCC=C ZGTMOVNINHSRRK-UHFFFAOYSA-N 0.000 description 1
- SJMKHCGKNIXLKH-UHFFFAOYSA-N propan-2-yl undec-10-enoate Chemical compound CC(C)OC(=O)CCCCCCCCC=C SJMKHCGKNIXLKH-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 229920001384 propylene homopolymer Polymers 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- DKYPZNSPQXLRRQ-UHFFFAOYSA-M sodium;undec-10-enoate Chemical compound [Na+].[O-]C(=O)CCCCCCCCC=C DKYPZNSPQXLRRQ-UHFFFAOYSA-M 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- JQPMDTQDAXRDGS-UHFFFAOYSA-N triphenylalumane Chemical compound C1=CC=CC=C1[Al](C=1C=CC=CC=1)C1=CC=CC=C1 JQPMDTQDAXRDGS-UHFFFAOYSA-N 0.000 description 1
- CNWZYDSEVLFSMS-UHFFFAOYSA-N tripropylalumane Chemical compound CCC[Al](CCC)CCC CNWZYDSEVLFSMS-UHFFFAOYSA-N 0.000 description 1
- XGOZKNCGVJSRKD-UHFFFAOYSA-N undec-10-enoyl undec-10-enoate Chemical compound C=CCCCCCCCCC(=O)OC(=O)CCCCCCCCC=C XGOZKNCGVJSRKD-UHFFFAOYSA-N 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
Description
本発明は、二重結合含有カルボン酸誘導体を原料とした、２級水酸基および／または３級水酸基を有するオレフィン共重合体の製造方法に関する。 The present invention relates to a method for producing an olefin copolymer having a secondary hydroxyl group and / or a tertiary hydroxyl group using a double bond-containing carboxylic acid derivative as a raw material.
一般にポリオレフィンは、成形性、耐熱性、機械的特性、衛生適合性、耐水蒸気透過性などに優れ、成型品の外観が良好であるなどの特長を有することから、押出成型品、中空成型品、射出成型品などに広く使用されている。しかしながらポリオレフィンは分子中に極性基を含まず、極性樹脂に対する相容性が低いため、従来より極性モノマーをグラフトして極性材料との接着性や相容性を向上させる方法が広く行われている。 In general, polyolefin has features such as excellent moldability, heat resistance, mechanical properties, hygiene compatibility, water vapor permeability resistance, and good appearance of molded products. Widely used in injection molded products. However, since polyolefins do not contain polar groups in the molecule and have low compatibility with polar resins, methods for grafting polar monomers to improve adhesion and compatibility with polar materials have been widely used. .
しかし、この方法ではグラフト反応と並行してポリオレフィン同士の分子間架橋や分子鎖の切断が起こるため、十分な性能を発現させえない場合があった。また、分子間架橋によって生成するゲル分や、分子鎖の切断によって生成する目やに（ダイのリップに付着する異物）などによって成形物の外観が悪くなる場合もあった。 However, in this method, intermolecular crosslinking between molecular polyolefins and molecular chain scission occur in parallel with the grafting reaction, so that sufficient performance may not be achieved. In addition, the appearance of the molded product may be deteriorated due to a gel component generated by intermolecular crosslinking or an eye generated by cutting a molecular chain (foreign matter adhering to the lip of the die).
このような問題を解決する方法として、特許文献１〜４には、Ｔｉ触媒やＶ触媒を用いて、α−オレフィンと極性基含有モノマーを共重合する方法が記載されている。更に、特許文献５〜７、非特許文献１〜４では、メタロセン系触媒の高共重合性を生かし、水酸基含有ビニルモノマーを高効率でオレフィン類と共重合させる技術が開示されている。これらの技術では、得られる水酸基含有共重合体における水酸基の構造は、使用する水酸基含有ビニルモノマーの構造に依存するため、専ら、より安価な一級水酸基が一般的であり、２級水酸基や3級水酸基などの高級水酸基を含有する共重合体を安価に得ることは難しい。また、これらの手法では、触媒の被毒物質となるモノマーの水酸基をアルキルアルミニウム、メチルアルモキサンやシリル基により保護することで触媒の失活を抑制する方法がとられているが、一般的に、水酸基含有ビニルモノマーは、エチレンやプロピレンなどの非極性オレフィン比べ格段に高価であり、用途拡大には、より経済的な水酸基含有オレフィン共重合体の製造方法の開発が求められている。 As a method for solving such a problem, Patent Documents 1 to 4 describe a method of copolymerizing an α-olefin and a polar group-containing monomer using a Ti catalyst or a V catalyst. Further, Patent Documents 5 to 7 and Non-Patent Documents 1 to 4 disclose techniques for copolymerizing hydroxyl group-containing vinyl monomers with olefins with high efficiency by taking advantage of the high copolymerization properties of metallocene catalysts. In these techniques, since the structure of the hydroxyl group in the resulting hydroxyl group-containing copolymer depends on the structure of the hydroxyl group-containing vinyl monomer to be used, a less expensive primary hydroxyl group is generally used. It is difficult to obtain a copolymer containing a higher hydroxyl group such as a hydroxyl group at low cost. In these methods, a method of suppressing the deactivation of the catalyst by protecting the hydroxyl group of the monomer that becomes a poisoning substance of the catalyst with an alkylaluminum, methylalumoxane or silyl group is generally used. Hydroxyl group-containing vinyl monomers are much more expensive than non-polar olefins such as ethylene and propylene, and development of a more economical method for producing a hydroxyl group-containing olefin copolymer is demanded for expanding applications.
本発明は、水酸基含有オレフィン共重合体（Ｐ）およびその経済的で効率的な製造方法を提供することを課題とする。 This invention makes it a subject to provide a hydroxyl-containing olefin copolymer (P) and its economical and efficient manufacturing method.
本発明者らは上記課題の解決を鋭意検討した結果、通常、水酸基含有ビニルモノマーより安価であり、かつトリアルキルアルミニウムによる保護では共重合が難しいカルボン酸基またはその誘導体基を含有するビニルモノマーを原料とし、アルキルアルミニウム化合物で処理し、次いで、遷移金属触媒によるオレフィンと共重合を行うことで、触媒活性を著しく損なうことなく、水酸基を含有するオレフィン共重合体を効率よく製造しえることを見出し、本発明を完成するに至った。 As a result of earnestly examining the solution of the above problems, the present inventors have generally found that a vinyl monomer containing a carboxylic acid group or a derivative group thereof, which is cheaper than a hydroxyl group-containing vinyl monomer and difficult to be copolymerized by protection with trialkylaluminum. It has been found that an olefin copolymer containing a hydroxyl group can be efficiently produced by treating with an alkylaluminum compound as a raw material and then copolymerizing with an olefin by a transition metal catalyst without significantly impairing the catalytic activity. The present invention has been completed.
すなわち本発明は、下記一般式（１）で表される水酸基含有オレフィン共重合体およびその効率的製造法に関する。 That is, this invention relates to the hydroxyl-containing olefin copolymer represented by following General formula (1), and its efficient manufacturing method.
（式（１）中、Ｒ１は炭素原子数１〜２０の２価のアルキレン基もしくはアリーレン基を表し、Ｒ2は炭素原子数１〜１０のアルキル基、アリル基、アリール基、もしくはアリールアルキル基を表し、Ｒ3は水素原子あるいは炭素原子数１〜１０のアルキル基、アリル基、アリール基、もしくはアリールアルキル基を表し、Ｐ１およびＰ２はそれぞれ独立に水素原子または共重合鎖を表す） (In the formula (1), R 1 represents a divalent alkylene or arylene group having 1 to 20 carbon atoms, and R 2 represents an alkyl group, allyl group, aryl group, or arylalkyl having 1 to 10 carbon atoms. R 3 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, an allyl group, an aryl group, or an arylalkyl group, and P 1 and P 2 each independently represent a hydrogen atom or a copolymer chain. )
本発明の方法によれば、上記一般式（１）で示される水酸基共重合体を、実質的に水酸基を含まない安価な出発原料を用い経済的かつ効率的に製造することが可能となる。 According to the method of the present invention, the hydroxyl group copolymer represented by the general formula (1) can be produced economically and efficiently using an inexpensive starting material substantially free of hydroxyl groups.
水酸基含有オレフィン共重合体（Ｐ）
本発明の水酸基含有オレフィン共重合体（Ｐ）は、下記一般式（１）で表される水酸基含有構造を有する。
Hydroxyl-containing olefin copolymer (P)
The hydroxyl group-containing olefin copolymer (P) of the present invention has a hydroxyl group-containing structure represented by the following general formula (1).
式（１）中、Ｒ１は炭素原子数１〜２０の２価のアルキレン基もしくはアリーレン基を表し、好ましくは炭素原子数１〜２０の２価のアルキレン基を表す。 In the formula (1), R 1 represents a divalent alkylene or arylene group having 1 to 20 carbon atoms, preferably a divalent alkylene group having 1 to 20 carbon atoms.
前記アルキレン基としては、例えば、メチレン基、エチレン基、プロピレン基、ブチレン基、ペンチレン基、ヘキシレン基、ヘプチレン基、オクチレン基、ノニレン基、デシレン基、ウンデシレン基、ドデシレン基、テトラデシレン基、ヘキサデシレン基およびオクタデシレン基などの直鎖状アルキレン基や、該直鎖状アルキレン基の任意の１つ以上の水素原子がメチル、エチル、ｎ−プロピル、イソプロピル、ｎ−ブチル、イソブチル、ｔ−ブチルなどのアルキル基で置換された分岐状アルキレン基を挙げることができる。 Examples of the alkylene group include methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group, decylene group, undecylene group, dodecylene group, tetradecylene group, hexadecylene group, and A linear alkylene group such as an octadecylene group, or any one or more hydrogen atoms of the linear alkylene group is an alkyl group such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or t-butyl. And a branched alkylene group substituted with.
前記アリーレン基としては、例えば、フェニレン基、トリレン基、キシリレン基、ナフチレン基を挙げることができる。 Examples of the arylene group include a phenylene group, a tolylene group, a xylylene group, and a naphthylene group.
式（１）中、Ｒ２は炭素原子数１〜１０のアルキル基、アリル基、アリール基、もしくはアリールアルキル基を表し、好ましくは、炭素原子数１〜１０のアルキル基を表す。 In Formula (1), R 2 represents an alkyl group having 1 to 10 carbon atoms, an allyl group, an aryl group, or an arylalkyl group, and preferably represents an alkyl group having 1 to 10 carbon atoms.
アルキル基としては、例えば、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｓｅｃ−ブチル基、ｔ−ブチル基、ｎ−ペンチル基、ネオペンチル基、ヘキシル基、ヘプチル基、オクチル基、２−エチルヘキシル基、ノニル基、およびデシル基などが挙げられる。 Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, n-pentyl group, neopentyl group, hexyl group, Examples include heptyl group, octyl group, 2-ethylhexyl group, nonyl group, and decyl group.
また前記アリール基としては、例えば、フェニル基、トリル基、キシリル基、ヒドロキシフェニル基、ニトロフェニル基、ナフチル基などが挙げられ、前記アリールアルキル基としては、例えば、ベンジル基、フェニルエチル基、フェニルプロピル基、ニトロベンジル基などが挙げられる。 Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group, a hydroxyphenyl group, a nitrophenyl group, and a naphthyl group. Examples of the arylalkyl group include a benzyl group, a phenylethyl group, and a phenylpropylene group. Group, nitrobenzyl group and the like.
式（１）中、Ｒ3は水素原子または、Ｒ２で規定した炭素原子数１〜１０のアルキル基、アリル基、アリール基、もしくはアリールアルキル基を表し、好ましくは水素原子を表す。 In formula (1), R 3 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, an allyl group, an aryl group, or an arylalkyl group defined by R 2 , preferably a hydrogen atom.
Ｐ１およびＰ２はそれぞれ独立に水素原子または共重合鎖を表す。すなわち、Ｐ１およびＰ２が共に共重合鎖の場合、水酸基が主鎖よりＲ1のスペーサーを介しグラフト化している構造を有し、Ｐ１またはＰ２のどちらか一方が水素原子の場合、水酸基が共重合鎖の末端部位に存在することを示す。 P 1 and P 2 each independently represent a hydrogen atom or a copolymer chain. That is, when both P 1 and P 2 are copolymer chains, the hydroxyl group has a structure grafted from the main chain through a spacer of R 1 , and when either P 1 or P 2 is a hydrogen atom, It shows that a hydroxyl group exists in the terminal site | part of a copolymer chain.
水酸基含有オレフィン共重合体（Ｐ）に含まれる水酸基含有量は、特に限定されるものではなく、極性材料との反応性や親水性を増加させることが目的の用途に用いる場合、当該含有量が多いほうが好ましい。 The hydroxyl group content contained in the hydroxyl group-containing olefin copolymer (P) is not particularly limited. When used for the purpose of increasing reactivity with a polar material or hydrophilicity, the content is More is preferable.
本発明は、［工程１］、［工程２］および［工程３］を含む製造工程を順次実施することで、前述の水酸基含有オレフィン共重合体（Ｐ）を製造する。以下、それぞれの工程について具体的に説明する。 This invention manufactures the above-mentioned hydroxyl-containing olefin copolymer (P) by implementing sequentially the manufacturing process containing [Process 1], [Process 2], and [Process 3]. Hereinafter, each process is demonstrated concretely.
［工程１］
［工程１］は、二重結合含有カルボン酸誘導体（Ｅ）とアルキルアルミニウム化合物（Ａ）とを反応させて、二重結合含有アルミノキシ化合物（Ｍ）を製造する工程である。
[Step 1]
[Step 1] is a step of producing a double bond-containing aluminoxy compound (M) by reacting the double bond-containing carboxylic acid derivative (E) with the alkylaluminum compound (A).
（Ｅ）は、一般式（２）で表され、ビニル基とカルボン酸、その金属塩、またはそのエステル体が分子中に存在する化合物である。 (E) is a compound represented by the general formula (2), in which a vinyl group and a carboxylic acid, a metal salt thereof, or an ester thereof is present in the molecule.
式（２）中、Ｒ１は炭素原子数１〜２０の２価のアルキレン基もしくはアリーレン基を表す。前記アルキレン基としては、例えば、メチレン基、エチレン基、プロピレン基、ブチレン基、ペンチレン基、ヘキシレン基、ヘプチレン基、オクチレン基、ノニレン基、デシレン基、ウンデシレン基、ドデシレン基、テトラデシレン基、ヘキサデシレン基およびオクタデシレン基などの直鎖状アルキレン基や、該直鎖状アルキレン基の任意の１つ以上の水素原子がメチル、エチル、ｎ−プロピル、イソプロピル、ｎ−ブチル、イソブチル、ｔ−ブチルなどのアルキル基で置換された分岐状アルキレン基を挙げることができる。 In formula (2), R 1 represents a divalent alkylene group having 1 to 20 carbon atoms or an arylene group. Examples of the alkylene group include methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group, decylene group, undecylene group, dodecylene group, tetradecylene group, hexadecylene group, and A linear alkylene group such as an octadecylene group, or any one or more hydrogen atoms of the linear alkylene group is an alkyl group such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or t-butyl. And a branched alkylene group substituted with.
前記アリーレン基としては、例えば、フェニレン基、トリレン基、キシリレン基、ナフチレン基を挙げることができる。 Examples of the arylene group include a phenylene group, a tolylene group, a xylylene group, and a naphthylene group.
また、式（２）中、Ｒ4は水素原子、金属原子、または炭素原子数１〜１０のアルキル基、アリール基、もしくはアリールアルキル基を表す。前記アルキル基としては、例えば、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｓｅｃ−ブチル基、ｔ−ブチル基、ｎ−ペンチル基、ネオペンチル基、ヘキシル基、ヘプチル基、オクチル基、２−エチルヘキシル基、ノニル基、およびデシル基などが挙げられる。 In Formula (2), R 4 represents a hydrogen atom, a metal atom, or an alkyl group, aryl group, or arylalkyl group having 1 to 10 carbon atoms. Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, n-pentyl group, neopentyl group, and hexyl group. , Heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group and the like.
また前記アリール基としては、例えば、フェニル基、トリル基、キシリル基、ヒドロキシフェニル基、ニトロフェニル基、ナフチル基などが挙げられ、前記アリールアルキル基としては、例えば、ベンジル基、フェニルエチル基、フェニルプロピル基、ニトロベンジル基などが挙げられる。 Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group, a hydroxyphenyl group, a nitrophenyl group, and a naphthyl group. Examples of the arylalkyl group include a benzyl group, a phenylethyl group, and a phenylpropylene group. Group, nitrobenzyl group and the like.
上記の二重結合含有カルボン酸誘導体（Ｅ）として具体的には、例えば、５−ヘキセン酸、６−ヘプテン酸、７−オクテン酸、８−ノネン酸、９−デセン酸、１０−ウンデセン酸、１１−ドデセン酸、２−メチル−５−ヘキセン酸、２−メチル−６−ヘプテン酸、２−メチル−７−オクテン酸、２−メチル−８−ノネン酸、２−メチル−９−デセン酸、２−メチル−１０−ウンデセン酸、２−メチル−１１−ドデセン酸、２−エチル−５−ヘキセン酸、２−エチル−６−ヘプテン酸、２−エチル−７−オクテン酸、２−エチル−８−ノネン酸、２−エチル−９−デセン酸、２−エチル−１０−ウンデセン酸、２−プロピル−５−ヘキセン酸、２−プロピル−６−ヘプテン酸、２−プロピル−７−オクテン酸、２−プロピル−８−ノネン酸、２−プロピル−９−デセン酸、２−プロピル−１０−ウンデセン酸、２−ブチル−５−ヘキセン酸、２−ブチル−６−ヘプテン酸、２−ブチル−７−オクテン酸、２−ブチル−８−ノネン酸、２−ブチル−９−デセン酸、２−ブチル−１０−ウンデセン酸、２−イソプロピル−５−ヘキセン酸、２−イソプロピル−６−ヘプテン酸、２−イソプロピル−７−オクテン酸、２−イソプロピル−８−ノネン酸、２−イソプロピル−９−デセン酸、２−イソプロピル−１０−ウンデセン酸、２−イソブチル−５−ヘキセン酸、２−ｔ−ブチル−６−ヘプテン酸、２−イソプロピル−３−メチル−７−オクテン酸、２−メチル−３−イソプロピル−８−ノネン酸、３−イソブチル−３−メチル−９−デセン酸、２，２−ジメチル−１０−ウンデセン酸、２，３，３−トリメチル−１１−ドデセン酸などのビニル基とカルボキシル基を有する化合物、
５−ヘキセン酸メチル、６−ヘプテン酸メチル、７−オクテン酸メチル、８−ノネン酸メチル、９−デセン酸メチル、１０−ウンデセン酸メチル、１１−ドデセン酸メチル、５−ヘキセン酸エチル、６−ヘプテン酸エチル、７−オクテン酸エチル、８−ノネン酸エチル、９−デセン酸エチル、１０−ウンデセン酸エチル、１１−ドデセン酸エチル、５−ヘキセン酸イソプロピル、６−ヘプテン酸イソプロピル、７−オクテン酸イソプロピル、８−ノネン酸イソプロピル、９−デセン酸イソプロピル、１０−ウンデセン酸イソプロピル、１１−ドデセン酸イソプロピル、５−ヘキセン酸ブチル、６−ヘプテン酸ブチル、７−オクテン酸ブチル、８−ノネン酸ブチル、９−デセン酸ブチル、１０−ウンデセン酸ブチル、１１−ドデセン酸ブチル、２−メチル−５−ヘキセン酸メチル、２−メチル−６−ヘプテン酸メチル、２−メチル−７−オクテン酸エチル、２−メチル−８−ノネン酸メチル、２−メチル−９−デセン酸ブチル、２−メチル−１０−ウンデセン酸エチル、２−エチル−５−ヘキセン酸ブチル、２−エチル−６−ヘプテン酸エチル、２−エチル−７−オクテン酸イソプロピル、２−エチル−８−ノネン酸エチル、２−エチル−９−デセン酸メチル、２−エチル−１０−ウンデセン酸エチル、２−プロピル−５−ヘキセン酸メチル、２−プロピル−６−ヘプテン酸メチル、２−プロピル−７−オクテン酸エチル、２−プロピル−９−デセン酸メチル、２−プロピル−１０−ウンデセン酸エチル、２−ブチル−７−オクテン酸メチル、２−ブチル−８−ノネン酸メチル、２−ブチル−９−デセン酸メチル、２−ブチル−１０−ウンデセン酸メチル、２−イソプロピル−５−ヘキセン酸ブチル、２−イソプロピル−６−ヘプテン酸エチル、２−イソプロピル−７−オクテン酸メチル、２−イソプロピル−８−ノネン酸メチル、２−イソプロピル−９−デセン酸ブチル、２−イソプロピル−１０−ウンデセン酸メチル、２−イソブチル−５−ヘキセン酸メチル、２−ｔ−ブチル−６−ヘプテン酸メチル、２−イソプロピル−３−メチル−７−オクテン酸エチル、３−イソブチル−３−メチル−９−デセン酸プロピル、１０−ウンデセン酸フェニル、１０−ウンデセン酸−（４−ヒドロキシ）フェニル、１０−ウンデセン酸−ベンジル、１０−ウンデセン酸−（４−ニトロ）ベンジルなどのビニル基とエステル基を有する化合物が挙げられる。
Specific examples of the double bond-containing carboxylic acid derivative (E) include, for example, 5-hexenoic acid, 6-heptenoic acid, 7-octenoic acid, 8-nonenoic acid, 9-decenoic acid, 10-undecenoic acid, 11-dodecenoic acid, 2-methyl-5-hexenoic acid, 2-methyl-6-heptenoic acid, 2-methyl-7-octenoic acid, 2-methyl-8-nonenoic acid, 2-methyl-9-decenoic acid, 2-methyl-10-undecenoic acid, 2-methyl-11-dodecenoic acid, 2-ethyl-5-hexenoic acid, 2-ethyl-6-heptenoic acid, 2-ethyl-7-octenoic acid, 2-ethyl-8 -Nonenoic acid, 2-ethyl-9-decenoic acid, 2-ethyl-10-undecenoic acid, 2-propyl-5-hexenoic acid, 2-propyl-6-heptenoic acid, 2-propyl-7-octenoic acid, 2 -Propyl-8-nonenoic acid, 2 Propyl-9-decenoic acid, 2-propyl-10-undecenoic acid, 2-butyl-5-hexenoic acid, 2-butyl-6-heptenoic acid, 2-butyl-7-octenoic acid, 2-butyl-8-nonene Acid, 2-butyl-9-decenoic acid, 2-butyl-10-undecenoic acid, 2-isopropyl-5-hexenoic acid, 2-isopropyl-6-heptenoic acid, 2-isopropyl-7-octenoic acid, 2-isopropyl -8-nonenoic acid, 2-isopropyl-9-decenoic acid, 2-isopropyl-10-undecenoic acid, 2-isobutyl-5-hexenoic acid, 2-t-butyl-6-heptenoic acid, 2-isopropyl-3- Methyl-7-octenoic acid, 2-methyl-3-isopropyl-8-nonenoic acid, 3-isobutyl-3-methyl-9-decenoic acid, 2,2-dimethyl-10-undecenoic acid, , Compounds having a vinyl group and a carboxyl group, such as 3,3-trimethyl-11-dodecenoic acid,
Methyl 5-hexenoate, methyl 6-heptenoate, methyl 7-octenoate, methyl 8-nonenoate, methyl 9-decenoate, methyl 10-undecenoate, methyl 11-dodecenoate, ethyl 5-hexenoate, 6- Ethyl heptenoate, ethyl 7-octenoate, ethyl 8-nonenoate, ethyl 9-decenoate, ethyl 10-undecenoate, ethyl 11-dodecenoate, isopropyl 5-hexenoate, isopropyl 6-heptenoate, 7-octenoic acid Isopropyl, isopropyl 8-nonenoate, isopropyl 9-decenoate, isopropyl 10-undecenoate, isopropyl 11-dodecenoate, butyl 5-hexenoate, butyl 6-heptenoate, butyl 7-octenoate, butyl 8-nonenate, 9-butyl decenoate, 10-butyl undecenoate, 11-butyl dodecenoate, Methyl methyl-5-hexenoate, methyl 2-methyl-6-heptenoate, ethyl 2-methyl-7-octenoate, methyl 2-methyl-8-nonenoate, butyl 2-methyl-9-decenoate, -Ethyl methyl-10-undecenoate, butyl 2-ethyl-5-hexenoate, ethyl 2-ethyl-6-heptenoate, isopropyl 2-ethyl-7-octenoate, ethyl 2-ethyl-8-nonenoate, 2 Methyl ethyl-9-decenoate, ethyl 2-ethyl-10-undecenoate, methyl 2-propyl-5-hexenoate, methyl 2-propyl-6-heptenoate, ethyl 2-propyl-7-octenoate, 2 Methyl -propyl-9-decenoate, ethyl 2-propyl-10-undecenoate, methyl 2-butyl-7-octenoate, methyl 2-butyl-8-nonenoate, 2- Methyl til-9-decenoate, methyl 2-butyl-10-undecenoate, butyl 2-isopropyl-5-hexenoate, ethyl 2-isopropyl-6-heptenoate, methyl 2-isopropyl-7-octenoate, 2- Methyl isopropyl-8-nonenate, butyl 2-isopropyl-9-decenoate, methyl 2-isopropyl-10-undecenoate, methyl 2-isobutyl-5-hexenoate, methyl 2-t-butyl-6-heptenoate, 2-Isopropyl-3-methyl-7-octenoic acid ethyl, 3-isobutyl-3-methyl-9-decenoic acid propyl, 10-undecenoic acid phenyl, 10-undecenoic acid- (4-hydroxy) phenyl, 10-undecenoic acid -Benzyl, 10-undecenoic acid- (4-nitro) benzyl and other vinyl groups and ester groups Compound may be mentioned.
また、５−ヘキセン酸無水物、１０−ウンデセン酸無水物、１０−ウンデセン酸酢酸無水物のように、上述のビニル基とカルボキシル基を有する化合物が脱水した酸無水物も本発明の二重結合含有カルボン酸誘導体（Ｅ）として用いることが可能である。この場合、ビニル基とカルボキシル基を有する化合物は同一のものが脱水した酸無水物であっても、異なるものが脱水した酸無水物であっても構わない。 In addition, an acid anhydride obtained by dehydration of the above compound having a vinyl group and a carboxyl group, such as 5-hexenoic acid anhydride, 10-undecenoic acid anhydride, and 10-undecenoic acid acetic anhydride, is also a double bond of the present invention. It can be used as the containing carboxylic acid derivative (E). In this case, the same compound having a vinyl group and a carboxyl group may be a dehydrated acid anhydride, or a different compound may be a dehydrated acid anhydride.
また更に、Ｒ4が金属原子の１０−ウンデセン酸亜鉛や１０−ウンデセン酸ナトリウムのように、上述のビニル基とカルボキシル基を有する化合物のカルボキシル基がナトリウムや亜鉛などの金属塩となっている化合物も、本発明の二重結合含有カルボン酸誘導体（Ｅ）として用いることが可能である。 Furthermore, a compound in which the carboxyl group of the above compound having a vinyl group and a carboxyl group is a metal salt such as sodium or zinc, such as zinc 4- undecenoate or sodium 10-undecenoate in which R 4 is a metal atom. Can also be used as the double bond-containing carboxylic acid derivative (E) of the present invention.
このような、二重結合含有カルボン酸誘導体（Ｅ）の例示化合物の中でも、環境調和性および経済的観点より、ひまし油を原料とした熱分解反応により得られるウンデセン酸及びその誘導体が好適である。具体的には、１０−ウンデセン酸、１０−ウンデセン酸メチル、１０−ウンデセン酸エチル、１０−ウンデセン酸−ｎ−プロピル、１０−ウンデセン酸−ｎ−ブチルが挙げられる。 Among such exemplified compounds of the double bond-containing carboxylic acid derivative (E), undecenoic acid obtained by a thermal decomposition reaction using castor oil as a raw material and derivatives thereof are preferable from the viewpoint of environmental harmony and economy. Specific examples include 10-undecenoic acid, 10-undecenoic acid methyl, 10-undecenoic acid ethyl, 10-undecenoic acid-n-propyl, and 10-undecenoic acid-n-butyl.
なお（Ｅ）は、従来公知の方法で合成することができ、また市販品を入手することも可能である。 (E) can be synthesized by a conventionally known method, and a commercially available product can also be obtained.
アルキルアルミニウム化合物（Ａ）は、分子中に少なくとも一つのアルキル基、アリール基、またはアリル基がアルミニウムに結合した構造を有するものであり、したがって高い反応性を有すＣ-Ａｌ結合を有す化合物である。 The alkylaluminum compound (A) is a compound having a structure in which at least one alkyl group, aryl group, or allyl group is bonded to aluminum in the molecule, and thus has a highly reactive C—Al bond. It is.
具体的には、トリメチルアルミニウム、トリエチルアルミニウム、トリ-n-プロピルアルミニウム、トリ-n-ブチルアルミニウム、トリイソブチルアルミニウム、トリ-n-ヘキシルアルミニウム、トリフェニルアルミニウム、トリ-n-へプチルアルミニウム、トリ-n-オクチルアルミニウム、トリ-n-デシルアルミニウム、トリアリルアルミニウム、ジエチルアルミニウムクロリド、ジエチルアルミニウムブロミド、ジエチルアルミニウムアイオダイド、エチルアルミニウムセスキクロリド、エチルアルミニウムジクロリド、テトラエチルジアルミノキサン、テトライソブチルジアルミノキサン、トリイソブチルジアルミノキサン、ジメチルアルミニウムイソプロポキシド、ジエチルアルミニウムハイドライド、ジイソブチルアルミニウムハイドライドなどが挙げられる。 Specifically, trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, triphenylaluminum, tri-n-heptylaluminum, tri- n-octyl aluminum, tri-n-decyl aluminum, triallyl aluminum, diethylaluminum chloride, diethylaluminum bromide, diethylaluminum iodide, ethylaluminum sesquichloride, ethylaluminum dichloride, tetraethyldialuminoxane, tetraisobutyldialuminoxane, triisobutyldi Such as aluminoxane, dimethylaluminum isopropoxide, diethylaluminum hydride, diisobutylaluminum hydride And the like.
本発明の水酸基含有オレフィン共重合体（Ｐ）への水酸基の効率導入の観点、および後述する［工程２］における触媒耐被毒性の観点より、一般式（５）で表されるトリアルキル体が好ましい。具体的には、トリメチルアルミニウム、トリエチルアルミニウム、トリ-n-ブチルアルミニウム、トリイソブチルアルミニウム、トリ-n-ヘキシルアルミニウム、トリ-n-へプチルアルミニウム、トリ-n-オクチルアルミニウム、トリ-n-デシルアルミニウムが挙げられ、経済的実用性から、トリエチルアルミニウム、トリイソブチルアルミニウムが好ましく用いられる。 From the viewpoint of introducing efficiency of the hydroxyl group into the hydroxyl group-containing olefin copolymer (P) of the present invention and from the viewpoint of catalyst poisoning resistance in [Step 2] described later, the trialkyl compound represented by the general formula (5) is preferable. Specifically, trimethylaluminum, triethylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-heptylaluminum, tri-n-octylaluminum, tri-n-decylaluminum In view of economic practicality, triethylaluminum and triisobutylaluminum are preferably used.
二重結合含有カルボン酸誘導体（Ｅ）とアルキルアルミニウム化合物（Ａ）の反応は、（Ｅ）のカルボン酸基またはその誘導体基部位に、（Ａ）のアルキル基、アリール基、またはアリル基が付加反応を起こした結果の生成物と考えられる。すなわち、この反応により得られる二重結合含有アルミノキシ化合物（Ｍ）は、以下の式（Ｉ）に示されるような、アルミノキシ結合（Ａｌ−Ｏ）を有し、かつ酸素原子のα位炭素原子にアルキル化した（Ｍ−１）に示される構造と推定される。式（Ｉ）中、Ｒ2、Ｒ3およびＲ5は、（Ａ）由来の基である。 In the reaction between the double bond-containing carboxylic acid derivative (E) and the alkylaluminum compound (A), the alkyl group, aryl group, or allyl group of (A) is added to the carboxylic acid group of (E) or its derivative group site. The product resulting from the reaction is considered. That is, the double bond-containing aluminoxy compound (M) obtained by this reaction has an aluminoxy bond (Al—O) as shown in the following formula (I), and is attached to the α-position carbon atom of the oxygen atom. The structure is presumed to be alkylated (M-1). In formula (I), R 2 , R 3 and R 5 are groups derived from (A).
（Ｍ−２）は、酸素原子を有しているものの、その酸素原子にＡｌが直接結合し、かつ嵩高いＲ5基の存在により、後述する工程２における共重合モノマーとして、活性の著しい低下を招くことなく好適に用いることが出来る。式（Ｉ）中、Ｘは通常１〜２である。 Although (M-2) has an oxygen atom, Al is directly bonded to the oxygen atom, and due to the presence of a bulky R 5 group, the activity is significantly reduced as a copolymerization monomer in Step 2 described later. It can be suitably used without incurring. In formula (I), X is usually 1-2.
また、非特許文献５に示されるごとく、式（Ｉ）が単独で存在していることもあれば、マルチコンプレックスとして存在する場合もあるが、本発明の（Ｍ）を満たす構造として何ら問題はない。
[工程１]終了時における未反応の（E）の存在は、[工程２]における重合反応の被毒物質となるため、本発明の水酸基含有ポリオレフィンを得ることが出来ない場合が生じる。従って、［工程１］におけるガスクロマトグラフィーで追跡する（E）の転化率は、９５％以上、好ましくは、１００％である。
Further, as shown in Non-Patent Document 5, the formula (I) may exist alone or as a multi-complex, but there is no problem as a structure satisfying (M) of the present invention. Absent.
Since the presence of unreacted (E) at the end of [Step 1] becomes a poisoning substance for the polymerization reaction in [Step 2], the hydroxyl group-containing polyolefin of the present invention may not be obtained. Therefore, the conversion rate of (E) monitored by gas chromatography in [Step 1] is 95% or more, preferably 100%.
このように、[工程１]において（E）の高転化率を達成するため、（Ｅ）と（Ａ）の使用量は、通常、１：１〜１：１０、好ましくは１：２〜１：４のモル比である。 Thus, in order to achieve a high conversion rate of (E) in [Step 1], the amount of (E) and (A) used is usually 1: 1 to 1:10, preferably 1: 2 to 1. : 4 molar ratio.
[工程１]における反応は、無溶媒でも可能であるが、有機溶剤を用いる場合は、［工程２］における重合を阻害しない公知の脱水炭化水素系有機溶剤が用いられる。具体的には、ヘキサン、メチルシクロヘキサン、シクロヘキサン、ヘプタン、トルエン、キシレン、デカンなどが好適である。また溶媒の使用量は、通常、二重結合含有カルボン酸誘導体（Ｅ）に対し、０．１〜１００００重量倍、好ましくは０．１〜１０００重量倍の範囲である。 The reaction in [Step 1] can be performed without a solvent, but when an organic solvent is used, a known dehydrated hydrocarbon organic solvent that does not inhibit the polymerization in [Step 2] is used. Specifically, hexane, methylcyclohexane, cyclohexane, heptane, toluene, xylene, decane, and the like are preferable. Moreover, the usage-amount of a solvent is 0.1-10000 weight times normally with respect to a double bond containing carboxylic acid derivative (E), Preferably it is the range of 0.1-1000 weight times.
［工程１］における（Ａ）と（Ｅ）の反応時間は、通常１分間以上、好ましくは１分〜５時間の範囲である。また、反応温度は、通常−１００〜２００℃、好ましくは０〜１２０℃で行われる。 The reaction time of (A) and (E) in [Step 1] is usually 1 minute or longer, preferably 1 minute to 5 hours. The reaction temperature is usually -100 to 200 ° C, preferably 0 to 120 ° C.
このようにして得られた二重結合含有アルミノキシ化合物（Ｍ）は、そのままで次の［工程２］に用いることができるが、必要に応じて、使用した溶媒や残存する原料および副生物等を除去してから用いることもできる。溶媒等の除去あるいは濃縮の方法としては、留去法等の一般的な方法を適宜用いることができる。 The double bond-containing aluminoxy compound (M) thus obtained can be used as it is in the next [Step 2], but if necessary, the used solvent, the remaining raw materials and by-products, etc. It can also be used after removal. As a method for removing or concentrating the solvent or the like, a general method such as a distillation method can be appropriately used.
［工程２］
［工程２］は遷移金属触媒を用い、前記［工程１］で得られた二重結合含有アルミノキシ化合物（Ｍ）と炭素原子数２〜２０のオレフィン（Ｌ）とを共重合する工程である。
［工程２］における、遷移金属触媒とは、一般に用いられるオレフィン重合用配位重合触媒であり、通常、（ａ）周期表第３〜１０族（３族にはランタノイドおよびアクチノイドも含まれる。）から選ばれる遷移金属化合物と、（ｂ）（ｂ−１）有機アルミニウムオキシ化合物、（ｂ−２）前記化合物（ａ）と反応してイオン対を形成する化合物、および（ｂ−３）有機アルキルアルミニウム化合物から選ばれる少なくとも１種の化合物からなる。
[Step 2]
[Step 2] is a step of copolymerizing the double bond-containing aluminoxy compound (M) obtained in [Step 1] with an olefin (L) having 2 to 20 carbon atoms using a transition metal catalyst.
The transition metal catalyst in [Step 2] is a commonly used coordination polymerization catalyst for olefin polymerization, and usually (a) Groups 3 to 10 of the periodic table (Group 3 includes lanthanoids and actinoids). A transition metal compound selected from: (b) (b-1) an organoaluminum oxy compound, (b-2) a compound that reacts with the compound (a) to form an ion pair, and (b-3) an organic alkyl. It consists of at least one compound selected from aluminum compounds.
遷移金属化合物（ａ）としては、チーグラーナッタ触媒、メタロセン触媒、ポストメタロセン触媒の他に、公知の有機金属錯体を用いることができる。特に好ましい遷移金属化合物（ａ）として、高活性性能や高共重合性能の観点より、例えば、特開２０００-１９１７１３号公報、国際公開２０００−４３４２６号パンフレットおよび国際公開２００１−２７１２４号パンフレットに記載された化合物を制限無く用いることができる。 As the transition metal compound (a), a known organometallic complex can be used in addition to the Ziegler-Natta catalyst, the metallocene catalyst, and the post-metallocene catalyst. Particularly preferred transition metal compounds (a) are described in, for example, JP 2000-191713 A, International Publication 2000-43426, and International Publication 2001-27124, from the viewpoint of high activity performance and high copolymerization performance. These compounds can be used without limitation.
［工程２］で用いられる有機アルミニウムオキシ化合物（ｂ−１）は、従来公知のアルミノキサン（アルモキサンともいう。）であってもよく、また特開平２−７８６８７号公報に例示されているようなベンゼン不溶性の有機アルミニウムオキシ化合物であってもよい。さらに有機アルミニウムオキシ化合物としては、下記一般式で表されるホウ素を含んだ有機アルミニウムオキシ化合物を挙げることもできる。 The organoaluminum oxy compound (b-1) used in [Step 2] may be a conventionally known aluminoxane (also referred to as alumoxane), and benzene as exemplified in JP-A-2-78687. It may be an insoluble organoaluminum oxy compound. Furthermore, as an organic aluminum oxy compound, the organic aluminum oxy compound containing the boron represented by the following general formula can also be mentioned.
式中、Ｒ８は炭素原子数１〜１０の炭化水素基を示す。Ｒ９は、互いに同一でも異なっていてもよく、水素原子、ハロゲン原子、炭素原子数１〜１０の炭化水素基を示す。 In the formula, R 8 represents a hydrocarbon group having 1 to 10 carbon atoms. R 9 may be the same as or different from each other, and represents a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 10 carbon atoms.
［工程２］で用いられる前記遷移金属化合物（ａ）と反応してイオン対を形成する化合物（ｂ−２）（以下「イオン化イオン性化合物」ということがある）としては、特表平１−５０１９５０号公報、特表平１−５０２０３６号公報、特開平３−１７９００５号公報、特開平３−１７９００６号公報、特開平３−２０７７０３号公報、特開平３−２０７７０４号公報、米国特許５３２１１０６号などに記載されたルイス酸、イオン性化合物およびボラン化合物、カルボラン化合物が挙げられる。さらにヘテロポリ化合物およびイソポリ化合物を挙げることもできる。 As the compound (b-2) (hereinafter sometimes referred to as “ionized ionic compound”) that reacts with the transition metal compound (a) used in [Step 2] to form an ion pair, No. 501950, JP-A-1-502036, JP-A-3-179905, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, US Pat. No. 5,321,106, etc. And Lewis acids, ionic compounds, borane compounds, and carborane compounds described in 1). Heteropoly compounds and isopoly compounds can also be mentioned.
ルイス酸としてはマグネシウム含有ルイス酸、アルミニウム含有ルイス酸、ホウ素含有ルイス酸などが挙げられ、こられのうちホウ素含有ルイス酸が好ましい。イオン性化合物は、カチオン性化合物とアニオン性化合物とからなる塩である。アニオンは前記遷移金属化合物と反応することにより遷移金属化合物をカチオン化し、イオン対を形成することにより遷移金属カチオン種を安定化させる働きがある。そのようなアニオンとしては、有機ホウ素化合物アニオン、有機ヒ素化合物アニオン、有機アルミニウム化合物アニオンなどがあり、比較的嵩高で遷移金属カチオン種を安定化させるものが好ましい。このようなイオン化イオン性化合物は、２種以上混合して用いることができる。 Examples of the Lewis acid include magnesium-containing Lewis acid, aluminum-containing Lewis acid, and boron-containing Lewis acid. Among these, boron-containing Lewis acid is preferable. The ionic compound is a salt composed of a cationic compound and an anionic compound. The anion functions to cationize the transition metal compound by reacting with the transition metal compound and stabilize the transition metal cation species by forming an ion pair. Such anions include organoboron compound anions, organoarsenic compound anions, organoaluminum compound anions, and the like, and those that are relatively bulky and stabilize the transition metal cation species are preferred. Such ionized ionic compounds can be used as a mixture of two or more.
［工程２］で用いられる有機アルミニウム化合物（ｂ−３）は、炭素原子数１〜１２の炭化水素基および／またはハロゲン原子、アルコキシ基、シロキシ基、アミド基、水素原子で置換されている有機アルミニウム化合物である。これらの有機アルミニウム化合物は、２種以上組合わせて用いることもできる。 The organoaluminum compound (b-3) used in [Step 2] is an organic substituted with a hydrocarbon group having 1 to 12 carbon atoms and / or a halogen atom, an alkoxy group, a siloxy group, an amide group or a hydrogen atom. It is an aluminum compound. These organoaluminum compounds can be used in combination of two or more.
本発明で用いられるオレフィン重合触媒は、上記遷移金属化合物（ａ）と、有機アルミニウムオキシ化合物（ｂ−１）、イオン化イオン性化合物（ｂ−２）および有機アルミニウム化合物（ｂ−３）から選ばれる少なくとも１種の化合物（ｂ）から形成され、例えば遷移金属化合物（ａ）がシクロペンタジエニル骨格を有する配位子を含む遷移金属化合物である場合には、該化合物と、有機アルミニウムオキシ化合物（ｂ−１）および／またはイオン化イオン性化合物（ｂ−２）と、必要に応じて有機アルミニウム化合物（ｂ−３）とから形成される。 The olefin polymerization catalyst used in the present invention is selected from the transition metal compound (a), the organoaluminum oxy compound (b-1), the ionized ionic compound (b-2), and the organoaluminum compound (b-3). When formed from at least one compound (b), for example, when the transition metal compound (a) is a transition metal compound containing a ligand having a cyclopentadienyl skeleton, the compound and an organoaluminum oxy compound ( b-1) and / or an ionized ionic compound (b-2) and, if necessary, an organoaluminum compound (b-3).
［工程２］で用いられるオレフィン重合触媒には、遷移金属化合物（ａ）、有機アルミニウムオキシ化合物（ｂ−１）、イオン化イオン性化合物（ｂ−２）および有機アルミニウム化合物（ｂ−３）のうち少なくとも１つの成分が粒子状担体に担持されてなる固体状触媒、および粒子状担体、遷移金属化合物（ａ）、有機アルミニウムオキシ化合物（ｂ−１）（またはイオン化イオン性化合物（ｂ−２））および予備重合により生成するオレフィン重合体と、必要に応じて有機アルミニウム化合物（ｂ−３）とからなる予備重合触媒が含まれる。 The olefin polymerization catalyst used in [Step 2] includes a transition metal compound (a), an organoaluminum oxy compound (b-1), an ionized ionic compound (b-2), and an organoaluminum compound (b-3). Solid catalyst comprising at least one component supported on a particulate carrier, and particulate carrier, transition metal compound (a), organoaluminum oxy compound (b-1) (or ionized ionic compound (b-2)) And a prepolymerization catalyst comprising an olefin polymer produced by prepolymerization and, if necessary, an organoaluminum compound (b-3).
［工程２］において用いるオレフィン重合触媒の成分、組成および調製方法は、前記記載および従来公知の方法を基に、適宜設定することができる。 The components, composition and preparation method of the olefin polymerization catalyst used in [Step 2] can be appropriately set based on the above description and conventionally known methods.
［工程２］では、このようなオレフィン重合触媒を用い、前記［工程１］で得られた二重結合含有アルミノキシ化合物（Ｍ）と炭素原子数２〜２０のオレフィン（Ｌ）との共重合を行う。 In [Step 2], using such an olefin polymerization catalyst, copolymerization of the double bond-containing aluminoxy compound (M) obtained in [Step 1] and an olefin (L) having 2 to 20 carbon atoms is carried out. Do.
炭素原子数２〜２０のオレフィンは、上記のオレフィン重合用配位重合触媒にて重合が可能なモノマーであれば限定されるものではないが、例えば、エチレン、プロピレン、１−ブテン、２−ブテン、１−ペンテン、３−メチル−１−ブテン、１−ヘキセン、４−メチル−１−ペンテン、３−メチル−１−ペンテン、３−エチル−１−ペンテン、４，４−ジメチル−１−ペンテン、４−メチル−１−ヘキセン、４，４−ジメチル−１−ヘキセン、４−エチル−１−ヘキセン、３−エチル−１−ヘキセン、１−オクテン、１−デセン、１−ドデセン、１−テトラデセン、１−ヘキサデセン、１−オクタデセン、１−エイコセンや一般に環状オレフィンと呼ばれるノルボルネンやテトラシクロドデセンなどが挙げられる。これらの中でもエチレン、プロピレン、１−ブテン、４−メチル−１−ペンテン、１−ヘキセン、１−オクテン、ノルボルネン、テトラシクロドデセンから選ばれることが好ましい。オレフィン（Ｌ）は、一種類用いても良いが、２種類以上の多元共重合でも構わない。 The olefin having 2 to 20 carbon atoms is not limited as long as it is a monomer that can be polymerized by the above coordination polymerization catalyst for olefin polymerization. For example, ethylene, propylene, 1-butene, 2-butene 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4,4-dimethyl-1-pentene 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene 1-hexadecene, 1-octadecene, 1-eicosene, norbornene generally called cyclic olefin, and tetracyclododecene. Among these, ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, norbornene, and tetracyclododecene are preferable. One type of olefin (L) may be used, but two or more types of multi-component copolymerization may be used.
［工程２］において用いる、前記［工程１］で得られた二重結合含有アルミノキシ化合物（Ｍ）と炭素原子数２〜２０のオレフィン（Ｌ）との量比は、通常モル比で１：１〜１：１００００、好ましくは１：１０〜１：５０００の範囲で適宜設定される。また、前記のオレフィン重合触媒と二重結合含有アルミノキシ化合物（Ｍ）および炭素原子数２〜２０のオレフィン（Ｌ）との量比は、前記記載および従来公知の方法を基に、適宜設定することができる。 The amount ratio of the double bond-containing aluminoxy compound (M) obtained in [Step 1] and the olefin (L) having 2 to 20 carbon atoms used in [Step 2] is usually 1: 1 by molar ratio. ˜1: 10000, preferably in the range of 1:10 to 1: 5000. The quantity ratio of the olefin polymerization catalyst to the double bond-containing aluminoxy compound (M) and the olefin (L) having 2 to 20 carbon atoms should be appropriately set based on the above description and a conventionally known method. Can do.
［工程２］の共重合工程は、スラリー重合プロセス、溶液重合プロセス、気相重合プロセス、バルク重合プロセスなど、従来公知のオレフィン重合プロセスにて、適宜条件を設定して行うことができる。 The copolymerization step of [Step 2] can be performed by appropriately setting conditions in a conventionally known olefin polymerization process such as a slurry polymerization process, a solution polymerization process, a gas phase polymerization process, and a bulk polymerization process.
以上のように、［工程２］では、遷移金属触媒の存在下、前記［工程１］で得られた二重結合含有アルミノキシ化合物（Ｍ）と炭素原子数２〜２０のオレフィン（Ｌ）とを共重合させることにより、下記一般式（４）で表される部分構造を有するアルミノキシ基含有オレフィン共重合体（Ｐ’）が製造される。 As described above, in [Step 2], the double bond-containing aluminoxy compound (M) obtained in [Step 1] and the olefin (L) having 2 to 20 carbon atoms are obtained in the presence of a transition metal catalyst. By copolymerization, an aluminoxy group-containing olefin copolymer (P ′) having a partial structure represented by the following general formula (4) is produced.
式（４）中、Ｒ１、Ｒ2、Ｒ3、Ｒ5、Ｐ１およびＰ２はそれぞれ前記式（１）、式（２）および式（２）中で定義したものと同様の構造を表す。 In formula (4), R 1 , R 2 , R 3 , R 5 , P 1 and P 2 have the same structures as those defined in formula (1), formula (2) and formula (2), respectively. To express.
［工程２］で得られたアルミノキシ基含有オレフィン共重合体（Ｐ’）は、必要に応じて、次の［工程３］に先立って、取り出し、精製を行うこともできる。 The aluminoxy group-containing olefin copolymer (P ′) obtained in [Step 2] can be taken out and purified prior to the next [Step 3], if necessary.
［工程３］
［工程３］は、前記［工程２］で得られたアルミノキシ基含有オレフィン共重合体（Ｐ’）を、プロトン供与性化合物で処理し、脱Ａｌ保護を行い、前記式（１）または／および（２）で表される部分構造を有する水酸基含有オレフィン共重合体（Ｐ）に変換する工程である。
[Step 3]
In [Step 3], the aluminoxy group-containing olefin copolymer (P ′) obtained in [Step 2] is treated with a proton-donating compound to remove Al, and the formula (1) or / and This is a step of converting to a hydroxyl group-containing olefin copolymer (P) having a partial structure represented by (2).
［工程３］で用いる、プロトン供与性化合物とは、［工程２］で得られたアルミノキシ基含有オレフィン共重合体（Ｐ’）のＯ−Ａｌ結合を効果的に切断し、水酸基を生成させうる化合物である。 The proton donating compound used in [Step 3] can effectively cleave the O—Al bond of the aluminoxy group-containing olefin copolymer (P ′) obtained in [Step 2] to generate a hydroxyl group. A compound.
プロトン供与性化合物として、具体的には、水素、水、塩酸水、苛性ソーダー水、またはメタノール、エタノール、１−プロパノール、２−プロパノール、ｎ−ブタノール、イソブタノール等のアルコール類、ギ酸、酢酸、プロピオン酸などのカルボン酸化合物などが好適に用いられる。これらのプロトン供与性化合物は、単独で系に添加しても良いし、２種以上を混合したり逐次的に添加しても良い。これらのうち、反応性や経済性の観点から塩酸水、苛性ソーダー水、またはメタノールが好ましく用いられる。 Specific examples of the proton-donating compound include hydrogen, water, hydrochloric acid water, caustic soda water, or alcohols such as methanol, ethanol, 1-propanol, 2-propanol, n-butanol, and isobutanol, formic acid, acetic acid, A carboxylic acid compound such as propionic acid is preferably used. These proton donating compounds may be added alone to the system, or two or more of them may be mixed or added sequentially. Of these, hydrochloric acid water, caustic soda water, or methanol is preferably used from the viewpoint of reactivity and economy.
プロトン供与性化合物によるアルミノキシ基含有オレフィン共重合体（Ｐ’）の処理方法としては、 [工程２]を経た重合反応混合物に、その中に含まれるアルミ総量に対し、プロトン供与性化合物を通常１〜１０００００等量、好ましくは、１０〜１００００等量加え、０〜１５０℃の温度で１分間〜３時間反応させる。
［工程３］は均一相での反応であっても良いが、脱離したアルミニウム残渣を水相に抽出させ効率的に除去するため有機相／水相の２相での反応でもよい。２相での反応は、水相として塩酸水または苛性ソーダー水を用い反応させ、反応後の水相を除去する過程を１回〜５回繰り返すことでＯ−Ａｌ結合の切断とアルミニウム残渣の抽出除去を効果的に行うことが可能となる。
As a method of treating the aluminoxy group-containing olefin copolymer (P ′) with a proton donating compound, the proton donating compound is usually added to the total amount of aluminum contained in the polymerization reaction mixture that has undergone [Step 2]. ˜100,000 equivalents, preferably 10 to 10000 equivalents, and reacted at a temperature of 0 to 150 ° C. for 1 minute to 3 hours.
[Step 3] may be a reaction in a homogeneous phase, or may be a reaction in two phases of an organic phase and an aqueous phase in order to efficiently remove the detached aluminum residue into the aqueous phase. In the two-phase reaction, hydrochloric acid water or caustic soda water is used as the aqueous phase, and the process of removing the aqueous phase after the reaction is repeated 1 to 5 times to break the O-Al bond and extract the aluminum residue. Removal can be performed effectively.
上記の処理により得られた水酸基含有オレフィン共重合体（Ｐ）は、従来公知のオレフィン重合における脱灰技術により容易に精製することができる。 The hydroxyl group-containing olefin copolymer (P) obtained by the above treatment can be easily purified by a conventionally known deashing technique in olefin polymerization.
以下、本発明を実施例により説明するが、本発明は、これらの実施例により何ら限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited at all by these Examples.
本発明においてモノマーの転化率、製造されるポリマーの分子量、水酸基含量は以下に示す方法で決定した。
（１）モノマー転化率
二重結合含有カルボン酸誘導体（Ｅ）の転化率は、［工程１］反応終了後の溶液を約１ｍＬ分取し、１Ｎ塩酸水約５ｍｌに接触させた後の有機層をガスクロマトグラフィー（島津製作所社製，ＧＣ−１７００）により分析することで求めた。
（２）共重合体の分子量
［工程３］にて得られた水酸基含有オレフィン共重合体（Ｐ）の分子量は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）を用いて、以下に示した条件で測定した。
ＧＰＣ：Ｗａｔｅｒｓ社製 ２０００型
カラム：東ソー社製 ＴＳＫｇｅｌ ＧＭＨ６−ＨＴ×２本，ＴＳＫｇｅｌ ＧＭＨ６−ＨＴＬ×２本
注入量：５００μｌ（ポリマー濃度１．５ｇ／Ｌ）
流量：１ｍｌ／ｍｉｎ
カラム温度：１４０℃
溶媒：ｏ−ジクロルベンゼン
東ソー社製の標準ポリスチレンを用いて溶出体積と分子量の検量線を作成した。検量線を用いて検体のポリスチレン換算の重量平均分子量（Ｍｗ）、数平均分子量（Ｍｎ）を求め、汎用較正法にてポリエチレン換算値またはポリプロピレン換算値に換算した。
（３）共重合体の水酸基含量
［工程３］を経て得られた水酸基含有オレフィン共重合体（Ｐ）の２級水酸基、３級水酸基の同定および定量は、１Ｈ ＮＭＲ測定１３Ｃ ＮＭＲ測定によるピーク強度比より求めた。
測定条件 溶媒：ｏ−ジクロロベンゼン−ｄ４
温度：１２０℃
積算回数：１０２４回 (１Ｈ ＮＭＲ)、１０００回以上(１３Ｃ ＮＭＲ)
In the present invention, the monomer conversion rate, the molecular weight of the polymer produced, and the hydroxyl group content were determined by the following methods.
(1) Monomer conversion rate The conversion rate of the double bond-containing carboxylic acid derivative (E) is as follows. [Step 1] About 1 mL of the solution after completion of the reaction is taken and contacted with about 5 mL of 1N hydrochloric acid water. Was analyzed by gas chromatography (manufactured by Shimadzu Corporation, GC-1700).
(2) Molecular Weight of Copolymer The molecular weight of the hydroxyl group-containing olefin copolymer (P) obtained in [Step 3] was measured using gel permeation chromatography (GPC) under the conditions shown below. .
GPC: Waters 2000 Model Column: Tosoh TSKgel GMH6-HT × 2, TSKgel GMH6-HTL × 2 Injection volume: 500 μl (polymer concentration 1.5 g / L)
Flow rate: 1 ml / min
Column temperature: 140 ° C
Solvent: A standard curve of elution volume and molecular weight was prepared using standard polystyrene manufactured by o-dichlorobenzene Tosoh Corporation. Using the calibration curve, the polystyrene-equivalent weight average molecular weight (Mw) and number-average molecular weight (Mn) of the specimen were determined, and converted to polyethylene or polypropylene equivalents by a general calibration method.
(3) Hydroxyl content of copolymer The identification and quantification of the secondary hydroxyl group and tertiary hydroxyl group of the hydroxyl group-containing olefin copolymer (P) obtained through [Step 3] are based on 1 H NMR measurement and 13 C NMR measurement. It calculated | required from the peak intensity ratio.
Measurement conditions Solvent: o-dichlorobenzene-d 4
Temperature: 120 ° C
Number of integration: 1024 times (1 H NMR), or 1000 times (13 C NMR)
［実施例１］
［工程１］５００ｍＬガラス製重合器にトルエン４００ｍＬを入れ、二重結合含有カルボン酸誘導体（Ｅ）として１０−ウンデセン酸メチル１．１１ｍＬ（５．０ｍｍｏｌ）、アルキルアルミニウム化合物（Ａ）としてトリイソブチルアルミニウム（以下、ＴＩＢＡＬ）の０．９３Ｍ デカン調製液１１．８ｍＬ（１１．０ｍｍｏｌ）を加え、１０５℃、６００ｒｐｍの攪拌速度で１時間反応した。このとき、原料の１０−ウンデセン酸メチルの転化率は１００％であった。
[Example 1]
[Step 1] Put 400 mL of toluene in a 500 mL glass polymerizer, 1.11 mL (5.0 mmol) of methyl 10-undecenoate as the double bond-containing carboxylic acid derivative (E), and triisobutylaluminum as the alkylaluminum compound (A). 11.8 mL (11.0 mmol) of 0.93M decane preparation solution (hereinafter referred to as TIBAL) was added, and reacted at 105 ° C. and a stirring speed of 600 rpm for 1 hour. At this time, the conversion rate of the raw material, methyl 10-undecenoate, was 100%.
［工程２］［工程１］の反応液を５０℃まで冷却した後に、反応液中にオレフィン（Ｌ）としてプロピレンガス（１００Ｌ／ｈ）を流通させながら、別の窒素置換したシュレンク管に調製したエチレンビス（インデニル）ジルコニウムジクロリド（遷移金属化合物（ａ）） ２．０４ｍｇ（０．００５ｍｍｏｌ）とメチルアルモキサン （日本アルキルアルミニウム社製 アルミニウム含量 ４．０ｍｍｏｌ）のプレミックストルエン溶液 ２．３ｍｌを重合器に入れ、５０℃を保ちながら６００ｒｐｍの攪拌速度で１時間重合した。 [Step 2] After the reaction solution of [Step 1] was cooled to 50 ° C., propylene gas (100 L / h) was circulated as olefin (L) in the reaction solution, and was prepared in another nitrogen-substituted Schlenk tube. A premixed toluene solution of ethylenebis (indenyl) zirconium dichloride (transition metal compound (a)) 2.04 mg (0.005 mmol) and methylalumoxane (aluminum content 4.0 mmol manufactured by Nippon Alkyl Aluminum Co., Ltd.) 2.3 ml in a polymerizer And polymerized for 1 hour at a stirring speed of 600 rpm while maintaining 50 ° C.
［工程３］重合溶液を１Ｎ塩酸５ｍＬを含むメタノール１．５Ｌに注ぎ、アルミノキシ基を水酸基に変換すると共にポリマーを析出させた。桐山ロートにて析出したポリマーを濾別し、得られた白色ポリマーを、減圧下（６．６７ｋＰａ）、８０℃にて一晩乾燥させることで水酸基含有プロピレン共重合体８．８２ｇ（重合活性 １．７６ｋｇ／ｍｍｏｌ−ｃａｔ／ｈ）を得た。得られたポリマーは、Ｍｗ＝２５０００、Ｍn＝１２８００（Ｍw値およびＭn値は、ポリプロピレン換算値）であり、１Ｈ ＮＭＲ測定およびおよび13Ｃ ＮＭＲ測定より、２級水酸基が０．０３３ｍｍｏｌ／ｇ導入されたプロピレン共重合体であることを確認した。製造工程の概要および得られたポリマーの分析結果を表１にまとめた。 [Step 3] The polymerization solution was poured into 1.5 L of methanol containing 5 mL of 1N hydrochloric acid to convert an aluminoxy group into a hydroxyl group and to precipitate a polymer. The polymer precipitated in the Kiriyama funnel was filtered off, and the obtained white polymer was dried at 80 ° C. under reduced pressure (6.67 kPa) overnight to obtain 8.82 g of a hydroxyl group-containing propylene copolymer (polymerization activity 1 .76 kg / mmol-cat / h) was obtained. The obtained polymer had M w = 25000 and M n = 1800 (M w value and M n value are polypropylene equivalents), and the secondary hydroxyl group was 0.1 from 1 H NMR measurement and 13 C NMR measurement. It was confirmed that the propylene copolymer was introduced at 033 mmol / g. The outline of the production process and the analysis results of the obtained polymer are summarized in Table 1.
［実施例２］
［工程１］５００ｍＬガラス製重合器にトルエン４００ｍＬを入れ、二重結合含有カルボン酸誘導体（Ｅ）として１０−ウンデセン酸メチル１．１ｍＬ（５．０ｍｍｏｌ）、アルキルアルミニウム化合物（Ａ）としてトリエチルアルミニウム（以下、ＴＥＡＬ）の０．９６８Ｍ デカン調製液１１．３ｍＬ（１１．０ｍｍｏｌ）を加え、１０５℃、６００ｒｐｍの攪拌速度で６０分間反応した。このとき、１０−ウンデセン酸メチルの転化率が１００％に達していることを確認した。
[Example 2]
[Step 1] Put 400 mL of toluene in a 500 mL glass polymerizer, 1.1 mL (5.0 mmol) of methyl 10-undecenoate as the double bond-containing carboxylic acid derivative (E), and triethylaluminum (Al) as the alkylaluminum compound (A). Hereinafter, 0.968M decane preparation solution (TEAL) was added in an amount of 11.3 mL (11.0 mmol), and reacted at 105 ° C. and a stirring speed of 600 rpm for 60 minutes. At this time, it was confirmed that the conversion of methyl 10-undecenoate reached 100%.
［工程２］［工程１］の反応液を５０℃まで冷却した後に、オレフィン（Ｌ）としてプロピレンガス（１００Ｌ／ｈ）を流通させながら、別の窒素置換したシュレンク管に調製した1,1’-ジメチルシリレンビス（２−メチル−４−フェニルインデニル）ジルコニウムジクロリド（遷移金属化合物（ａ）） ３．１４ｍｇ（０．００５ｍｍｏｌ）とメチルアルモキサン （日本アルキルアルミニウム社製 アルミニウム含量 ４．０ｍｍｏｌ）のプレミックストルエン溶液 ２．３ｍｌを、重合器に入れ、５０℃を保ちながら６００ｒｐｍの攪拌速度で１５分間重合した。 [Step 2] After cooling the reaction solution of [Step 1] to 50 ° C., 1,1 ′ prepared in another nitrogen-substituted Schlenk tube while propylene gas (100 L / h) was circulated as olefin (L) -Dimethylsilylenebis (2-methyl-4-phenylindenyl) zirconium dichloride (transition metal compound (a)) 3.14 mg (0.005 mmol) and methylalumoxane (Nippon Alkyl Aluminum, Inc., aluminum content 4.0 mmol) 2.3 ml of the premixed toluene solution was placed in a polymerization vessel and polymerized for 15 minutes at a stirring speed of 600 rpm while maintaining 50 ° C.
［工程３］重合溶液を１Ｎ塩酸５ｍＬを含むメタノール１．５Ｌに注ぎ、アルミノキシ基を水酸基に変換すると共にポリマーを析出させた。桐山ロートにて濾別した白色ポリマーを、減圧下（６．６７ｋＰａ）、８０℃にて一晩乾燥させることで水酸基含有プロピレン共重合体２０．２ｇ（重合活性 １６．２ｋｇ／ｍｍｏｌ−ｃａｔ／ｈ）を得た。得られたポリマーは、Ｍｗ＝８０５００、Ｍｎ＝３９５００（Ｍw値およびＭn値は、ポリプロピレン換算値）であり、１Ｈ ＮＭＲ測定およびおよび13Ｃ ＮＭＲ測定より、２級水酸基が０．０５７ｍｍｏｌ／ｇ導入されたプロピレン共重合体であると確認した。製造工程の概要、および得られたポリマーの分析結果を表１にまとめた。 [Step 3] The polymerization solution was poured into 1.5 L of methanol containing 5 mL of 1N hydrochloric acid to convert an aluminoxy group into a hydroxyl group and to precipitate a polymer. The white polymer filtered off with a Kiriyama funnel was dried under reduced pressure (6.67 kPa) at 80 ° C. overnight to obtain 20.2 g of a hydroxyl group-containing propylene copolymer (polymerization activity 16.2 kg / mmol-cat / h). ) The obtained polymer, Mw = 80500, Mn = 39500 (M w values and M n values, in terms of polypropylene value), and from 1 H NMR measurements and and 13 C NMR measurements, a secondary hydroxyl group is 0.057 mmol / g Confirmed to be an introduced propylene copolymer. The outline of the production process and the analysis results of the obtained polymer are summarized in Table 1.
［実施例３］
［工程１］において二重結合含有カルボン酸誘導体（Ｅ）として１０−ウンデセン酸メチルの代わりに、１０−ウンデセン酸１．０ｍＬ（５．０ｍｍｏｌ）を用いる以外は、実施例１と同様な手法にて［工程１］〜［工程３］を順次行い、水酸基含有プロピレン共重合体２６．２ｇ（重合活性 ５．２ｋｇ／ｍｍｏｌ−ｃａｔ／ｈ）を得た。得られたポリマーは、Ｍｗ＝２６３００、Ｍｎ＝１３２００（いずれもポリプロピレン換算分子量）であり、１Ｈ ＮＭＲ測定およびおよび13Ｃ ＮＭＲ測定より、２級水酸基が０．０４０ｍｍｏｌ／ｇ導入されたプロピレン共重合体であることを確認した。製造工程の概要、および得られたポリマーの分析結果を表１にまとめた。
[Example 3]
The same procedure as in Example 1 was used except that 1.0 mL (5.0 mmol) of 10-undecenoic acid was used in place of methyl 10-undecenoate as the double bond-containing carboxylic acid derivative (E) in [Step 1]. Then, [Step 1] to [Step 3] were sequentially carried out to obtain 26.2 g of a hydroxyl group-containing propylene copolymer (polymerization activity 5.2 kg / mmol-cat / h). The obtained polymers had Mw = 26300 and Mn = 1200 (both molecular weights in terms of polypropylene), and from 1 H NMR measurement and 13 C NMR measurement, propylene copolymer in which a secondary hydroxyl group was introduced by 0.040 mmol / g. It was confirmed that they were coalesced. The outline of the production process and the analysis results of the obtained polymer are summarized in Table 1.
［実施例４］
［工程２］において、オレフィン（Ｌ）としてエチレンガス（１００Ｌ／ｈ）を流通させながら、別の窒素置換したシュレンク管に調製したエチレンビス（インデニル）ジルコニウムジクロリド（遷移金属化合物（ａ）） ０．３４ｍｇ（０．０００８ｍｍｏｌ）とメチルアルモキサン （日本アルキルアルミニウム社製 アルミニウム含量 ０．００２ｍｍｏｌ）のプレミックストルエン溶液 ０．５ｍｌを重合器に入れ、７５℃を保ちながら６００ｒｐｍの攪拌速度で５分間重合した。[工程２]以外は、実施例１と同様な手法にて、水酸基含有エチレン共重合体６．０ｇ（重合活性 ９０ｋｇ／ｍｍｏｌ−ｃａｔ／ｈ）を得た。得られたポリマーは、Ｍｗ＝８２０００、Ｍｎ＝４０５００（いずれもポリエチレン換算分子量）であり、１Ｈ ＮＭＲ測定およびおよび13Ｃ ＮＭＲ測定より、２級水酸基が０．０９５ｍｍｏｌ／ｇ導入されたエチレン共重合体であることを確認した。製造工程の概要、および得られたポリマーの分析結果を表１にまとめた。
[Example 4]
In [Step 2], ethylene bis (indenyl) zirconium dichloride (transition metal compound (a)) prepared in another Schlenk tube substituted with nitrogen while circulating ethylene gas (100 L / h) as olefin (L) 0. A premixed toluene solution of 34 mg (0.0008 mmol) and methylalumoxane (aluminum content: 0.002 mmol manufactured by Nippon Alkyl Aluminum Co., Ltd.) was placed in a polymerization vessel and polymerized for 5 minutes at a stirring rate of 600 rpm while maintaining 75 ° C. . Except for [Step 2], 6.0 g of a hydroxyl group-containing ethylene copolymer (polymerization activity 90 kg / mmol-cat / h) was obtained in the same manner as in Example 1. The obtained polymer had Mw = 82000, Mn = 40500 (both polyethylene equivalent molecular weight), and ethylene copolymer having 0.095 mmol / g of secondary hydroxyl group introduced from 1 H NMR measurement and 13 C NMR measurement. It was confirmed that they were coalesced. The outline of the production process and the analysis results of the obtained polymer are summarized in Table 1.
［比較例１］
［工程１］を省略した条件、すなわち、二重結合含有カルボン酸誘導体（Ｅ）とアルキルアルミニウム化合物（Ａ）の反応を実施せずに、５０℃に調製されたトルエン中で、[工程２]のプロピレンのホモ重合と［工程３］を実施例１と同様の方法にて行い、プロピレンホモポリマーを得た。製造工程の概要の概要および得られたポリマーの分析結果を表１にまとめた。
[Comparative Example 1]
Under the conditions in which [Step 1] is omitted, that is, in a toluene prepared at 50 ° C. without performing the reaction of the double bond-containing carboxylic acid derivative (E) and the alkylaluminum compound (A), [Step 2] The propylene homopolymerization and [Step 3] were carried out in the same manner as in Example 1 to obtain a propylene homopolymer. Table 1 summarizes the outline of the manufacturing process and the analysis results of the obtained polymer.
［比較例２］
［工程１］において、アルキルアルミニウム化合物（Ａ）を添加しない以外は実施例１と同様な方法にて［工程１］から［工程３］を順次行った。工程２において重合が進行せず、ポリマーが得られなかった。
[Comparative Example 2]
In [Step 1], [Step 1] to [Step 3] were sequentially performed in the same manner as in Example 1 except that the alkylaluminum compound (A) was not added. In step 2, polymerization did not proceed, and no polymer was obtained.
［比較例３］
［工程１］において、アルキルアルミニウム化合物（Ａ）を添加しない以外は実施例２と同様な方法にて［工程１］から［工程３］を順次行った。工程２において重合が進行せず、ポリマーが得られなかった。
[Comparative Example 3]
In [Step 1], [Step 1] to [Step 3] were sequentially performed in the same manner as in Example 2 except that the alkylaluminum compound (A) was not added. In step 2, polymerization did not proceed, and no polymer was obtained.
［参考例１］
５００ｍＬガラス製重合器にトルエン４００ｍＬを入れ、エチレンガス（１００Ｌ／ｈ）を流通させながら、１０−ウンデセノール１．０ｍＬ（５．０ｍｍｏｌ）、ＴＩＢＡＬ １．５ｍｌ（６．０ｍｍｏｌ）を順次加え、５０℃、６００ｒｐｍの攪拌速度で１０分間攪拌した後、別の窒素置換したシュレンク管に調製したエチレンビス（インデニル）ジルコニウムジクロリド ２．０４ｍｇ（０．００５ｍｍｏｌ）とメチルアルモキサン （日本アルキルアルミニウム社製 アルミニウム含量 ４．０ｍｍｏｌ）のプレミックストルエン溶液 ２．３ｍｌを、重合器に入れ、５０℃を保ちながら６００ｒｐｍの攪拌速度で１時間重合した。重合溶液を１Ｎ塩酸５ｍＬを含むメタノール１．５Ｌに注ぎ、ポリマーを析出させた。桐山ロートにて濾別した白色ポリマーを、減圧下（６．６７ｋＰａ）、８０℃にて一晩乾燥させることでプロピレン共重合体３６．０ｇ（重合活性 ７．２ｋｇ／ｍｍｏｌ−ｃａｔ／ｈ）を得た。得られたポリマーは、Ｍｗ＝２２９００、Ｍｎ＝１２４００であり、１Ｈ ＮＭＲ測定より、１級水酸基が０．０９２ｍｍｍｏｌ／ｇ導入されたプロピレン共重合体であった。
以上の実施例および比較例の結果を、纏めて表１に示した。
[Reference Example 1]
400 mL of toluene was put into a 500 mL glass polymerization vessel, and 10 mL of 10-undecenol 1.0 mL (5.0 mmol) and TIBAL 1.5 mL (6.0 mmol) were sequentially added while flowing ethylene gas (100 L / h), and 50 ° C. , After stirring for 10 minutes at a stirring speed of 600 rpm, 2.04 mg (0.005 mmol) of ethylenebis (indenyl) zirconium dichloride prepared in another nitrogen-substituted Schlenk tube and methylalumoxane (Nippon Alkyl Aluminum, Inc., aluminum content 4) 0.0 mmol) of a premixed toluene solution was placed in a polymerization vessel and polymerized at a stirring speed of 600 rpm for 1 hour while maintaining 50 ° C. The polymerization solution was poured into 1.5 L of methanol containing 5 mL of 1N hydrochloric acid to precipitate a polymer. The white polymer filtered off with a Kiriyama funnel was dried at 80 ° C. under reduced pressure (6.67 kPa) overnight to obtain 36.0 g of a propylene copolymer (polymerization activity 7.2 kg / mmol-cat / h). Obtained. The obtained polymer had a Mw of 22900 and Mn of 12400, and was a propylene copolymer into which a primary hydroxyl group was introduced by 0.092 mmol / g from 1 H NMR measurement.
The results of the above examples and comparative examples are summarized in Table 1.
実施例１〜４に示される如く、１０−ウンデセン酸メチルや１０−ウンデセン酸などの二重結合含有カルボン酸誘導体は、アルキルアルミニウム化合物（Ａ）と接触させると高転化率（１００％）にて、二重結合含有アルミノキシ化合物（Ｍ）に変換され、このモノマーは、酸素原子を含むにも関わらず、オレフィン重合触媒の被毒を起こすことなく高活性でオレフィン類と共重合が可能であることが実証された。得られたポリマーには、参考例１に示す如く水酸基を有するビニルモノマーをアルキルアルミニウムにて保護し共重合させる技術では得ることができない２級水酸基を含有していることが明らかとなった。実施例１と比較例１を比較することで明らかなように、本発明では、同条件のプロピレンホモ重合結果に比べ、著しい重合活性低下は観察されず、効率的に水酸基含有ポリマーが得られている。
また、比較例２および比較例３で示される如く、アルキルアルミニウム化合物（Ａ）を添加しないと、二重結合含有カルボン酸誘導体が触媒の被毒を起こすため重合活性を発現せず、ポリマーを得ることさえできない。すなわち、（Ｅ）と（Ａ）の接触が必須となる。
As shown in Examples 1 to 4, double bond-containing carboxylic acid derivatives such as methyl 10-undecenoate and 10-undecenoic acid have a high conversion (100%) when brought into contact with the alkylaluminum compound (A). It is converted into a double bond-containing aluminoxy compound (M), and this monomer can be copolymerized with olefins with high activity without causing poisoning of the olefin polymerization catalyst even though it contains oxygen atoms. Has been demonstrated. As shown in Reference Example 1, the obtained polymer was found to contain secondary hydroxyl groups that cannot be obtained by a technique in which a vinyl monomer having a hydroxyl group is protected with alkylaluminum and copolymerized. As is clear from comparison between Example 1 and Comparative Example 1, in the present invention, a significant decrease in polymerization activity was not observed as compared with the results of propylene homopolymerization under the same conditions, and a hydroxyl group-containing polymer was efficiently obtained. Yes.
Further, as shown in Comparative Example 2 and Comparative Example 3, if the alkylaluminum compound (A) is not added, the double bond-containing carboxylic acid derivative causes poisoning of the catalyst, so that the polymerization activity is not exhibited and a polymer is obtained. I can't even do that. That is, the contact between (E) and (A) is essential.
本発明の方法により、参考例１に示したような水酸基含有ビニルモノマーを出発原料として用いずとも、安価なカルボン酸誘導体ビニルモノマーを用いることで、各種用途に好適に使用できる水酸基含有オレフィン共重合体を従来より簡便にかつ安価に製造することが可能となった。 According to the method of the present invention, the hydroxyl group-containing olefin copolymer can be suitably used for various applications by using an inexpensive carboxylic acid derivative vinyl monomer without using the hydroxyl group-containing vinyl monomer as shown in Reference Example 1 as a starting material. The coalescence can be produced more easily and inexpensively than before.
Claims (4)
A hydroxyl group-containing olefin copolymer (P) represented by the following general formula (1).
［工程１］ 下記一般式（２）で表される二重結合含有カルボン酸誘導体（Ｅ）とアルキルアルミニウム化合物（Ａ）とを反応させて、二重結合含有アルミノキシ化合物（Ｍ）を製造する工程、
［工程２］ その後、遷移金属触媒の存在下、二重結合含有アルミノキシ化合物（Ｍ）と炭素原子数２〜２０のオレフィン（Ｌ）とを共重合させて、前記二重結合含有アルミノキシ化合物（Ｍ）が共重合したアルミノキシ基を含有オレフィン共重合体（Ｐ’）を製造する工程、
［工程３］ さらに、アルミノキシ基含有オレフィン共重合体（Ｐ’）を、プロトン供与性化合物で処理し水酸基含有オレフィン共重合体（Ｐ）に変換する工程。
The method for producing a hydroxyl group-containing olefin copolymer (P) according to claim 1, comprising the following [Step 1], [Step 2] and [Step 3];
[Step 1] A step of producing a double bond-containing aluminoxy compound (M) by reacting a double bond-containing carboxylic acid derivative (E) represented by the following general formula (2) with an alkylaluminum compound (A). ,
[Step 2] Then, in the presence of a transition metal catalyst, a double bond-containing aluminoxy compound (M) and an olefin (L) having 2 to 20 carbon atoms are copolymerized to form the double bond-containing aluminoxy compound (M A process for producing an olefin copolymer (P ′) containing an aluminoxy group copolymerized with
[Step 3] A step of converting the aluminoxy group-containing olefin copolymer (P ′) with a proton-donating compound to convert it into a hydroxyl group-containing olefin copolymer (P).
The method for producing a hydroxyl group-containing olefin copolymer (P) according to claim 2, wherein the alkylaluminum compound (A) is a trialkylaluminum compound represented by the following general formula (3).
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2017082404A1 (en) * | 2015-11-11 | 2017-05-18 | 国立大学法人東京大学 | Polar-group-containing propylene-based olefin copolymer and production process therefor |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05320256A (en) * | 1992-05-15 | 1993-12-03 | Mitsubishi Petrochem Co Ltd | Production of alpha-olefin polymer |
| JPH06172447A (en) * | 1992-12-09 | 1994-06-21 | Mitsubishi Petrochem Co Ltd | Production of alpha-olefin copolymer |
| JP2007262330A (en) * | 2006-03-29 | 2007-10-11 | Japan Polypropylene Corp | Laminated material comprising propylene copolymer or composition thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05320256A (en) * | 1992-05-15 | 1993-12-03 | Mitsubishi Petrochem Co Ltd | Production of alpha-olefin polymer |
| JPH06172447A (en) * | 1992-12-09 | 1994-06-21 | Mitsubishi Petrochem Co Ltd | Production of alpha-olefin copolymer |
| JP2007262330A (en) * | 2006-03-29 | 2007-10-11 | Japan Polypropylene Corp | Laminated material comprising propylene copolymer or composition thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017082404A1 (en) * | 2015-11-11 | 2017-05-18 | 国立大学法人東京大学 | Polar-group-containing propylene-based olefin copolymer and production process therefor |
| JP2017088883A (en) * | 2015-11-11 | 2017-05-25 | 国立大学法人 東京大学 | Polar group-containing propylene olefin copolymer and manufacturing method therefor |
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