JP2009132898A - Preparation of alpha-olefin-(meth)acrylic acid ester copolymer, and alpha-olefin-(meth)acrylic acid ester copolymer - Google Patents
Preparation of alpha-olefin-(meth)acrylic acid ester copolymer, and alpha-olefin-(meth)acrylic acid ester copolymer Download PDFInfo
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- JP2009132898A JP2009132898A JP2008280078A JP2008280078A JP2009132898A JP 2009132898 A JP2009132898 A JP 2009132898A JP 2008280078 A JP2008280078 A JP 2008280078A JP 2008280078 A JP2008280078 A JP 2008280078A JP 2009132898 A JP2009132898 A JP 2009132898A
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- Prior art keywords
- meth
- acrylic acid
- olefin
- acid ester
- group
- Prior art date
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- 229920003067 (meth)acrylic acid ester copolymer Polymers 0.000 title claims abstract description 34
- 239000004711 α-olefin Substances 0.000 claims abstract description 51
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229920001577 copolymer Polymers 0.000 claims description 55
- 238000007334 copolymerization reaction Methods 0.000 claims description 48
- 125000004432 carbon atom Chemical group C* 0.000 claims description 29
- 239000003446 ligand Substances 0.000 claims description 27
- 239000001257 hydrogen Substances 0.000 claims description 22
- 229910052739 hydrogen Inorganic materials 0.000 claims description 22
- 125000005842 heteroatom Chemical group 0.000 claims description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 14
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 150000004696 coordination complex Chemical class 0.000 claims description 8
- 150000002431 hydrogen Chemical class 0.000 claims description 8
- 125000001424 substituent group Chemical group 0.000 claims description 8
- 239000011593 sulfur Chemical group 0.000 claims description 8
- 229910052717 sulfur Chemical group 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 239000004593 Epoxy Substances 0.000 claims description 6
- 125000002723 alicyclic group Chemical group 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 6
- 125000000623 heterocyclic group Chemical group 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 5
- 101100294102 Caenorhabditis elegans nhr-2 gene Proteins 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- 229910052703 rhodium Inorganic materials 0.000 claims description 4
- 239000010948 rhodium Substances 0.000 claims description 4
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical compound [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 claims description 3
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 3
- 229910052787 antimony Inorganic materials 0.000 claims description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052785 arsenic Inorganic materials 0.000 claims description 3
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 3
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 3
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 claims description 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 claims description 3
- HRGDZIGMBDGFTC-UHFFFAOYSA-N platinum(2+) Chemical compound [Pt+2] HRGDZIGMBDGFTC-UHFFFAOYSA-N 0.000 claims description 3
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 8
- 229920000642 polymer Polymers 0.000 abstract description 33
- 238000000034 method Methods 0.000 abstract description 20
- 239000006227 byproduct Substances 0.000 abstract description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 57
- 230000015572 biosynthetic process Effects 0.000 description 49
- 238000003786 synthesis reaction Methods 0.000 description 45
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 40
- 239000005977 Ethylene Substances 0.000 description 40
- -1 acrylate ester Chemical class 0.000 description 40
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 38
- 238000006116 polymerization reaction Methods 0.000 description 38
- 239000000243 solution Substances 0.000 description 38
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 30
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 30
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 28
- 150000002430 hydrocarbons Chemical group 0.000 description 25
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 24
- 239000003054 catalyst Substances 0.000 description 21
- 239000000203 mixture Substances 0.000 description 21
- 238000003756 stirring Methods 0.000 description 21
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 20
- 239000007787 solid Substances 0.000 description 20
- 239000000178 monomer Substances 0.000 description 19
- 239000002904 solvent Substances 0.000 description 19
- 239000004912 1,5-cyclooctadiene Substances 0.000 description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 14
- 238000005259 measurement Methods 0.000 description 14
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 12
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 11
- 239000000725 suspension Substances 0.000 description 11
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 10
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 10
- 238000005481 NMR spectroscopy Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 239000000706 filtrate Substances 0.000 description 9
- 229910052759 nickel Inorganic materials 0.000 description 9
- 229910052723 transition metal Inorganic materials 0.000 description 9
- 150000003624 transition metals Chemical class 0.000 description 9
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 8
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 239000000523 sample Substances 0.000 description 8
- 238000005160 1H NMR spectroscopy Methods 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- 229910004298 SiO 2 Inorganic materials 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 239000012300 argon atmosphere Substances 0.000 description 6
- 239000012986 chain transfer agent Substances 0.000 description 6
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-VMNATFBRSA-N methanol-d1 Chemical compound [2H]OC OKKJLVBELUTLKV-VMNATFBRSA-N 0.000 description 6
- 229910052763 palladium Inorganic materials 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- 229910000275 saponite Inorganic materials 0.000 description 6
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 6
- 229920002554 vinyl polymer Polymers 0.000 description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- 229920006125 amorphous polymer Polymers 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 230000037048 polymerization activity Effects 0.000 description 5
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005755 formation reaction Methods 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
- 229910017053 inorganic salt Inorganic materials 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000011707 mineral Substances 0.000 description 4
- 235000010755 mineral Nutrition 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 239000012044 organic layer Substances 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 description 4
- 235000011152 sodium sulphate Nutrition 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- 229910052902 vermiculite Inorganic materials 0.000 description 4
- 239000010455 vermiculite Substances 0.000 description 4
- 235000019354 vermiculite Nutrition 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical class [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- RJDOZRNNYVAULJ-UHFFFAOYSA-L [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[F-].[F-].[Mg++].[Mg++].[Mg++].[Al+3].[Si+4].[Si+4].[Si+4].[K+] Chemical compound [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[F-].[F-].[Mg++].[Mg++].[Mg++].[Al+3].[Si+4].[Si+4].[Si+4].[K+] RJDOZRNNYVAULJ-UHFFFAOYSA-L 0.000 description 3
- 125000005396 acrylic acid ester group Chemical group 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- VNSBYDPZHCQWNB-UHFFFAOYSA-N calcium;aluminum;dioxido(oxo)silane;sodium;hydrate Chemical compound O.[Na].[Al].[Ca+2].[O-][Si]([O-])=O VNSBYDPZHCQWNB-UHFFFAOYSA-N 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000004927 clay Substances 0.000 description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 3
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 3
- QHZOMAXECYYXGP-UHFFFAOYSA-N ethene;prop-2-enoic acid Chemical compound C=C.OC(=O)C=C QHZOMAXECYYXGP-UHFFFAOYSA-N 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910000271 hectorite Inorganic materials 0.000 description 3
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 239000011256 inorganic filler Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 229910052901 montmorillonite Inorganic materials 0.000 description 3
- 229910000273 nontronite Inorganic materials 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 239000002516 radical scavenger Substances 0.000 description 3
- 229910000276 sauconite Inorganic materials 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 3
- AZJYLVAUMGUUBL-UHFFFAOYSA-A u1qj22mc8e Chemical compound [F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].O=[Si]=O.O=[Si]=O.O=[Si]=O.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3 AZJYLVAUMGUUBL-UHFFFAOYSA-A 0.000 description 3
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- ICKWICRCANNIBI-UHFFFAOYSA-N 2,4-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C(C(C)(C)C)=C1 ICKWICRCANNIBI-UHFFFAOYSA-N 0.000 description 2
- XWKFPIODWVPXLX-UHFFFAOYSA-N 2-methyl-5-methylpyridine Natural products CC1=CC=C(C)N=C1 XWKFPIODWVPXLX-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 238000003811 acetone extraction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
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Landscapes
- Polymerization Catalysts (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
本発明は、α−オレフィンと（メタ）アクリル酸エステル共重合体の新規な製造方法および、新規なα−オレフィンと（メタ）アクリル酸エステル共重合体に関する。 The present invention relates to a novel method for producing an α-olefin and a (meth) acrylic acid ester copolymer, and a novel α-olefin and a (meth) acrylic acid ester copolymer.
エチレンと極性基含有ビニルモノマーである酢酸ビニルや（メタ）アクリル酸エステルとを高温高圧のラジカル重合で共重合する方法はよく知られている。しかしながら、この方法では、多数の分岐生成により結晶性の低い共重合体となるため、得られた共重合体の強度が低いという欠点がある。 A method of copolymerizing ethylene and vinyl acetate or (meth) acrylic acid ester which is a polar group-containing vinyl monomer by radical polymerization at high temperature and high pressure is well known. However, this method has a drawback in that the strength of the obtained copolymer is low because a copolymer having low crystallinity is formed by a large number of branch formations.
また、Ｂｒｏｏｋｈａｒｔらは、α−ジイミン配位子を用いたパラジウム錯体を触媒として、エチレンとアクリル酸エステルの共重合体が製造できることを報告している。しかしながら、得られた共重合体は分岐構造に富むものであり、分岐は、メチル基、エチル基をはじめ、種々の炭素数であって、かつ、分岐の数も非常に多く、結果として、得られた共重合体は結晶性の低いものであった（例えば、非特許文献１参照。）。 Brookhart et al. Reported that a copolymer of ethylene and an acrylate ester can be produced using a palladium complex using an α-diimine ligand as a catalyst. However, the obtained copolymer has a rich branched structure, and the branches have various carbon numbers including methyl group and ethyl group, and the number of branches is very large. The obtained copolymer had low crystallinity (see, for example, Non-Patent Document 1).
リンと酸素を配位原子として有するリガンドを用いたニッケル触媒で、いわゆるＳＨＯＰ系触媒と呼ばれる触媒を用いると、極性溶媒中でエチレン重合が可能であり、分岐の少ない直鎖状重合体が得られることが知られている。ＳＨＯＰ系触媒のこうした極性基耐性に期待し、ＳＨＯＰ系触媒を用いたエチレンと極性モノマーの共重合が試みられている。しかしながら、エチレンとの共重合が進行するのは、極性モノマー中の極性基がオレフィンから離れている場合に限られることが報告されており、極性基がオレフィンに直接結合している（メタ）アクリル酸エステルとα−オレフィンとの共重合例は報告されていない（例えば、非特許文献２および特許文献１参照。）。なお、例外的に、ＧｉｂｓｏｎらはＳＨＯＰ系のニッケル錯体を用いてエチレンとメタクリル酸メチルの共重合を行っているが（例えば、非特許文献８参照。）、触媒構成成分として、ビスシクロオクタジエンニッケル（Ｎｉ（ＣＯＤ）２）がフォスフィンスカベンジャーとして必要であり、かつ、メタクリル酸メチルは重合体の末端のみに存在し、末端以外の主鎖中には取り込まれていない。 A nickel catalyst using a ligand having phosphorus and oxygen as coordination atoms, so-called a SHOP-based catalyst can be used for ethylene polymerization in a polar solvent, and a linear polymer with few branches can be obtained. It is known. In anticipation of such polar group resistance of the SHOP catalyst, copolymerization of ethylene and a polar monomer using the SHOP catalyst has been attempted. However, it has been reported that the copolymerization with ethylene proceeds only when the polar group in the polar monomer is separated from the olefin, and the (meth) acrylic in which the polar group is directly bonded to the olefin. No examples of copolymerization of an acid ester and an α-olefin have been reported (for example, see Non-Patent Document 2 and Patent Document 1). As an exception, Gibson et al. Copolymerize ethylene and methyl methacrylate using a SHOP-based nickel complex (see, for example, Non-Patent Document 8), but biscyclooctadiene is used as a catalyst component. Nickel (Ni (COD) 2 ) is required as a phosphine scavenger, and methyl methacrylate is present only at the end of the polymer and is not incorporated into the main chain other than the end.
一方、同様のＳＨＯＰ系のニッケル（０価）キレート錯体とアルミノキサンの組み合わせからなる触媒で、エチレンと不飽和カルボン酸エステルの共重合を行う方法が開示されている（例えば、特許文献２参照。）。特許文献２の実施例においては、エチレンとアクリル酸メチルの共重合例が記載されているが、非晶性重合体が副生するため、該非晶性重合体をアセトン抽出にて除去する必要があった。また、得られた共重合体については、アクリル酸メチル含量に関する記載があるのみで、その他、構造に関する記載はない。 On the other hand, a method of copolymerizing ethylene and an unsaturated carboxylic acid ester with a catalyst comprising a combination of a similar SHOP-based nickel (zero-valent) chelate complex and an aluminoxane is disclosed (for example, see Patent Document 2). . In Examples of Patent Document 2, an example of copolymerization of ethylene and methyl acrylate is described. However, since an amorphous polymer is by-produced, it is necessary to remove the amorphous polymer by acetone extraction. there were. Moreover, about the obtained copolymer, there is only description regarding a methyl acrylate content, and there is no description regarding a structure other than that.
Ｐｕｇｈら（例えば、非特許文献５参照。）、野崎ら（例えば、非特許文献６参照。）、Ｇｏｏｄａｌｌら（例えば、特許文献３参照。）は、ホスフィノスルホン酸配位子を有するパラジウム錯体を触媒として用いることにより、エチレンとアクリル酸メチルの共重合体が得られることを報告している。しかしながら、これらの公知文献で用いられている触媒は、希少な資源であり、かつ、高価なパラジウムを用いているため、工業的な応用には問題が大きい。
かかる状況において、本発明が解決しようとする課題は、分岐が少なく結晶性を有する新規なα−オレフィン・（メタ）アクリル酸エステル共重合体、および、非晶質重合体の副生がきわめて少なく、かつ、工業的に有利な新規なα−オレフィン・（メタ）アクリル酸エステル共重合体の製造方法を提供することにある。 In such a situation, the problem to be solved by the present invention is that there is very little by-product of a novel α-olefin / (meth) acrylate copolymer having few branches and crystallinity, and an amorphous polymer. And it is providing the manufacturing method of the novel alpha olefin * (meth) acrylic acid ester copolymer industrially advantageous.
本発明者らは、鋭意研究した結果、特定の遷移金属錯体の存在下にα−オレフィンと（メタ）アクリル酸エステルとの共重合を行うことにより、上記課題が解決できることを見出し、本発明に到達した。 As a result of intensive studies, the present inventors have found that the above problem can be solved by copolymerizing an α-olefin and a (meth) acrylic acid ester in the presence of a specific transition metal complex. Reached.
すなわち、本発明の第１の発明によれば、下記一般式（Ａ）および／または（Ｂ）で表される金属錯体の存在下、（ａ）α−オレフィンと（ｂ）（メタ）アクリル酸エステルを共重合することを特徴とするα−オレフィン・（メタ）アクリル酸エステル共重合体の製造方法が提供される。 That is, according to the first invention of the present invention, (a) an α-olefin and (b) (meth) acrylic acid in the presence of a metal complex represented by the following general formula (A) and / or (B): There is provided a method for producing an α-olefin / (meth) acrylic acid ester copolymer, characterized by copolymerizing an ester.
（式（Ａ）、（Ｂ）において、Ｍは、ニッケル（ＩＩ）、パラジウム（ＩＩ）、白金（ＩＩ）、コバルト（ＩＩ）、銅（Ｉ）またはロジウム（ＩＩＩ）を表す。Ｘ１は、酸素または硫黄を表す。Ｅ１は、リン、砒素またはアンチモンを表す。Ｒ３およびＲ４は、それぞれ独立に、水素または炭素数１ないし２０のヘテロ原子を含有していてもよい炭化水素基を表す。Ｒ５およびＲ６は、それぞれ独立に、水素、ハロゲン、炭素数１ないし３０のヘテロ原子を含有していてもよい炭化水素基、ＯＲ２、ＣＯ２Ｒ２、ＣＯ２Ｍ’、Ｃ（Ｏ）Ｎ（Ｒ１）２、Ｃ（Ｏ）Ｒ２、ＳＲ２、ＳＯ２Ｒ２、ＳＯＲ２、ＯＳＯ２Ｒ２、Ｐ（Ｏ）（ＯＲ２）２−ｙ（Ｒ１）ｙ、ＣＮ、ＮＨＲ２、Ｎ（Ｒ２）２、Ｓｉ（ＯＲ１）３−ｘ（Ｒ１）ｘ、ＯＳｉ（ＯＲ１）３−ｘ（Ｒ１）ｘ、ＮＯ２、ＳＯ３Ｍ’、ＰＯ３Ｍ’２、Ｐ（Ｏ）（ＯＲ２）２Ｍ’またはエポキシ含有基を表す。Ｍ’は、アルカリ金属、アルカリ土類金属、アンモニウム、４級アンモニウムまたはフォスフォニウムを表し、ｘは、０から３までの整数、ｙは、０から２までの整数を表す。なお、Ｒ５とＲ６が互いに連結し、脂環式環、芳香族環、または酸素、窒素、硫黄から選ばれるヘテロ原子を含有する複素環を形成してもよい。この時、環員数は５〜８であり、該環上に置換基を有していても、有していなくてもよい。Ｒ１は、水素または炭素数１ないし２０の炭化水素基を表す。Ｒ２は、炭素数１ないし２０の炭化水素基を表す。Ｌ１は、Ｍに弱く配位したリガンドを表す。また、Ｒ３とＬ１が互いに結合して環を形成してもよい。） (In the formulas (A) and (B), M represents nickel (II), palladium (II), platinum (II), cobalt (II), copper (I) or rhodium (III). X 1 is E 1 represents phosphorus, arsenic, or antimony, and R 3 and R 4 each independently represent hydrogen or a hydrocarbon group that may contain 1 to 20 carbon atoms. R 5 and R 6 are each independently hydrogen, halogen, a hydrocarbon group optionally containing a heteroatom having 1 to 30 carbon atoms, OR 2 , CO 2 R 2 , CO 2 M ′, C (O) N (R 1 ) 2 , C (O) R 2 , SR 2 , SO 2 R 2 , SOR 2 , OSO 2 R 2 , P (O) (OR 2 ) 2-y (R 1 ) y , CN, NHR 2, N (R 2) 2, Si (OR 1) 3 x (R 1) x, OSi (OR 1) 3-x (R 1) x, NO 2, SO 3 M ', PO 3 M' 2, P (O) (OR 2) 2 M ' or epoxy containing group M ′ represents an alkali metal, an alkaline earth metal, ammonium, quaternary ammonium, or phosphonium, x represents an integer from 0 to 3, and y represents an integer from 0 to 2. , R 5 and R 6 may be connected to each other to form an alicyclic ring, an aromatic ring, or a heterocyclic ring containing a heteroatom selected from oxygen, nitrogen, and sulfur. -8, which may or may not have a substituent on the ring, R 1 represents hydrogen or a hydrocarbon group having 1 to 20 carbon atoms, and R 2 represents a carbon number. 1 to .L 1 representing a hydrocarbon group of 20 represents a weakly coordinating ligand to M. the R 3 and L 1 are bonded to each other may form a ring.)
また、本発明の第２の発明によれば、下記一般式（Ｃ）で表される金属錯体の存在下、（ａ）α−オレフィンと（ｂ）（メタ）アクリル酸エステルを共重合することを特徴とするα−オレフィン・（メタ）アクリル酸エステル共重合体の製造方法が提供される。 Moreover, according to 2nd invention of this invention, (a) alpha-olefin and (b) (meth) acrylic acid ester are copolymerized in presence of the metal complex represented by the following general formula (C). The manufacturing method of the alpha olefin * (meth) acrylic acid ester copolymer characterized by these is provided.
（式（Ｃ）において、Ｍ、Ｘ１、Ｅ１、Ｌ１、Ｒ３およびＲ４は、一般式（Ａ）および（Ｂ）と同義である。Ｒ１０、Ｒ１１、Ｒ１２、Ｒ１３は、それぞれ独立に、水素、ハロゲン、炭素数１ないし３０のヘテロ原子を含有していてもよい炭化水素基、ＯＲ２、ＣＯ２Ｒ２、ＣＯ２Ｍ’、Ｃ（Ｏ）Ｎ（Ｒ１）２、Ｃ（Ｏ）Ｒ２、ＳＲ２、ＳＯ２Ｒ２、ＳＯＲ２、ＯＳＯ２Ｒ２、Ｐ（Ｏ）（ＯＲ２）２−ｙ（Ｒ１）ｙ、ＣＮ、ＮＨＲ２、Ｎ（Ｒ２）２、Ｓｉ（ＯＲ１）３−ｘ（Ｒ１）ｘ、ＯＳｉ（ＯＲ１）３−ｘ（Ｒ１）ｘ、ＮＯ２、ＳＯ３Ｍ’、ＰＯ３Ｍ’２、Ｐ（Ｏ）（ＯＲ２）２Ｍ’またはエポキシ含有基を表す。Ｒ１、Ｒ２、Ｍ’、ｘおよびｙは、一般式（Ａ）および（Ｂ）と同義である。なお、Ｒ１０〜Ｒ１３から適宜選択された複数の基が互いに連結し、脂環式環、芳香族環、または酸素、窒素、硫黄から選ばれるヘテロ原子を含有する複素環を形成してもよい。この時、環員数は５〜８であり、該環上に置換基を有していても、有していなくてもよい。） (In the formula (C), M, X 1 , E 1 , L 1 , R 3 and R 4 have the same meanings as the general formulas (A) and (B). R 10 , R 11 , R 12 , R 13 Are each independently hydrogen, halogen, a hydrocarbon group optionally containing a heteroatom having 1 to 30 carbon atoms, OR 2 , CO 2 R 2 , CO 2 M ′, C (O) N (R 1 ) 2 , C (O) R 2 , SR 2 , SO 2 R 2 , SOR 2 , OSO 2 R 2 , P (O) (OR 2 ) 2 -y (R 1 ) y , CN, NHR 2 , N ( R 2 ) 2 , Si (OR 1 ) 3-x (R 1 ) x , OSi (OR 1 ) 3-x (R 1 ) x , NO 2 , SO 3 M ′, PO 3 M ′ 2 , P (O ) (oR 2) 2 M ' .R 1, R 2 representing the or epoxy-containing group, M', x and y, and the general formula (a) and (B) Righteous. Incidentally, appropriately selected plurality of groups are connected to each other from R 10 to R 13, alicyclic, aromatic ring, or oxygen, nitrogen, a heterocyclic ring containing a hetero atom selected from sulfur (At this time, the number of ring members is 5 to 8, and it may or may not have a substituent on the ring.)
また、本発明の第３の発明によれば、第１又は２の発明において、有機アルミニウム化合物の非存在下で共重合を行うことを特徴とするα−オレフィン・（メタ）アクリル酸エステル共重合体の製造方法が提供される。 According to a third invention of the present invention, in the first or second invention, the copolymerization is carried out in the absence of an organoaluminum compound, and an α-olefin / (meth) acrylic acid ester copolymer A method for producing a coalescence is provided.
また、本発明の第４の発明によれば、（ａ）α−オレフィンと（ｂ）（メタ）アクリル酸エステルの共重合体であって、主鎖のメチル分岐数が主鎖炭素１０００個あたり２個未満であり、かつ、炭素数２以上の炭化水素基の分岐を持たず、かつ、末端以外の主鎖中に（ｂ）成分が共重合されていることを特徴とする高度にリニアなα−オレフィン・（メタ）アクリル酸エステル共重合体が提供される。 Further, according to the fourth invention of the present invention, it is a copolymer of (a) an α-olefin and (b) (meth) acrylic acid ester, and the number of methyl branches in the main chain per 1000 main chain carbons. Highly linear, characterized in that it is less than 2 and does not have a branch of hydrocarbon group having 2 or more carbon atoms, and (b) component is copolymerized in the main chain other than the terminal An α-olefin / (meth) acrylic acid ester copolymer is provided.
また、本発明の第５の発明によれば、（ａ）α−オレフィンと（ｂ）（メタ）アクリル酸エステルを共重合体であって、主鎖末端がエチル基、ビニル基、および（ｂ）成分として共重合に用いた（メタ）アクリル酸エステル由来の一般式（Ｄ）で表される基からなり、かつ、一般式（Ｄ）における炭素−炭素二重結合が、Ｚ体とＥ体の２種の幾何異性体構造からなることを特徴とするα−オレフィン・（メタ）アクリル酸エステル共重合体が提供される。
−ＣＨ＝Ｃ（Ｒ８）ＣＯ２（Ｒ９） ・・・（Ｄ）
（式（Ｄ）において、Ｒ８は水素または炭素数１〜１０の炭化水素基であり、分岐、環、および／または不飽和結合を有していてもよい。Ｒ９は炭素数１〜３０の炭化水素基であり、分岐、環、および／または不飽和結合を有していてもよい。さらに、Ｒ９内の任意の位置にヘテロ原子を含有していてもよい。）
According to a fifth aspect of the present invention, (a) an α-olefin and (b) a (meth) acrylic acid ester are copolymers, and the main chain ends are ethyl groups, vinyl groups, and (b ) Comprising a group represented by the general formula (D) derived from the (meth) acrylic acid ester used for copolymerization as a component, and the carbon-carbon double bond in the general formula (D) is Z-form and E-form An α-olefin / (meth) acrylic acid ester copolymer comprising the following two types of geometric isomer structures is provided.
-CH = C (R 8) CO 2 (R 9) ··· (D)
(In Formula (D), R 8 is hydrogen or a hydrocarbon group having 1 to 10 carbon atoms, and may have a branch, a ring, and / or an unsaturated bond. R 9 has 1 to 30 carbon atoms. And may have a branched, ring, and / or unsaturated bond, and may contain a hetero atom at any position within R 9. )
また、本発明の第６の発明によれば、第５の発明において、α−オレフィン・（メタ）アクリル酸エステル共重合体が、主鎖のメチル分岐数が主鎖炭素１０００個あたり２個未満であり、かつ、炭素数２以上の炭化水素基の分岐を持たないことを特徴とする、高度にリニアなα−オレフィン・（メタ）アクリル酸エステル共重合体が提供される。 According to the sixth aspect of the present invention, in the fifth aspect, the α-olefin / (meth) acrylic acid ester copolymer has less than 2 methyl branches in the main chain per 1000 main chain carbons. And a highly linear α-olefin / (meth) acrylic acid ester copolymer characterized by not having a branched hydrocarbon group having 2 or more carbon atoms.
本発明により、工業的に容易に入手可能な（メタ）アクリル酸エステルとα−オレフィンとの共重合体が製造可能となり、得られた共重合体は分岐が少なく結晶性が高い。また、コモノマーとして用いられる（メタ）アクリル酸エステルは、共重合体の末端のみならず、末端以外の主鎖中にも取り込まれる。したがって、本発明においては、（メタ）アクリル酸エステルの含量を上げることが可能となる。このため、該共重合体は機械的・熱的物性に優れ、有用な成形体として応用可能である。また、該共重合体の製造工程において、非晶質重合体の副生量がきわめて少ないため、こうした副生物を目的とする共重合体から除去する工程が不要である。さらに、本発明においては、希少かつ高価なパラジウムの代わりに、ニッケルを金属中心とした触媒を使用することができる。 According to the present invention, it is possible to produce a copolymer of (meth) acrylic acid ester and α-olefin which can be easily obtained industrially, and the obtained copolymer has few branches and high crystallinity. Further, the (meth) acrylic acid ester used as a comonomer is incorporated not only into the terminal of the copolymer but also into the main chain other than the terminal. Therefore, in the present invention, the content of (meth) acrylic acid ester can be increased. Therefore, the copolymer is excellent in mechanical and thermal properties and can be applied as a useful molded product. Further, in the production process of the copolymer, the amount of by-product of the amorphous polymer is extremely small, so that a process of removing such by-products from the intended copolymer is unnecessary. Further, in the present invention, a nickel-centered catalyst can be used in place of rare and expensive palladium.
本発明は、特定の金属錯体の存在下、（ａ）α−オレフィンと（ｂ）（メタ）アクリル酸エステルとを共重合するα−オレフィン・（メタ）アクリル酸エステル共重合体の製造方法およびそれから得られるα−オレフィン・（メタ）アクリル酸エステル共重合体である。以下、重合体の構成、触媒成分、製造方法等について詳細に説明する。 The present invention relates to a method for producing an α-olefin / (meth) acrylate copolymer in which (a) an α-olefin and (b) (meth) acrylate are copolymerized in the presence of a specific metal complex, and An α-olefin / (meth) acrylic acid ester copolymer obtained therefrom. Hereinafter, the structure of the polymer, the catalyst component, the production method and the like will be described in detail.
１．重合体の構成モノマー
（ａ）α−オレフィン
本発明における成分（ａ）は、一般式ＣＨ２＝ＣＨＲ７で表されるα−オレフィンである。ここで、Ｒ７は、水素または炭素数１〜２０の炭化水素基であり、分岐、環、および／または不飽和結合を有していてもよい。なかでも、好ましい（ａ）成分として、Ｒ７は水素または炭素数１〜１０の炭化水素基であるα−オレフィンが挙げられる。
1. Constituent monomer (a) α-olefin of polymer The component (a) in the present invention is an α-olefin represented by the general formula CH 2 ═CHR 7 . Here, R < 7 > is hydrogen or a C1-C20 hydrocarbon group, and may have a branch, a ring, and / or an unsaturated bond. Among them, as a preferable component (a), R 7 is hydrogen or an α-olefin which is a hydrocarbon group having 1 to 10 carbon atoms.
さらに好ましい（ａ）成分としては、エチレン、プロピレン、１−ブテン、１−ペンテン、１−ヘキセン、１−オクテン、１−デセン、３−メチル−１−ブテン、４−メチル−１−ペンテン、ビニルシクロヘキセン、スチレンが挙げられる。なお、単独の（ａ）成分を使用してもよいし、複数の（ａ）成分を併用してもよい。 More preferable component (a) is ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 3-methyl-1-butene, 4-methyl-1-pentene, vinyl. Examples thereof include cyclohexene and styrene. In addition, a single component (a) may be used, or a plurality of components (a) may be used in combination.
（ｂ）（メタ）アクリル酸エステル
本発明における成分（ｂ）は、一般式ＣＨ２＝Ｃ（Ｒ８）ＣＯ２（Ｒ９）で表される（メタ）アクリル酸エステルである。ここで、Ｒ８は、水素または炭素数１〜１０の炭化水素基であり、分岐、環、および／または不飽和結合を有していてもよい。Ｒ９は、炭素数１〜３０の炭化水素基であり、分岐、環、および／または不飽和結合を有していてもよい。さらに、Ｒ９内の任意の位置にヘテロ原子を含有していてもよい。
好ましい（ｂ）成分として、Ｒ８は水素または炭素数１〜５の炭化水素基である（メタ）アクリル酸エステルが挙げられる。より好ましい（ｂ）成分としては、Ｒ８がメチル基であるメタクリル酸エステルまたはＲ８が水素であるアクリル酸エステルが挙げられる。
(B) (Meth) acrylic acid ester Component (b) in the present invention is a (meth) acrylic acid ester represented by the general formula CH 2 ═C (R 8 ) CO 2 (R 9 ). Here, R < 8 > is hydrogen or a C1-C10 hydrocarbon group, and may have a branch, a ring, and / or an unsaturated bond. R 9 is a hydrocarbon group having 1 to 30 carbon atoms, and may have a branch, a ring, and / or an unsaturated bond. Further, it may contain a hetero atom at an arbitrary position in R 9 .
As a preferred component (b), R 8 is hydrogen or a (meth) acrylic acid ester having 1 to 5 carbon atoms. More preferable component (b) includes a methacrylic ester in which R 8 is a methyl group or an acrylate ester in which R 8 is hydrogen.
さらに好ましい（ｂ）成分としては、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ｎ−プロピル、（メタ）アクリル酸イソプロピル、（メタ）アクリル酸ｎ−ブチル、（メタ）アクリル酸イソブチル、（メタ）アクリル酸ｔ−ブチル、（メタ）アクリル酸ペンチル、（メタ）アクリル酸ヘキシル、（メタ）アクリル酸シクロヘキシル、（メタ）アクリル酸オクチル、（メタ）アクリル酸２−エチルヘキシル、（メタ）アクリル酸ノニル、（メタ）アクリル酸デシル、（メタ）アクリル酸ドデシル、（メタ）アクリル酸フェニル、（メタ）アクリル酸トルイル、（メタ）アクリル酸ベンジル、（メタ）アクリル酸ヒドロキシエチル、（メタ）アクリル酸ジメチルアミノエチル、（メタ）アクリル酸ジエチルアミノエチル、（メタ）アクリル酸−２−アミノエチル、（メタ）アクリル酸−２−メトキシエチル、（メタ）アクリル酸−３−メトキシプロピル、（メタ）アクリル酸グリシジル、（メタ）アクリル酸エチレンオキサイド、（メタ）アクリル酸トリフルオロメチル、（メタ）アクリル酸−２−トリフルオロメチルエチル、（メタ）アクリル酸パーフルオロエチル、（メタ）アクリルアミド、（メタ）アクリルジメチルアミド等が挙げられる。なお、単独の（ｂ）成分を使用してもよいし、複数の（ｂ）成分を併用してもよい。 More preferable components (b) include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, (meth ) Isobutyl acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate Nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, phenyl (meth) acrylate, toluyl (meth) acrylate, benzyl (meth) acrylate, hydroxyethyl (meth) acrylate , Dimethylaminoethyl (meth) acrylate, diethylamino (meth) acrylate Ethyl, (meth) acrylic acid-2-aminoethyl, (meth) acrylic acid-2-methoxyethyl, (meth) acrylic acid-3-methoxypropyl, (meth) acrylic acid glycidyl, (meth) acrylic acid ethylene oxide, (Meth) acrylic acid trifluoromethyl, (meth) acrylic acid-2-trifluoromethylethyl, (meth) acrylic acid perfluoroethyl, (meth) acrylamide, (meth) acryldimethylamide and the like. In addition, a single component (b) may be used, or a plurality of components (b) may be used in combination.
２．触媒（金属錯体）
本発明に用いられる金属錯体は、下記一般式（Ａ）および／または（Ｂ）で表される遷移金属錯体である。
2. Catalyst (metal complex)
The metal complex used in the present invention is a transition metal complex represented by the following general formula (A) and / or (B).
一般式（Ａ）および（Ｂ）において、Ｍは、ニッケル（ＩＩ）、パラジウム（ＩＩ）、白金（ＩＩ）、コバルト（ＩＩ）、銅（Ｉ）またはロジウム（ＩＩＩ）を表す。Ｘ１は、酸素または硫黄を表す。Ｅ１は、リン、砒素またはアンチモンを表す。 In the general formulas (A) and (B), M represents nickel (II), palladium (II), platinum (II), cobalt (II), copper (I) or rhodium (III). X 1 represents oxygen or sulfur. E 1 represents phosphorus, arsenic or antimony.
また、一般式（Ａ）および（Ｂ）において、Ｒ３およびＲ４は、それぞれ独立に、水素または炭素数１ないし２０のヘテロ原子を含有していてもよい炭化水素基を表す。Ｒ３およびＲ４の具体例としては、水素、アルキル基、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、ｔ−ブチル基、ｎ−ペンチル基、シクロペンチル基、ｎ−ヘキシル基、シクロヘキシル基、ｎ−オクチル基、ｎ−デシル基、ベンジル基、アリール基、例えば、フェニル基、トルイル基、２，６−ジメチルフェニル基、２，４，６−トリメチルフェニル基、２，６−ジイソプロピルフェニル基、２−フェニルフェニル基、２，６−ジフェニルフェニル基、２−メトキシフェニル基、２，６−ジメトキシフェニル基などを例示することができる。 In the general formulas (A) and (B), R 3 and R 4 each independently represent hydrogen or a hydrocarbon group that may contain a heteroatom having 1 to 20 carbon atoms. Specific examples of R 3 and R 4 include hydrogen, alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group, Cyclopentyl group, n-hexyl group, cyclohexyl group, n-octyl group, n-decyl group, benzyl group, aryl group, for example, phenyl group, toluyl group, 2,6-dimethylphenyl group, 2,4,6-trimethyl Examples thereof include a phenyl group, a 2,6-diisopropylphenyl group, a 2-phenylphenyl group, a 2,6-diphenylphenyl group, a 2-methoxyphenyl group, and a 2,6-dimethoxyphenyl group.
Ｒ５およびＲ６は、それぞれ独立に、水素、ハロゲン、炭素数１ないし３０のヘテロ原子を含有していてもよい炭化水素基、ＯＲ２、ＣＯ２Ｒ２、ＣＯ２Ｍ’、Ｃ（Ｏ）Ｎ（Ｒ１）２、Ｃ（Ｏ）Ｒ２、ＳＲ２、ＳＯ２Ｒ２、ＳＯＲ２、ＯＳＯ２Ｒ２、Ｐ（Ｏ）（ＯＲ２）２−ｙ（Ｒ１）ｙ、ＣＮ、ＮＨＲ２、Ｎ（Ｒ２）２、Ｓｉ（ＯＲ１）３−ｘ（Ｒ１）ｘ、ＯＳｉ（ＯＲ１）３−ｘ（Ｒ１）ｘ、ＮＯ２、ＳＯ３Ｍ’、ＰＯ３Ｍ’２、Ｐ（Ｏ）（ＯＲ２）２Ｍ’またはエポキシ含有基を表す。ここで、Ｍ’は、アルカリ金属、アルカリ土類金属、アンモニウム、 ４級アンモニウムまたはフォスフォニウムを表し、ｘは、０から３までの整数、ｙは、０から２までの整数を表す。なお、Ｒ５とＲ６が互いに連結し、脂環式環、芳香族環、または酸素、窒素、硫黄から選ばれるヘテロ原子を含有する複素環を形成してもよい。この時、環員数は５〜８であり、該環上に置換基を有していても、有していなくてもよい。
Ｒ１は、水素または炭素数１ないし２０の炭化水素基を表す。Ｒ２は、炭素数１ないし２０の炭化水素基を表す。
R 5 and R 6 are each independently hydrogen, halogen, a hydrocarbon group optionally containing a heteroatom having 1 to 30 carbon atoms, OR 2 , CO 2 R 2 , CO 2 M ′, C (O ) N (R 1 ) 2 , C (O) R 2 , SR 2 , SO 2 R 2 , SOR 2 , OSO 2 R 2 , P (O) (OR 2 ) 2 -y (R 1 ) y , CN, NHR 2, N (R 2) 2, Si (OR 1) 3-x (R 1) x, OSi (OR 1) 3-x (R 1) x, NO 2, SO 3 M ', PO 3 M' 2 , P (O) (OR 2 ) 2 M ′ or an epoxy-containing group. Here, M ′ represents an alkali metal, an alkaline earth metal, ammonium, quaternary ammonium or phosphonium, x represents an integer from 0 to 3, and y represents an integer from 0 to 2. R 5 and R 6 may be connected to each other to form an alicyclic ring, an aromatic ring, or a heterocyclic ring containing a heteroatom selected from oxygen, nitrogen, and sulfur. At this time, the number of ring members is 5 to 8, and it may or may not have a substituent on the ring.
R 1 represents hydrogen or a hydrocarbon group having 1 to 20 carbon atoms. R 2 represents a hydrocarbon group having 1 to 20 carbon atoms.
Ｌ１は、Ｍに弱く配位したリガンドを表す。ここで、Ｍに弱く配位したリガンドとは、Ｍと配位結合形成可能であり、Ｌ１をＭから取り除く化合物（スカベンジャー）を使用することなしに、（ａ）成分と（ｂ）成分の共重合が進行可能な化合物を表す。そのような特徴を有するリガンドＬ１は、配位結合可能な原子として酸素、窒素、硫黄を有する炭素数１〜２０の炭化水素化合物である。また、Ｌ１として、炭素−炭素不飽和結合を有し、ヘテロ原子を有していてもよい炭化水素化合物も使用することができる。 L 1 represents a ligand coordinated weakly to M. Here, the ligand weakly coordinated with M is capable of forming a coordination bond with M, and without using a compound (scavenger) that removes L 1 from M, the components (a) and (b) It represents a compound capable of proceeding copolymerization. The ligand L 1 having such characteristics is a hydrocarbon compound having 1 to 20 carbon atoms having oxygen, nitrogen, and sulfur as atoms capable of coordination bonding. Further, as L 1 , a hydrocarbon compound having a carbon-carbon unsaturated bond and optionally having a hetero atom can also be used.
好ましいＬ１としては、ピリジン誘導体、ピペリジン誘導体、アルキルエーテル誘導体、アリールエーテル誘導体、アルキルアリールエーテル誘導体、環状エーテル類、アルキルニトリル誘導体、アリールニトリル誘導体、アルコール類、アミド類、脂肪族エステル類、芳香族エステル類、アミン類、環状不飽和炭化水素類などを挙げることができる。さらに好ましいＬ１としては、ピリジン誘導体、環状エーテル類、脂肪族エステル類、芳香族エステル類、環状オレフィン類であり、特に好ましいＬ１として、ピリジン、ルチジン、ピコリン、Ｒ１ＣＯ２Ｒ２ （Ｒ１およびＲ２の定義は前記の通り）を挙げることができる。なお、Ｒ３とＬ１が互いに結合して環を形成してもよい。そのような例として、シクロオクタ−１−エニル基を挙げることができる。 Preferred L 1 includes pyridine derivatives, piperidine derivatives, alkyl ether derivatives, aryl ether derivatives, alkyl aryl ether derivatives, cyclic ethers, alkyl nitrile derivatives, aryl nitrile derivatives, alcohols, amides, aliphatic esters, aromatics. Examples thereof include esters, amines, and cyclic unsaturated hydrocarbons. More preferred L 1 is a pyridine derivative, a cyclic ether, an aliphatic ester, an aromatic ester, or a cyclic olefin. Particularly preferred L 1 is pyridine, lutidine, picoline, R 1 CO 2 R 2 (R 1 and R 2 can be defined as described above. R 3 and L 1 may be bonded to each other to form a ring. As such an example, a cyclooct-1-enyl group can be mentioned.
なお、いわゆるＳＨＯＰ系金属錯体には、本発明におけるＬ１の代わりに、金属Ｍに強く配位したリガンドを用いても錯体を合成することができる。このような強く配位したリガンドとしては、フォスフィンがよく知られており、なかでも、トリメチルフォスフィンやトリフェニルフォスフィンよく知られている。しかしながら、このように強く配位したリガンドをＳＨＯＰ系金属錯体の一構成成分として用いた場合には、該リガンドをＭから取り除くスカベンジャーを併用することが、オレフィンの重合能発現のために必須であることが知られている（非特許文献７）。
このような目的のために用いられるスカベンジャーとしては、Ｎｉ（ＣＯＤ）２（ＣＯＤ：シクロオクタジエン）、Ｂ（Ｃ６Ｆ５）３、アルミノキサン類、ロジウム錯体などが知られている。
For so-called SHOP-based metal complexes, the complex can also be synthesized by using a ligand strongly coordinated to the metal M instead of L 1 in the present invention. As such a strongly coordinated ligand, phosphine is well known, and among them, trimethylphosphine and triphenylphosphine are well known. However, when such a strongly coordinated ligand is used as one component of a SHOP-based metal complex, it is essential to use a scavenger that removes the ligand from M in order to develop the ability to polymerize olefins. It is known (Non-Patent Document 7).
As scavengers used for such purposes, Ni (COD) 2 (COD: cyclooctadiene), B (C 6 F 5 ) 3 , aluminoxanes, rhodium complexes and the like are known.
一般式（Ａ）で示される遷移金属錯体は公知であり、前述の特許文献１および該特許文献１に記載されている参考文献の記載にしたがって合成することができる。また、一般式（Ｂ）で示される遷移金属錯体も公知であり、前述の非特許文献３や非特許文献４に記載の方法を用いて合成することができる。これらの金属錯体は、単離したものを用いてもよいし、担体に担持して用いてもよい。さらに、一般式（Ａ）または（Ｂ）の遷移金属錯体の合成に用いられる原料を接触・反応させ、反応生成物を単離することなく使用してもよい。こうした接触・反応をα−オレフィンと（メタ）アクリル酸エステルの共重合に使用する反応器中で、これらのモノマーの存在下または非存在下で行ってもよいし、該反応器とは別の容器中で行ってもよい。また、一般式（Ａ）および／または（Ｂ）で示される遷移金属錯体は、単独の錯体を用いてもよいし、複数種の錯体を併用してもよい。特に、分子量分布やコモノマー含量分布を広げる目的には、こうした複数種の錯体の併用が有用である。 The transition metal complex represented by the general formula (A) is known, and can be synthesized according to the description of Patent Document 1 and the reference described in Patent Document 1. Moreover, the transition metal complex shown by general formula (B) is also well-known, and can be synthesize | combined using the method as described in the nonpatent literature 3 and the nonpatent literature 4 mentioned above. These metal complexes may be used isolated or may be used by being supported on a carrier. Furthermore, the raw materials used for the synthesis of the transition metal complex of the general formula (A) or (B) may be contacted and reacted, and the reaction product may be used without isolation. Such contact / reaction may be carried out in the reactor used for copolymerization of α-olefin and (meth) acrylic acid ester in the presence or absence of these monomers, or separately from the reactor. You may carry out in a container. In addition, as the transition metal complex represented by the general formula (A) and / or (B), a single complex may be used, or a plurality of types of complexes may be used in combination. Particularly, for the purpose of widening the molecular weight distribution and the comonomer content distribution, the combined use of these plural kinds of complexes is useful.
本発明で使用可能な錯体は、一般式（Ａ）および／または（Ｂ）で示される構造であって、Ｅ１とＸ１が脂肪族炭化水素基で結合された構造を有するものである。これらのうち、一般式（Ａ）で示される構造を有する錯体が好ましく用いられる。また、一般式（Ａ）で示される構造のうち、Ｅ１とＸ１が芳香族炭化水素基で結合された構造を有する錯体（Ｃ）も好適に使用可能である。特に、錯体（Ｃ）は、リガンドと遷移金属を含有する前駆体とを何らかの媒体中で接触させることにより容易に得られるため、ｉｎ ｓｉｔｕで錯体を形成する必要性がある場合、特に好ましく用いられる。 The complex that can be used in the present invention has a structure represented by the general formula (A) and / or (B), and has a structure in which E 1 and X 1 are bonded with an aliphatic hydrocarbon group. Among these, a complex having a structure represented by the general formula (A) is preferably used. In addition, among the structure represented by the general formula (A), a complex (C) having a structure in which E 1 and X 1 are bonded with an aromatic hydrocarbon group can also be suitably used. In particular, since the complex (C) can be easily obtained by contacting a ligand and a precursor containing a transition metal in some medium, it is particularly preferably used when it is necessary to form a complex in situ. .
一般式（Ｃ）において、Ｍ、Ｘ１、Ｅ１、Ｌ１、Ｒ３およびＲ４は、一般式（Ａ）および（Ｂ）と同義である。Ｒ１０、Ｒ１１、Ｒ１２、Ｒ１３は、それぞれ独立に、水素、ハロゲン、炭素数１ないし３０のヘテロ原子を含有していてもよい炭化水素基、ＯＲ２、ＣＯ２Ｒ２、ＣＯ２Ｍ’、Ｃ（Ｏ）Ｎ（Ｒ１）２、Ｃ（Ｏ）Ｒ２、ＳＲ２、ＳＯ２Ｒ２、ＳＯＲ２、ＯＳＯ２Ｒ２、Ｐ（Ｏ）（ＯＲ２）２−ｙ（Ｒ１）ｙ、ＣＮ、ＮＨＲ２、Ｎ（Ｒ２）２、Ｓｉ（ＯＲ１）３−ｘ（Ｒ１）ｘ、ＯＳｉ（ＯＲ１）３−ｘ（Ｒ１）ｘ、ＮＯ２、ＳＯ３Ｍ’、ＰＯ３Ｍ’２、Ｐ（Ｏ）（ＯＲ２）２Ｍ’またはエポキシ含有基を表す。Ｒ１、Ｒ２、Ｍ’、ｘおよびｙは、一般式（Ａ）および（Ｂ）と同義である。なお、Ｒ１０〜Ｒ１３から適宜選択された複数の基が互いに連結し、脂環式環、芳香族環、または酸素、窒素、硫黄から選ばれるヘテロ原子を含有する複素環を形成してもよい。この時、環員数は５〜８であり、該環上に置換基を有していても、有していなくてもよい。 In the general formula (C), M, X 1 , E 1 , L 1 , R 3 and R 4 are synonymous with the general formulas (A) and (B). R 10 , R 11 , R 12 , and R 13 are each independently hydrogen, halogen, a hydrocarbon group that may contain 1 to 30 carbon atoms, OR 2 , CO 2 R 2 , CO 2. M ′, C (O) N (R 1 ) 2 , C (O) R 2 , SR 2 , SO 2 R 2 , SOR 2 , OSO 2 R 2 , P (O) (OR 2 ) 2-y (R 1) y, CN, NHR 2 , N (R 2) 2, Si (OR 1) 3-x (R 1) x, OSi (OR 1) 3-x (R 1) x, NO 2, SO 3 M ', Represents PO 3 M' 2 , P (O) (OR 2 ) 2 M 'or an epoxy-containing group. R 1 , R 2 , M ′, x and y have the same meanings as in the general formulas (A) and (B). A plurality of groups appropriately selected from R 10 to R 13 may be connected to each other to form an alicyclic ring, an aromatic ring, or a heterocyclic ring containing a heteroatom selected from oxygen, nitrogen, and sulfur. Good. At this time, the number of ring members is 5 to 8, and it may or may not have a substituent on the ring.
以下、本発明で使用可能な錯体を例示するが、本発明に使用可能な錯体は、下記例示に限定されるものではない。
なお、下記例示において、Ｍｅはメチル基を、Ｐｈはフェニル基を、Ｃｙはシクロヘキシル基を、ｔＢｕはターシャリーブチル基を示す。なお、以下の例示では、Ｍとしてニッケルの場合を示したが、前記したパラジウム、白金、コバルト、銅、ロジウム等の金属も使用可能である。
Hereinafter, although the complex which can be used by this invention is illustrated, the complex which can be used for this invention is not limited to the following illustration.
In the following examples, Me represents a methyl group, Ph represents a phenyl group, Cy represents a cyclohexyl group, and tBu represents a tertiary butyl group. In the following examples, M is nickel, but metals such as palladium, platinum, cobalt, copper, rhodium, etc. can be used.
使用可能な担体としては、本発明の主旨をそこなわない限りにおいて、任意の担体を用いることができる。一般に、無機酸化物やポリマー担体が好適に使用できる。具体的には、ＳｉＯ２、Ａｌ２Ｏ３、ＭｇＯ、ＺｒＯ２、ＴｉＯ２、Ｂ２Ｏ３、ＣａＯ、ＺｎＯ、ＢａＯ、ＴｈＯ２等またはこれらの混合物が挙げられ、ＳｉＯ２−Ａｌ２Ｏ３、ＳｉＯ２−Ｖ２Ｏ５、ＳｉＯ２−ＴｉＯ２、ＳｉＯ２−ＭｇＯ、ＳｉＯ２−Ｃｒ２Ｏ３等の混合酸化物も使用することができ、無機ケイ酸塩、ポリエチレン担体、ポリプロピレン担体、ポリスチレン担体、ポリアクリル酸担体、ポリメタクリル酸担体、ポリアクリル酸エステル担体、ポリエステル担体、ポリアミド担体、ポリイミド担体などが使用可能である。これらの担体については、粒径、粒径分布、細孔容積、比表面積などに特に制限はなく、任意のものが使用可能である。 As a usable carrier, any carrier can be used as long as the gist of the present invention is not impaired. In general, inorganic oxides and polymer carriers can be preferably used. Specific examples include SiO 2 , Al 2 O 3 , MgO, ZrO 2 , TiO 2 , B 2 O 3 , CaO, ZnO, BaO, ThO 2, or a mixture thereof, and SiO 2 —Al 2 O 3. , SiO 2 —V 2 O 5 , SiO 2 —TiO 2 , SiO 2 —MgO, SiO 2 —Cr 2 O 3 and other mixed oxides can also be used, inorganic silicate, polyethylene carrier, polypropylene carrier, A polystyrene carrier, polyacrylic acid carrier, polymethacrylic acid carrier, polyacrylic acid ester carrier, polyester carrier, polyamide carrier, polyimide carrier and the like can be used. These carriers are not particularly limited in particle size, particle size distribution, pore volume, specific surface area, etc., and any one can be used.
上記無機ケイ酸塩としては、粘土、粘土鉱物、ゼオライト、珪藻土等が使用可能である。これらは、合成品を用いてもよいし、天然に産出する鉱物を用いてもよい。
粘土、粘土鉱物の具体例としては、アロフェン等のアロフェン族、ディッカイト、ナクライト、カオリナイト、アノーキサイト等のカオリン族、メタハロイサイト、ハロイサイト等のハロイサイト族、クリソタイル、リザルダイト、アンチゴライト等の蛇紋石族、モンモリロナイト、ザウコナイト、バイデライト、ノントロナイト、サポナイト、ヘクトライト等のスメクタイト、バーミキュライト等のバーミキュライト鉱物、イライト、セリサイト、海緑石等の雲母鉱物、アタパルジャイト、セピオライト、パイゴルスカイト、ベントナイト、木節粘土、ガイロメ粘土、ヒシンゲル石、パイロフィライト、リョクデイ石群等が挙げられる。これらは混合層を形成していてもよい。
人工合成物としては、合成雲母、合成ヘクトライト、合成サポナイト、合成テニオライト等が挙げられる。
As the inorganic silicate, clay, clay mineral, zeolite, diatomaceous earth, or the like can be used. A synthetic product may be used for these, and the mineral produced naturally may be used.
Specific examples of clays and clay minerals include allophanes such as allophane, kaolins such as dickite, nacrite, kaolinite and anorcite, halloysites such as metahalloysite and halloysite, and serpentine such as chrysotile, lizardite and antigolite. Stone group, montmorillonite, sauconite, beidellite, nontronite, saponite, hectorite, etc. Examples include clay, gyrome clay, hysingelite, pyrophyllite, and ryokdeite group. These may form a mixed layer.
Examples of the artificial compound include synthetic mica, synthetic hectorite, synthetic saponite, and synthetic teniolite.
これら具体例のうち好ましくは、ディッカイト、ナクライト、カオリナイト、アノーキサイト等のカオリン族、メタハロサイト、ハロサイト等のハロサイト族、クリソタイル、リザルダイト、アンチゴライト等の蛇紋石族、モンモリロナイト、ザウコナイト、バイデライト、ノントロナイト、サポナイト、ヘクトライト等のスメクタイト、バーミキュライト等のバーミキュライト鉱物、イライト、セリサイト、海緑石等の雲母鉱物、合成雲母、合成ヘクトライト、合成サポナイト、合成テニオライトが挙げられ、特に好ましくはモンモリロナイト、ザウコナイト、バイデライト、ノントロナイト、サポナイト、ヘクトライト等のスメクタイト、バーミキュライト等のバーミキュライト鉱物、合成雲母、合成ヘクトライト、合成サポナイト、合成テニオライトが挙げられる。 Among these specific examples, preferably, kaolins such as dickite, nacrite, kaolinite, anorcite, halosites such as metahalosite, halosite, chrysotile, lizardite, serpentine such as antigolite, montmorillonite, Smectites such as sauconite, beidellite, nontronite, saponite, hectorite, vermiculite minerals such as vermiculite, mica minerals such as illite, sericite, sea chlorite, synthetic mica, synthetic hectorite, synthetic saponite, synthetic teniolite Particularly preferred are montmorillonite, sauconite, beidellite, nontronite, saponite, hectorite and other smectites, vermiculite and other vermiculite minerals, synthetic mica, synthetic hectorite, synthetic saponite, synthetic Taeniolite.
これらの担体は、そのまま用いてもよいが、塩酸、硝酸、硫酸等による酸処理および／または、ＬｉＣｌ、ＮａＣｌ、ＫＣｌ、ＣａＣｌ２、ＭｇＣｌ２、Ｌｉ２ＳＯ４、ＭｇＳＯ４、ＺｎＳＯ４、Ｔｉ（ＳＯ４）２、Ｚｒ（ＳＯ４）２、Ａｌ２（ＳＯ４）３等の塩類処理を行ってもよい。該処理において、対応する酸と塩基を混合して反応系内で塩を生成させて処理を行ってもよい。また粉砕や造粒等の形状制御や乾燥処理を行ってもよい。 These carriers may be used as they are, but may be treated with hydrochloric acid, nitric acid, sulfuric acid, etc. and / or LiCl, NaCl, KCl, CaCl 2 , MgCl 2 , Li 2 SO 4 , MgSO 4 , ZnSO 4 , Ti ( Salt treatment such as SO 4 ) 2 , Zr (SO 4 ) 2 , Al 2 (SO 4 ) 3 may be performed. In the treatment, the corresponding acid and base may be mixed to produce a salt in the reaction system. Further, shape control such as pulverization and granulation and drying treatment may be performed.
３．共重合反応
本発明における共重合反応は、プロパン、ｎ−ブタン、イソブタン、ｎ−ヘキサン、ｎ−ヘプタン、トルエン、キシレン、シクロヘキサン、メチルシクロヘキサン等の炭化水素溶媒や液化α−オレフィン等の液体、また、ジエチルエーテル、エチレングリコールジメチルエーテル、テトラヒドロフラン、ジオキサン、酢酸エチル、安息香酸メチル、アセトン、メチルエチルケトン、ホルミアミド、アセトニトリル、メタノール、イソプロピルアルコール、エチレングリコール等のような極性溶媒の存在下あるいは非存在下に行われる。また、ここで記載した液体化合物の混合物を溶媒として使用してもよい。なお、高い重合活や高い分子量を得るうえでは、上述の炭化水素溶媒がより好ましい。
3. Copolymerization Reaction The copolymerization reaction in the present invention is carried out by using a hydrocarbon solvent such as propane, n-butane, isobutane, n-hexane, n-heptane, toluene, xylene, cyclohexane and methylcyclohexane, a liquid such as a liquefied α-olefin, , Diethyl ether, ethylene glycol dimethyl ether, tetrahydrofuran, dioxane, ethyl acetate, methyl benzoate, acetone, methyl ethyl ketone, formamide, acetonitrile, methanol, isopropyl alcohol, ethylene glycol, etc. in the presence or absence of a polar solvent . Moreover, you may use the mixture of the liquid compound described here as a solvent. In addition, in order to obtain high polymerization activity and high molecular weight, the above-mentioned hydrocarbon solvent is more preferable.
本発明における共重合に際して、公知の添加剤の存在下または非存在下で共重合を行うことができる。添加剤としては、（ｂ）成分のラジカル重合禁止剤や、生成共重合体を安定化する作用を有する添加剤が好ましい。例えば、キノン誘導体やヒンダードフェノール誘導体などが好ましい添加剤の例として挙げられる。具体的には、モノメチルエーテルハイドロキノンや、２，６−ジ−ｔ−ブチル−４−メチルフェノール（ＢＨＴ）、トリメチルアルミニウムとＢＨＴとの反応生成物、４価チタンのアルコキサイドとＢＨＴとの反応生成物などが使用可能である。また、添加剤として、無機およびまたは有機フィラーを使用し、これらのフィラーの存在下で重合を行っても良い。さらに、本発明のＬ１を添加剤として用いてもよい。 In the copolymerization in the present invention, the copolymerization can be performed in the presence or absence of a known additive. As the additive, a radical polymerization inhibitor as the component (b) and an additive having an action of stabilizing the produced copolymer are preferable. Examples of preferable additives include quinone derivatives and hindered phenol derivatives. Specifically, monomethyl ether hydroquinone, 2,6-di-t-butyl-4-methylphenol (BHT), reaction product of trimethylaluminum and BHT, reaction product of tetravalent titanium alkoxide and BHT Etc. can be used. Further, as an additive, inorganic and / or organic fillers may be used and polymerization may be performed in the presence of these fillers. Further, it may be used L 1 of the present invention as an additive.
本発明において、重合形式に特に制限はない。媒体中で少なくとも一部の生成重合体がスラリーとなるスラリー重合、液化したモノマー自身を媒体とするバルク重合、気化したモノマー中で行う気相重合、または、高温高圧で液化したモノマーに生成重合体の少なくとも一部が溶解する高圧イオン重合などが好ましく用いられる。また、バッチ重合、セミバッチ重合、連続重合のいずれの形式でもよい。また、リビング重合であってもよいし、連鎖移動を併発しながら重合を行ってもよい。さらに、いわゆるｃｈａｉｎ ｔｒａｎｓｆｅｒ ａｇｅｎｔ（ＣＳＡ）を併用し、ｃｈａｉｎ ｓｈｕｔｔｌｉｎｇや、ｃｏｏｒｄｉｎａｔｉｖｅ ｃｈａｉｎ ｔｒａｎｓｆｅｒ ｐｏｌｙｍｅｒｉｚａｔｉｏｎ（ＣＣＴＰ）を行ってもよい。 In the present invention, the polymerization mode is not particularly limited. Slurry polymerization in which at least a part of the generated polymer in the medium becomes a slurry, bulk polymerization using the liquefied monomer itself as a medium, gas phase polymerization performed in a vaporized monomer, or a polymer generated in a monomer liquefied at high temperature and high pressure High-pressure ionic polymerization in which at least a part of the polymer is dissolved is preferably used. Further, any of batch polymerization, semi-batch polymerization, and continuous polymerization may be used. Moreover, living polymerization may be sufficient and it may superpose | polymerize, combining chain transfer. Furthermore, so-called chain transfer agent (CSA) may be used in combination, and chain shuffling or coordinative chain transfer polymerization (CCTP) may be performed.
未反応モノマーや媒体は、生成共重合体から分離し、リサイクルして使用してもよい。リサイクルの際、これらのモノマーや媒体は、精製して再使用してもよいし、精製せずに再使用してもよい。生成共重合体と未反応モノマーおよび媒体との分離には、従来公知の方法が使用できる。例えば、濾過、遠心分離、溶媒抽出、貧溶媒を使用した再沈などの方法が使用できる。 Unreacted monomers and media may be separated from the produced copolymer and recycled. In recycling, these monomers and media may be purified and reused, or may be reused without purification. A conventionally known method can be used to separate the produced copolymer from the unreacted monomer and the medium. For example, methods such as filtration, centrifugation, solvent extraction, and reprecipitation using a poor solvent can be used.
共重合温度、共重合圧力および共重合時間に特に制限はないが、通常は、以下の範囲から生産性やプロセスの能力を考慮して、最適な設定を行うことができる。
すなわち、共重合温度は、通常−２０℃から２９０℃、好ましくは０℃から２５０℃、共重合圧力は、０．１ＭＰａから１００ＭＰａ、好ましくは、０．３ＭＰａから９０ＭＰａ、共重合時間は、０．１分から１０時間、好ましくは、０．５分から７時間、さらに好ましくは１分から６時間の範囲から選ぶことができる。
There are no particular restrictions on the copolymerization temperature, copolymerization pressure, and copolymerization time, but usually optimum settings can be made in consideration of productivity and process capability from the following ranges.
That is, the copolymerization temperature is usually −20 ° C. to 290 ° C., preferably 0 ° C. to 250 ° C., the copolymerization pressure is 0.1 MPa to 100 MPa, preferably 0.3 MPa to 90 MPa, and the copolymerization time is 0.00. It can be selected from the range of 1 minute to 10 hours, preferably 0.5 minutes to 7 hours, more preferably 1 minute to 6 hours.
本発明において、共重合は、一般に不活性ガス雰囲気下で行われる。例えば、窒素、アルゴン、二酸化炭素雰囲気が使用でき、窒素雰囲気が好ましく使用される。なお、少量の酸素や空気の混入があってもよい。 In the present invention, the copolymerization is generally performed in an inert gas atmosphere. For example, a nitrogen, argon or carbon dioxide atmosphere can be used, and a nitrogen atmosphere is preferably used. A small amount of oxygen or air may be mixed.
共重合反応器への触媒とモノマーの供給に関しても特に制限はなく、目的に応じてさまざまな供給法をとることができる。たとえばバッチ重合の場合、あらかじめ所定量のモノマーを共重合反応器に供給しておき、そこに触媒を供給する手法をとることが可能である。この場合、追加のモノマーや追加の触媒を共重合反応器に供給してもよい。また、連続重合の場合、所定量のモノマーと触媒を共重合反応器に連続的に、または間歇的に供給し、共重合反応を連続的に行う手法をとることができる。 There are no particular restrictions on the supply of catalyst and monomer to the copolymerization reactor, and various supply methods can be used depending on the purpose. For example, in the case of batch polymerization, it is possible to take a technique in which a predetermined amount of monomer is supplied to a copolymerization reactor in advance and a catalyst is supplied thereto. In this case, an additional monomer or an additional catalyst may be supplied to the copolymerization reactor. In the case of continuous polymerization, a method in which a predetermined amount of monomer and catalyst are continuously or intermittently supplied to the copolymerization reactor to carry out the copolymerization reaction continuously can be employed.
共重合体の組成の制御に関しては、複数のモノマーを反応器に供給し、その供給比率を変えることによって制御する方法を一般に用いることができる。その他、触媒の構造の違いによるモノマー反応性比の違いを利用して共重合組成を制御する方法や、モノマー反応性比の重合温度依存性を利用して共重合組成を制御する方法が挙げられる。 Regarding the control of the copolymer composition, a method of controlling a copolymer by supplying a plurality of monomers to a reactor and changing the supply ratio thereof can be generally used. Other methods include controlling the copolymer composition using the difference in monomer reactivity ratio due to the difference in catalyst structure, and controlling the copolymer composition using the polymerization temperature dependence of the monomer reactivity ratio. .
共重合体の分子量制御には、従来公知の方法を使用することができる。すなわち、重合温度を制御して分子量を制御する方法、モノマー濃度を制御して分子量を制御する方法、連鎖移動剤を使用して分子量を制御する方法、遷移金属錯体中のリガンド構造の制御により分子量を制御する等が挙げられる。連鎖移動剤を使用する場合には、従来公知の連鎖移動剤を用いることができる。例えば、水素、メタルアルキルなどを使用することができる。また、（ｂ）成分自身が一種の連鎖移動剤となる場合には、（ｂ）成分の（ａ）成分に対する比率や、（ｂ）成分の濃度を制御することによっても分子量調節が可能である。遷移金属錯体中のリガンド構造を制御して分子量調節を行う場合には、金属Ｍのまわりにかさだかい置換基を配置したり、金属Ｍにアリール基やヘテロ原子含有置換基などの電子供与性基が相互作用可能となるように配置したり、前記したＲ５および／またはＲ６中にヘテロ原子を導入することにより、一般に分子量が向上する傾向を利用することができる。 A conventionally known method can be used for controlling the molecular weight of the copolymer. That is, a method for controlling the molecular weight by controlling the polymerization temperature, a method for controlling the molecular weight by controlling the monomer concentration, a method for controlling the molecular weight by using a chain transfer agent, and a molecular weight by controlling the ligand structure in the transition metal complex. For example. When a chain transfer agent is used, a conventionally known chain transfer agent can be used. For example, hydrogen, metal alkyl, etc. can be used. In addition, when the component (b) itself becomes a kind of chain transfer agent, the molecular weight can be adjusted by controlling the ratio of the component (b) to the component (a) and the concentration of the component (b). . When the molecular weight is adjusted by controlling the ligand structure in the transition metal complex, a bulky substituent is arranged around the metal M, or an electron donating property such as an aryl group or a hetero atom-containing substituent is provided on the metal M. Generally, the tendency to increase the molecular weight can be utilized by arranging the groups so that the groups can interact with each other or introducing heteroatoms into the aforementioned R 5 and / or R 6 .
４．α−オレフィン・（メタ）アクリル酸エステル共重合体の特徴
本発明においては、従来知られていなかった新規な構造を有するα−オレフィン・（メタ）アクリル酸エステル共重合体が得られる。このような新規な構造は、α−オレフィン・（メタ）アクリル酸エステル共重合体の１３Ｃ−ＮＭＲスペクトルや、必要に応じて１Ｈ−ＮＭＲスペクトルを解析することによって知ることができる。
4). Characteristics of α-olefin / (meth) acrylic acid ester copolymer In the present invention, an α-olefin / (meth) acrylic acid ester copolymer having a novel structure not conventionally known is obtained. Such a novel structure can be known by analyzing a 13 C-NMR spectrum of an α-olefin / (meth) acrylic acid ester copolymer and, if necessary, a 1 H-NMR spectrum.
本発明において、１３Ｃ−ＮＭＲの測定は、以下のようにして行う。
試料約４００（ｍｇ）を外径１０（ｍｍ）のＮＭＲ試料管に量り取り、ｏ−ジクロロベンゼン（２．５ｍｌ）を加え、１３０℃に加熱する。試料が溶解した後、重ベンゼン（０．５ｍｌ）を加え、溶液が均一になるまで加熱する。Ｖａｒｉａｎ社製Ｉｎｏｖａ５００分光計を使用し、１３０℃でＦＩＤの取り込み時間のみ１Ｈを照射し、ＮＯＥのない１３Ｃ−ＮＭＲスペクトルを測定する。パルス繰り返し時間は１６．３秒、フリップ角は９０°
、積算回数は１，８００〜２，６００回とする。
なお、通常のＮＯＥのある１３Ｃ−ＮＭＲの測定を別途行い、ＮＯＥなしで十分なシグナル強度が得られていることを確認することが望ましい。また、必要に応じて、α−オレフィン・（メタ）アクリル酸エステル共重合体の末端基分析のため、１Ｈ−ＮＭＲスペクトルの測定も行うことが好ましい。
In the present invention, 13 C-NMR is measured as follows.
About 400 (mg) of the sample is weighed into an NMR sample tube having an outer diameter of 10 (mm), o-dichlorobenzene (2.5 ml) is added, and the mixture is heated to 130 ° C. After the sample is dissolved, add heavy benzene (0.5 ml) and heat until the solution is homogeneous. Using a Varian Inova 500 spectrometer, 1 H is irradiated only at the FID uptake time at 130 ° C., and a 13 C-NMR spectrum without NOE is measured. Pulse repetition time is 16.3 seconds, flip angle is 90 °
The number of integrations is 1,800-2,600.
Note that it is desirable to separately perform 13 C-NMR measurement with normal NOE to confirm that sufficient signal intensity is obtained without NOE. If necessary, it is also preferable to measure the 1 H-NMR spectrum for terminal group analysis of the α-olefin / (meth) acrylic acid ester copolymer.
化学シフトの基準については以下のようにする。
すなわち、１３Ｃ−ＮＭＲスペクトルにおいては、重ベンゼンのシグナルを１２８．０ｐｐｍとし、１Ｈ−ＮＭＲスペクトルにおいては、ｏ−ジクロロベンゼンの低周波数側のシグナルを６．９０ｐｐｍとする。
The standard of chemical shift is as follows.
That is, in the 13 C-NMR spectrum, the signal of heavy benzene is 128.0 ppm, and in the 1 H-NMR spectrum, the low-frequency signal of o-dichlorobenzene is 6.90 ppm.
以下、本発明で得られるα−オレフィン・（メタ）アクリル酸エステル共重合体のうち、一例としてエチレン・アクリル酸エステル共重合体における部分構造とその１３Ｃ−ＮＭＲスペクトルの帰属結果（部分構造中の炭素とそのケミカルシフト）を示す。 Hereinafter, of the α-olefin / (meth) acrylic acid ester copolymer obtained in the present invention, as an example, the partial structure in the ethylene / acrylic acid ester copolymer and the result of assignment of its 13 C-NMR spectrum (in the partial structure) Carbon and its chemical shift).
本発明で得られるα−オレフィン・（メタ）アクリル酸エステル共重合体の特徴のひとつとして、主鎖のメチル分岐数が主鎖炭素１０００個あたり２個未満であり、かつ、炭素数２以上の炭化水素基の分岐を持たず、かつ、末端以外の主鎖中に（ｂ）成分が共重合されていることが挙げられる。
ここで、主鎖のメチル分岐とは、上述の部分構造（ＩＩ）における炭素番号１３番で示される構造である。
As one of the characteristics of the α-olefin / (meth) acrylic acid ester copolymer obtained in the present invention, the number of methyl branches in the main chain is less than 2 per 1000 main chain carbons, and the number of carbons is 2 or more. It is mentioned that the component (b) is not copolymerized in the main chain other than the terminal and does not have a hydrocarbon group branch.
Here, the methyl branch of the main chain is a structure represented by carbon number 13 in the partial structure (II) described above.
本発明においては、主鎖の分岐構造（ただし（ｂ）成分にもとづく分岐は除く）は、かかるメチル分岐のみであり、炭素数２以上の炭化水素基の分岐を持たない。また、メチル分岐は存在するものの、その数は主鎖炭素１０００個あたり２個未満ときわめて少ない。このように、本発明のα−オレフィン・（メタ）アクリル酸エステル共重合体は、炭素数２以上の比較的長い分岐がなく、かつ、メチル分岐の数がきわめて少ないため、結晶性が高く、機械的ならびに熱的物性が優れている。本発明のα−オレフィン・（メタ）アクリル酸エステル共重合体においては、主鎖のメチル分岐数が主鎖炭素１０００個あたり２個未満であるが、好ましくは主鎖炭素１０００個あたり１．５個未満、より好ましくは主鎖炭素１０００個あたり１．３個未満、さらに好ましくは主鎖炭素１０００個あたり１．２個未満、最も好ましくは主鎖炭素１０００個あたり１．０個未満である。 In the present invention, the branched structure of the main chain (except for the branch based on the component (b)) is only such a methyl branch and does not have a branch of a hydrocarbon group having 2 or more carbon atoms. In addition, although there are methyl branches, the number is very small, less than 2 per 1000 main chain carbons. Thus, the α-olefin / (meth) acrylic acid ester copolymer of the present invention has no relatively long branch having 2 or more carbon atoms and has a very small number of methyl branches. Excellent mechanical and thermal properties. In the α-olefin / (meth) acrylic acid ester copolymer of the present invention, the number of methyl branches in the main chain is less than 2 per 1000 main chain carbons, but preferably 1.5 per 1000 main chain carbons. Less than 1.3, more preferably less than 1.3 per 1000 main chain carbons, more preferably less than 1.2 per 1000 main chain carbons, and most preferably less than 1.0 per 1000 main chain carbons.
上述のように、本発明のα−オレフィン・（メタ）アクリル酸エステル共重合体においては、末端以外の主鎖中に（ｂ）成分が共重合されている。末端以外の主鎖中に（ｂ）成分が共重合されているとは、例えば、α−オレフィンがエチレンで、（ｂ）成分がアクリル酸ｔ−ブチルやアクリル酸ｎ−ブチルの場合、上述の部分構造（ＩＩＩ）または部分構造（ＶＩ）によって示される構造を指す。前記したように、前述も非特許文献８においては、いわゆるＳＨＯＰ系のニッケル錯体を用いて、エチレンとメタクリル酸メチルの共重合が記載されているが、ここで得られた共重合体には、末端以外の主鎖中に共重合されたメタクリル酸メチルは存在せず、メタクリル酸メチルは主鎖末端のみに存在する点で、本発明と大きく異なる。（ｂ）成分が主鎖末端にしか存在しない場合には、共重合体中における（ｂ）成分の含量は、必然的にきわめて低い値になる。したがって、このような場合においては、極性基にもとづく（ｂ）成分の効果、たとえば、塗装性、印刷性、帯電防止性、無機フィラー分散性、他樹脂との接着性、他樹脂との相溶化能などが、不十分となる。これに対して、本発明においては、主鎖末端のみならず、末端以外の主鎖中に（ｂ）成分が共重合されることから、共重合体中における（ｂ）成分の含量を大きくすることができ、物性上有利である。 As described above, in the α-olefin / (meth) acrylic acid ester copolymer of the present invention, the component (b) is copolymerized in the main chain other than the terminal. That the component (b) is copolymerized in the main chain other than the end means that, for example, when the α-olefin is ethylene and the component (b) is t-butyl acrylate or n-butyl acrylate, It refers to the structure represented by partial structure (III) or partial structure (VI). As described above, also in Non-Patent Document 8, the copolymerization of ethylene and methyl methacrylate is described using a so-called SHOP-based nickel complex. There is no methyl methacrylate copolymerized in the main chain other than the terminal, and methyl methacrylate is greatly different from the present invention in that it exists only at the main chain terminal. When the component (b) is present only at the end of the main chain, the content of the component (b) in the copolymer is necessarily extremely low. Therefore, in such a case, the effect of the component (b) based on the polar group, for example, paintability, printability, antistatic properties, inorganic filler dispersibility, adhesion with other resins, and compatibility with other resins The performance will be insufficient. On the other hand, in the present invention, since the component (b) is copolymerized not only in the main chain terminal but also in the main chain other than the terminal, the content of the component (b) in the copolymer is increased. This is advantageous in terms of physical properties.
本発明で得られるα−オレフィン・（メタ）アクリル酸エステル共重合体の別の特徴のひとつとして、主鎖末端がエチル基、ビニル基、および（ｂ）成分として共重合に用いた（メタ）アクリル酸エステル由来の下記一般式（Ｄ）で表される基からなり、かつ、一般式（Ｄ）における炭素−炭素二重結合が、Ｚ体とＥ体の２種の幾何異性体構造からなることが挙げられる。
−ＣＨ＝Ｃ（Ｒ８）ＣＯ２（Ｒ９） …（Ｄ）
（ここで、Ｒ８は水素または炭素数１〜１０の炭化水素基であり、分岐、環、および／または不飽和結合を有していてもよい。Ｒ９は炭素数１〜３０の炭化水素基であり、分岐、環、および／または不飽和結合を有していてもよい。さらに、Ｒ９内の任意の位置にヘテロ原子を含有していてもよい。）
As another feature of the α-olefin / (meth) acrylic acid ester copolymer obtained in the present invention, the main chain terminal is an ethyl group, a vinyl group, and (b) component used for copolymerization (meth) It consists of a group represented by the following general formula (D) derived from an acrylate ester, and the carbon-carbon double bond in the general formula (D) consists of two types of geometric isomers, Z-form and E-form. Can be mentioned.
-CH = C (R 8) CO 2 (R 9) ... (D)
(Here, R 8 is hydrogen or a hydrocarbon group having 1 to 10 carbon atoms, and may have a branch, a ring, and / or an unsaturated bond. R 9 is a hydrocarbon having 1 to 30 carbon atoms. A group, which may have a branch, a ring, and / or an unsaturated bond, and further may contain a heteroatom at any position within R 9. )
以下、本特徴を、α−オレフィンがエチレンで、（ｂ）成分がアクリル酸ｔ−ブチルの場合を例にとって説明する。すなわち、本発明で得られるエチレン・アクリル酸ｔ−ブチル共重合体の主鎖末端は、エチル基、ビニル基、および、アクリル酸ｔ−ブチル由来の−ＣＨ＝ＣＨＣＯ２ｔＢｕ（ｔＢｕは、ｔ−ブチル基を表す）からなる。これらのうち、エチル末端は、部分構造（Ｉ）における炭素番号１および２の構造で示される。また、ビニル末端は、部分構造（Ｉ）における炭素番号７および８の構造で示される。また、アクリル酸ｔ−ブチル由来の−ＣＨ＝ＣＨＣＯ２ｔＢｕ末端は、部分構造（ＩＶ）または部分構造（Ｖ）によって示される構造を指し、部分構造（ＩＶ）および（Ｖ）の両者、すなわち、Ｅ体とＺ体の２種の幾何異性体構造が存在する。なお、部分構造（Ｉ）において、エチル末端とビニル末端を連結する主鎖部分は、−［ＣＨ２ＣＨ２］ｎ−で示されているが、これは、ポリエチレン主鎖構造を代表的に示したものであり、該連結部分において、部分構造（ＩＩ）、（ＩＩＩ）、（ＶＩ）のような構造が含まれていてもよい。 Hereinafter, this feature will be described by taking the case where the α-olefin is ethylene and the component (b) is t-butyl acrylate as an example. That is, the end of the main chain of the ethylene / t-butyl acrylate copolymer obtained in the present invention is ethyl group, vinyl group, and —CH═CHCO 2 tBu derived from t-butyl acrylate (tBu is t- Represents a butyl group). Among these, the ethyl terminal is shown by the structure of carbon numbers 1 and 2 in the partial structure (I). Moreover, the vinyl terminal is shown by the structure of carbon numbers 7 and 8 in the partial structure (I). The —CH═CHCO 2 tBu terminal derived from t-butyl acrylate refers to the structure represented by the partial structure (IV) or the partial structure (V), and both the partial structures (IV) and (V), that is, There are two types of geometric isomer structures, E and Z. In the partial structure (I), the main chain portion connecting the ethyl terminal and the vinyl terminal is represented by — [CH 2 CH 2 ] n —, which is representative of the polyethylene main chain structure. In the connecting portion, a structure such as partial structure (II), (III), or (VI) may be included.
前記した非特許文献５においては、パラジウム錯体によって得られたエチレン・アクリル酸メチル共重合体の構造が示されているが、該共重合体の主鎖末端は、エチル基、ビニル基に加え、アクリル酸メチル由来の−ＣＨ＝ＣＨＣＯ２ＣＨ３基およびＣＨ３ＣＨ（ＣＯ２ＣＨ３）ＣＨ２−基であり、−ＣＨ＝ＣＨＣＯ２ＣＨ３基はＺ体のみでＥ体はなく、また本発明では存在しないＣＨ３ＣＨ（ＣＯ２ＣＨ３）ＣＨ２−基からなる末端が存在し、本発明で得られる共重合体とは明らかに構造が異なる。また、このように末端の構造が異なるという事実は、本発明の重合触媒と非特許文献５で示された重合触媒において、両者は異なる重合機構を有しているということを意味する。 In the aforementioned Non-Patent Document 5, the structure of the ethylene / methyl acrylate copolymer obtained by the palladium complex is shown, but the main chain terminal of the copolymer is in addition to the ethyl group and the vinyl group, —CH═CHCO 2 CH 3 group and CH 3 CH (CO 2 CH 3 ) CH 2 — group derived from methyl acrylate, —CH═CHCO 2 CH 3 group is only Z-form, no E-form, not present in the invention CH 3 CH (CO 2 CH 3 ) CH 2 - end is present consisting of group clearly different structure from the copolymer obtained in the present invention. In addition, the fact that the terminal structures are different in this way means that the polymerization catalyst of the present invention and the polymerization catalyst shown in Non-Patent Document 5 have different polymerization mechanisms.
本発明の共重合体は、共重合体の極性基にもとづく効果により、良好な塗装性、印刷性、帯電防止性、無機フィラー分散性、他樹脂との接着性、他樹脂との相溶化能などが発現する。こうした性質を利用して、本発明の共重合体は、さまざまな用途に使用することができる。例えば、フィルム、シート、接着性樹脂、バインダー、相溶化剤などとして使用可能である。 The copolymer of the present invention has good paintability, printability, antistatic properties, inorganic filler dispersibility, adhesion to other resins, and compatibility with other resins due to the effects based on the polar groups of the copolymer. Etc. are expressed. Utilizing these properties, the copolymer of the present invention can be used in various applications. For example, it can be used as a film, sheet, adhesive resin, binder, compatibilizing agent and the like.
以下に本発明を実施例および比較例によって具体的に説明するが、本発明はこれらの実施例によって限定されるものではない。なお、実施例、比較例で用いた評価方法及び使用触媒は以下の通りである。
なお、以下の合成例で、特に断りのない限り、操作は精製窒素雰囲気下で行い、溶媒は脱水・脱酸素したものを用いた。
EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to these examples. The evaluation methods and catalysts used in the examples and comparative examples are as follows.
In the following synthesis examples, unless otherwise specified, the operation was performed in a purified nitrogen atmosphere, and the solvent was dehydrated and deoxygenated.
１．評価方法
（１）Ｔｃ、ΔＨｃ、Ｔｍ、ΔＨｍ：以下のＤＳＣ測定により求めた。
ＰｅｒｋｉｎＥｌｍｅｒ社製ＰＹＲＩＳ Ｄｉａｍｏｎｄ ＤＳＣ示差走査熱量測定装置を使用して、試料（約５ｍｇ）を２１０℃で５分間融解後、１０℃／ｍｉｎの速度で−２０℃まで降温し、−２０℃で５分保持した後に、１０℃／ｍｉｎの速度で２１０℃まで昇温することにより融解曲線を得た。降温段階における主発熱ピークのピークトップ温度を結晶化温度Ｔｃとし、該ピークのピーク面積をΔＨｃとした。また、融解曲線を得るために行った最後の昇温段階における主吸熱ピークのピークトップ温度を融点Ｔｍとし、該ピークのピーク面積をΔＨｍとした。
（２）重量平均分子量Ｍｗ、数平均分子量Ｍｎ、分子量分布Ｍｗ／Ｍｎ：以下のＧＰＣ測定により求めた。
はじめに、試料約２０（ｍｇ）をポリマーラボラトリー社製高温ＧＰＣ用前処理装置ＰＬ−ＳＰ ２６０ＶＳ用のバイアル瓶に採取し、安定剤としてＢＨＴを含有するｏ−ジクロロベンゼン（ＢＨＴ濃度＝０．５ｇ／Ｌ）を加え、ポリマー濃度が０．１（重量％）になるように調整した。ポリマーを上記高温ＧＰＣ用前処理装置ＰＬ−ＳＰ ２６０ＶＳ中で１３５℃に加熱して溶解させ、グラスフィルターにて濾過して試料を調製した。なお、本発明におけるＧＰＣ測定において、グラスフィルターに捕捉されたポリマーはなかった。次に、カラムとして、東ソー社製ＴＳＫｇｅｌ ＧＭＨ−ＨＴ（３０ｃｍ×４本）およびＲＩ検出器を装着したウォーターズ社製ＧＰＣＶ２０００を使用してＧＰＣ測定を行った。測定条件としては、試料溶液注入量：５２４．５（μｌ）、カラム温度：１３５℃、溶媒：ｏ−ジクロロベンゼン、流量：１．０（ｍｌ／ｍｉｎ）を採用した。分子量の算出は以下のように行った。すなわち、標準試料として市販の単分散のポリスチレンを使用し、該ポリスチレン標準試料およびエチレン系重合体の粘度式から、保持時間と分子量に関する校正曲線を作成し、該校正曲線に基づいて分子量の算出を行った。なお、粘度式としては、［η］＝Ｋ・Ｍαを使用し、ポリスチレンに対しては、Ｋ＝１．３８Ｅ−４、α＝０．７０を使用し、エチレン系重合体に対しては、Ｋ＝４．７７Ｅ−４、α＝０．７０を使用した。
1. Evaluation Method (1) Tc, ΔHc, Tm, ΔHm: Obtained by the following DSC measurement.
Using a PerkinElmer PYRIS Diamond DSC differential scanning calorimeter, the sample (about 5 mg) was melted at 210 ° C. for 5 minutes, cooled to −20 ° C. at a rate of 10 ° C./min, and then at −20 ° C. for 5 minutes. After being held, a melting curve was obtained by raising the temperature to 210 ° C. at a rate of 10 ° C./min. The peak top temperature of the main exothermic peak in the temperature lowering stage was defined as the crystallization temperature Tc, and the peak area of the peak was defined as ΔHc. In addition, the peak top temperature of the main endothermic peak in the final temperature rising stage performed for obtaining the melting curve was defined as the melting point Tm, and the peak area of the peak was defined as ΔHm.
(2) Weight average molecular weight Mw, number average molecular weight Mn, molecular weight distribution Mw / Mn: determined by the following GPC measurement.
First, about 20 (mg) of a sample was collected in a vial for a high temperature GPC pretreatment device PL-SP 260VS manufactured by Polymer Laboratories, and o-dichlorobenzene containing BHT as a stabilizer (BHT concentration = 0.5 g / L) was added to adjust the polymer concentration to 0.1 (% by weight). The polymer was heated and dissolved at 135 ° C. in the high-temperature GPC pretreatment apparatus PL-SP 260VS, and filtered through a glass filter to prepare a sample. In the GPC measurement in the present invention, no polymer was captured by the glass filter. Next, GPC measurement was performed using Tosoh's TSKgel GMH-HT (30 cm × 4) and a Waters GPCV2000 equipped with an RI detector. As measurement conditions, sample solution injection amount: 524.5 (μl), column temperature: 135 ° C., solvent: o-dichlorobenzene, flow rate: 1.0 (ml / min) were employed. The molecular weight was calculated as follows. That is, a commercially available monodispersed polystyrene is used as a standard sample, a calibration curve relating to the retention time and molecular weight is created from the polystyrene standard sample and the viscosity formula of the ethylene polymer, and the molecular weight is calculated based on the calibration curve. went. As the viscosity formula, [η] = K · M α is used, and for polystyrene, K = 1.38E-4 and α = 0.70 are used, and for the ethylene-based polymer. K = 4.77E-4, α = 0.70.
２．金属錯体
下記合成例で得られたニッケル錯体１〜４およびリガンドＢ−７、Ｂ−８、Ｂ−１０を用いた。
2. Metal Complexes Nickel complexes 1 to 4 and ligands B-7, B-8, and B-10 obtained in the following synthesis examples were used.
（合成例１）ニッケル錯体１の合成
１．２３７ｇ（４．０ｍｍｏｌ）のアシルトリフェニルフォスフォラニルメタレンと１．１０ｇ（４．０ｍｍｏｌ）のビス−１，５−シクロオクタジエンニッケル（０）（以下、Ｎｉ（ＣＯＤ）２と称する）の混合物に、室温で４０ｍｌのトルエンを加え、黄色懸濁液を得た。この懸濁液に、注射器を用いて０．８６ｇ（８．０ｍｍｏｌ）の２，６−ルチジンを加えた。得られた混合物を室温で攪拌した後、攪拌しながら６０℃まで昇温し、６０℃で３．５時間反応させ、暗褐色の溶液を得た。得られた溶液をカニューラにて濾過し、得られた暗黄色の濾液を減圧下に濃縮し、元の容積の１／４にした。この濃縮溶液に、液が濁りを生じるまでｎ−ヘキサン（約３ｍｌ）を滴下した。次いで、この濁りが生じた液を６５℃まで昇温し、透明な溶液を得た。得られた透明な溶液を室温まで２〜３時間かけてゆっくり冷却し、室温付近で黄色微結晶を析出させた。得られた結晶を、母液中で一晩保持した。その後、上澄みをカニューラで濾別し、残った固体を３ｍｌのｎ−ヘキサンで２回洗浄し、最後に固体を６×１０−３ｍｂａｒで減圧下１時間乾燥し、１．１７ｇの下記構造式で表される黄色結晶を得た（収率：６０．４％）。
１Ｈ−ＮＭＲ（Ｃ６Ｄ６，δｐｐｍ）：７．６７（ｍ，５Ｈ），７．３７（ｄ，２Ｈ），７．２−７．０（ｍ，４Ｈ），６．７７（ｍ，４Ｈ），６．５６（ｄ，１Ｈ），６．５０（ｔ，１Ｈ），６．１５（ｄ，１Ｈ），４．２０（ｓ，１Ｈ），３．４９（ｓ，６Ｈ），２．０６（ｓ，３Ｈ）；３１Ｐ−ＮＭＲ（Ｃ６Ｄ６，δｐｐｍ）：２１．７８ （ｓ）．
Synthesis Example 1 Synthesis of Nickel Complex 1 1.237 g (4.0 mmol) of acyltriphenylphosphoranylmetallene and 1.10 g (4.0 mmol) of bis-1,5-cyclooctadiene nickel (0) To a mixture of Ni (COD) 2 ), 40 ml of toluene was added at room temperature to obtain a yellow suspension. To this suspension, 0.86 g (8.0 mmol) of 2,6-lutidine was added using a syringe. The resulting mixture was stirred at room temperature, then heated to 60 ° C. with stirring, and reacted at 60 ° C. for 3.5 hours to obtain a dark brown solution. The resulting solution was filtered with a cannula, and the resulting dark yellow filtrate was concentrated under reduced pressure to ¼ of the original volume. To this concentrated solution, n-hexane (about 3 ml) was added dropwise until the liquid became cloudy. Next, the turbid liquid was heated to 65 ° C. to obtain a transparent solution. The obtained transparent solution was slowly cooled to room temperature over 2 to 3 hours, and yellow fine crystals were precipitated at around room temperature. The resulting crystals were kept overnight in the mother liquor. Thereafter, the supernatant was filtered off with a cannula, the remaining solid was washed twice with 3 ml of n-hexane, and finally the solid was dried at 6 × 10 −3 mbar under reduced pressure for 1 hour to obtain 1.17 g of the following structural formula. (Yield: 60.4%) was obtained.
1 H-NMR (C 6 D 6 , δ ppm): 7.67 (m, 5H), 7.37 (d, 2H), 7.2-7.0 (m, 4H), 6.77 (m, 4H), 6.56 (d, 1H), 6.50 (t, 1H), 6.15 (d, 1H), 4.20 (s, 1H), 3.49 (s, 6H), 2. 06 (s, 3H); 31 P-NMR (C 6 D 6 , δ ppm): 21.78 (s).
（合成例２）ニッケル錯体２の合成
１．５２２ｇ（４．０ｍｍｏｌ）の（ベンゾイルメタレン）トリフェニルフォスフォランと１．１０ｇ（４．０ｍｍｏｌ）のＮｉ（ＣＯＤ）２の混合物に、室温で１００ｍｌの
トルエンを加え、懸濁液を得た。この懸濁液に、注射器を用いて９．５ｇ（１２０ｍｍｏｌ）のピリジンを加えた。得られた混合物を室温で攪拌した後、攪拌しながら４５℃までゆっくり昇温し、透明な黄色溶液を得た。加熱のためのオイルバスをはずし、得られた溶液を室温で１８時間攪拌した。得られた反応混合物をカニューラで濾過し、残った固体を５ｍｌのトルエンで２回洗浄した。得られた固体を減圧下に乾燥し、粘着性のある黄色粉末を得た。この粉末を２０ ｍｌのトルエンに懸濁させ、４０℃まで加温し、さらに２０ｍｌのｎ−ヘキサンを添加した。さらに５５℃まで加温し、結晶を析出させた。その後室温に戻して１８時間引き続き結晶を析出させた。上澄みをカニューラで除去し、残った固体を１０ｍｌのｎ−ヘキサンで２回洗浄した。得られた固体を６×１０−３ｍｂａｒで減圧下５時間乾燥し、１．５１ｇの下記構造式で表される黄褐色結晶を得た（収率：７２．８％）。
１Ｈ−ＮＭＲ（Ｃ６Ｄ６，δｐｐｍ）：８．６０（ｄ，２Ｈ），８．１３（ｄ，２Ｈ），７．７５（ｍ，４Ｈ），７．５２（ｄ，２Ｈ），７．２１（ｍ，９Ｈ），７．０６（ｄ，３Ｈ），６．９３（ｍ，１Ｈ），６．３３（ｍ，２Ｈ），５．１１（ｓ，１Ｈ）；３１Ｐ−ＮＭＲ（Ｃ６Ｄ６，δｐｐｍ）：２４．０８（ｓ）．
Synthesis Example 2 Synthesis of Nickel Complex 2 To a mixture of 1.522 g (4.0 mmol) of (benzoylmethalene) triphenylphosphorane and 1.10 g (4.0 mmol) of Ni (COD) 2 was added 100 ml at room temperature. Of toluene was added to obtain a suspension. To this suspension, 9.5 g (120 mmol) of pyridine was added using a syringe. The resulting mixture was stirred at room temperature and then slowly heated to 45 ° C. with stirring to obtain a transparent yellow solution. The oil bath for heating was removed and the resulting solution was stirred at room temperature for 18 hours. The resulting reaction mixture was filtered through a cannula and the remaining solid was washed twice with 5 ml of toluene. The obtained solid was dried under reduced pressure to obtain a sticky yellow powder. This powder was suspended in 20 ml of toluene, heated to 40 ° C., and further 20 ml of n-hexane was added. The mixture was further heated to 55 ° C. to precipitate crystals. Thereafter, the temperature was returned to room temperature, and crystals were continuously precipitated for 18 hours. The supernatant was removed with a cannula and the remaining solid was washed twice with 10 ml of n-hexane. The obtained solid was dried under reduced pressure at 6 × 10 −3 mbar for 5 hours to obtain 1.51 g of a tan crystal represented by the following structural formula (yield: 72.8%).
1 H-NMR (C 6 D 6 , δ ppm): 8.60 (d, 2H), 8.13 (d, 2H), 7.75 (m, 4H), 7.52 (d, 2H), 7 .21 (m, 9H), 7.06 (d, 3H), 6.93 (m, 1H), 6.33 (m, 2H), 5.11 (s, 1H); 31 P-NMR (C 6 D 6, δppm): 24.08 (s).
（合成例３）ニッケル錯体３の合成
１３．９ｍｌ（１２０ｍｍｏｌ）の２，６−ルチジン中に、１．５２２ｇ（４．０ｍｍｏｌ）の（ベンゾイルメタレン）トリフェニルフォスフォランと１．１０ｇ（４．０ｍｍｏｌ）のＮｉ（ＣＯＤ）２を懸濁させ、さらに室温で１００ｍｌのトルエンを加えた。この懸濁液を室温で攪拌した後、攪拌しながら４５℃までゆっくり昇温し、すべての固体を溶解させ、透明な黄色溶液を得た。ここで得られた溶液を室温で１８時間攪拌した。得られた暗色の懸濁液に乾燥したセライトを加え、攪拌した後１０分間静置し、セライトを沈降させた。次いで、カニューラを用いてセライトと濾液を濾別した。濾別したセライトについては、３ｍｌのトルエンを用いて２回抽出を行い、得られた抽出液と先に得られた濾液をあわせ、それを減圧乾燥し、粘着性のある黄色粉末を得た。得られた粉末を５０ｍｌのトルエンに溶解させ、少量の不溶成分をカニューラで濾別した。透明な濾液を減圧下に容量が２５ｍｌになるまで濃縮したところ、黄色沈殿が生成し始めた。沈殿が生成したフラスコを遮光し室温で２４時間放置した。上澄みをカニューラで除去し、残った固体を恒量になるまで減圧乾燥し、０．８８ｇの下記構造式で表される目標生成物を得た（収率：４０．３％）。
１Ｈ−ＮＭＲ（Ｃ６Ｄ６，δｐｐｍ）：７．８２（ｄ，２Ｈ），７．６９（ｍ，４Ｈ），７．３９（ｄ，２Ｈ），７．２５−６．９５（ｍ，９Ｈ），６，７９（ｍ，３Ｈ），６．５５（ｍ，１Ｈ），６．２１（ｄ，２Ｈ），５．０３（ｓ，１Ｈ），３．４８（ｓ，６Ｈ）；３１Ｐ−ＮＭＲ（Ｃ６Ｄ６，δｐｐｍ）：１９．６３ｐｐｍ（約２％のダイマー｛［Ｐｈ２Ｐ−ＣＨ＝Ｃ（Ｐｈ）−Ｏ−］ＮｉＰｈ）｝２が存在し、このダイマーにもとづく３１Ｐ−ＮＭＲのシグナルが、１７．３５ｐｐｍに観測される）
Synthesis Example 3 Synthesis of Nickel Complex 3 In 13.9 ml (120 mmol) of 2,6-lutidine, 1.522 g (4.0 mmol) of (benzoylmethalene) triphenylphosphorane and 1.10 g (4. 0 mmol) of Ni (COD) 2 was suspended, and 100 ml of toluene was further added at room temperature. After stirring this suspension at room temperature, it heated up slowly to 45 degreeC, stirring, all the solids were dissolved, and the transparent yellow solution was obtained. The solution obtained here was stirred at room temperature for 18 hours. Dry celite was added to the obtained dark suspension, stirred, and allowed to stand for 10 minutes to precipitate celite. Subsequently, celite and the filtrate were separated by using a cannula. The Celite separated by filtration was extracted twice with 3 ml of toluene, and the obtained extract and the previously obtained filtrate were combined and dried under reduced pressure to obtain a sticky yellow powder. The obtained powder was dissolved in 50 ml of toluene, and a small amount of insoluble components was filtered off with a cannula. The clear filtrate was concentrated under reduced pressure to a volume of 25 ml and a yellow precipitate began to form. The flask in which the precipitate was formed was shielded from light and left at room temperature for 24 hours. The supernatant was removed with a cannula, and the remaining solid was dried under reduced pressure to a constant weight to obtain 0.88 g of the target product represented by the following structural formula (yield: 40.3%).
1 H-NMR (C 6 D 6 , δ ppm): 7.82 (d, 2H), 7.69 (m, 4H), 7.39 (d, 2H), 7.25-6.95 (m, 9H), 6, 79 (m, 3H), 6.55 (m, 1H), 6.21 (d, 2H), 5.03 (s, 1H), 3.48 (s, 6H); 31 P -NMR (C 6 D 6, δppm ): 19.63ppm ( about 2% of the dimer {[Ph 2 P-CH = C (Ph) -O-] NiPh)} 2 is present, 31 P based on the dimer -NMR signal is observed at 17.35 ppm)
（合成例４）ニッケル錯体４の合成
０．９６５ｇ（２．０ｍｍｏｌ）のＰｈ３Ｐ＝Ｃ（ＳＯ３Ｎａ）Ｃ（＝Ｏ）Ｐｈと０．５５０ｇ（２．０ｍｍｏｌ）のビス−１，５−シクロオクタジエンニッケル（０）（以下、Ｎｉ（ＣＯＤ）２と称する）の固体混合物に、−６０°
Ｃで４０ｍｌのテトラヒドロフラン（以下ＴＨＦと称する）を加え、黄色懸濁液を得た。得られた懸濁液を攪拌しながら、注射器を用いて２．４５ｍｌのピリジン（乾燥させて水分を除去したもの）を加えた。懸濁液は暗黄色となり、約１０分間で茶色になった。室温で引き続き２０時間攪拌した後、約１．５ｇの乾燥セライトを加えた。攪拌後数分間静置し、カニューラ濾過にて濾液を得た。残渣に対して５ｍｌの乾燥ＴＨＦで抽出操作を行い、カニューラ濾過にて濾液を得た。この操作をもう一度繰り返した。得られた濾液を集め、減圧下に濃縮し黄褐色の固体を得た。得られた固体を乾燥ｎ−ヘキサン（５ｍｌ）で洗浄し、カニューラにてｎ−ヘキサンを除去した。この操作をもう一度繰り返した。最後に固体を減圧下、恒量になるまで乾燥し、０．９５ｇの下記構造式で表される黄褐色固体を得た（収率：７６．６％）。
１Ｈ−ＮＭＲ（ＣＤ２Ｃｌ２，δｐｐｍ）：８．５９（ｂｒｏａｄ ｓ，２Ｈ），７．８０−６．８０（ｂｒｏａｄ ｍ，２１Ｈ），６．５９（ｂｒｏａｄ ｓ，２Ｈ）；３１Ｐ−ＮＭＲ（ＣＤ２Ｃｌ２，δｐｐｍ）：３７．２（ｂｒｏａｄ ｓ）．
Synthesis Example 4 Synthesis of Nickel Complex 4 0.965 g (2.0 mmol) of Ph 3 P═C (SO 3 Na) C (═O) Ph and 0.550 g (2.0 mmol) of bis-1,5 A solid mixture of cyclooctadiene nickel (0) (hereinafter referred to as Ni (COD) 2 )
In C, 40 ml of tetrahydrofuran (hereinafter referred to as THF) was added to obtain a yellow suspension. While stirring the resulting suspension, 2.45 ml of pyridine (dried to remove moisture) was added using a syringe. The suspension turned dark yellow and turned brown in about 10 minutes. After continuously stirring for 20 hours at room temperature, about 1.5 g of dry celite was added. The mixture was allowed to stand for several minutes after stirring, and a filtrate was obtained by cannula filtration. The residue was extracted with 5 ml of dry THF, and a filtrate was obtained by cannula filtration. This operation was repeated once more. The resulting filtrate was collected and concentrated under reduced pressure to give a tan solid. The obtained solid was washed with dry n-hexane (5 ml), and n-hexane was removed with a cannula. This operation was repeated once more. Finally, the solid was dried to a constant weight under reduced pressure to obtain 0.95 g of a tan solid represented by the following structural formula (yield: 76.6%).
1 H-NMR (CD 2 Cl 2 , δ ppm): 8.59 (broads, 2H), 7.80-6.80 (broad m, 21H), 6.59 (broads, 2H); 31 P- NMR (CD 2 Cl 2 , δ ppm): 37.2 (broad s).
（合成例５）リガンドＢ−７の合成
（１）中間体Ｂ−７＿５の合成
(Synthesis Example 5) Synthesis of Ligand B-7 (1) Synthesis of Intermediate B-7_5
上記のスキームにしたがって、中間体Ｂ−７＿５を合成した。ここで、ＭＯＭはメトキシメチル基を表す（以下同様）。
２，４−ジ−ｔ−ブチルフェノール（１０ｇ，４８．５ｍｍｏｌ）をＴＨＦ（１００ｍｌ）に溶解させた。この溶液を、別途調整した水素化ナトリウム（２．９１ｇ，１．５ｅｑ，ミネラルオイル中に６０％濃度で分散したもの）のＴＦＨ（２００ｍｌ）溶液に０℃で攪拌しながら滴下した。室温まで徐々に昇温し、室温で２時間反応させた。次いで、クロロメトキシメタン（７．７６ｇ）を０℃で滴下し、室温に昇温した後、室温で３時間反応させた。曇った白色溶液に対し、水および酢酸エチルを用いて抽出操作を行った。有機層をＫＯＨ水溶液（１Ｍ，１５０ｍｌ）、次いで水（１５０ｍｌ）で洗浄し、硫酸ナトリウム上で乾燥させた。無機塩を濾別した後、減圧下に濃縮し、淡黄色のオイルを得た。得られたオイルを、石油エーテル／酢酸エチル（４０／１）を溶媒としてカラムで精製し、目的とする中間体Ｂ−７＿５を１０．５ｇ得た。
（２）中間体Ｂ−７＿６の合成
Intermediate B-7_5 was synthesized according to the above scheme. Here, MOM represents a methoxymethyl group (the same applies hereinafter).
2,4-di-t-butylphenol (10 g, 48.5 mmol) was dissolved in THF (100 ml). This solution was added dropwise to a separately prepared TFH (200 ml) solution of sodium hydride (2.91 g, 1.5 eq, dispersed in mineral oil at a concentration of 60%) at 0 ° C. with stirring. The temperature was gradually raised to room temperature, and the reaction was allowed to proceed at room temperature for 2 hours. Next, chloromethoxymethane (7.76 g) was added dropwise at 0 ° C., and the temperature was raised to room temperature, followed by reaction at room temperature for 3 hours. The cloudy white solution was extracted with water and ethyl acetate. The organic layer was washed with aqueous KOH (1M, 150 ml), then water (150 ml) and dried over sodium sulfate. The inorganic salt was filtered off and concentrated under reduced pressure to obtain a pale yellow oil. The obtained oil was purified by a column using petroleum ether / ethyl acetate (40/1) as a solvent to obtain 10.5 g of the intended intermediate B-7_5.
(2) Synthesis of intermediate B-7_6
上記のスキームにしたがって、中間体Ｂ−７＿６を合成した。
０．７５ｇ（３．０ｍｍｏｌ）の中間体Ｂ−７＿５をＴＨＦ（３０ｍｌ）に溶解し、ここに、ｎ−ブチルリチウム（２．５Ｍ，１．２ｍｌ，３．０ｍｍｏｌ）をアルゴン雰囲気下、０℃で滴下した。室温まで徐々に昇温し、室温で３時間反応を行った。次いで、この反応混合物に、ビス（２−メトキシフェニル）クロロフォスフィン（７００ｍｇ，２．５０ｍｍｏｌ）を１５ｍｌのＴＨＦに溶解させた溶液を０℃で滴下した。徐々に室温まで昇温し、室温で終夜攪拌を行った。攪拌終了後、脱気した飽和塩化アンモニウム水溶液（１０ｍｌ）を加え、有機層を分離した後ジエチルエーテルで抽出し、食塩水（１０ｍｌ）で洗浄した後、硫酸ナトリウム上で乾燥し、中間体Ｂ−７＿６を得た。
同様の操作を繰り返し、最終的に中間体Ｂ−７＿６を８ｇ得た。
（３）中間体Ｂ−７＿ＨＣｌの合成
Intermediate B-7_6 was synthesized according to the above scheme.
0.75 g (3.0 mmol) of intermediate B-7_5 was dissolved in THF (30 ml), and n-butyllithium (2.5 M, 1.2 ml, 3.0 mmol) was added at 0 ° C. under an argon atmosphere. It was dripped at. The temperature was gradually raised to room temperature, and the reaction was carried out at room temperature for 3 hours. Next, a solution of bis (2-methoxyphenyl) chlorophosphine (700 mg, 2.50 mmol) dissolved in 15 ml of THF was added dropwise to the reaction mixture at 0 ° C. The temperature was gradually raised to room temperature, and the mixture was stirred at room temperature overnight. After completion of the stirring, deaerated saturated ammonium chloride aqueous solution (10 ml) was added, the organic layer was separated, extracted with diethyl ether, washed with brine (10 ml), dried over sodium sulfate, intermediate B- 7_6 was obtained.
The same operation was repeated to finally obtain 8 g of intermediate B-7_6.
(3) Synthesis of intermediate B-7_HCl
上記のスキームにしたがって、中間体Ｂ−７＿ＨＣｌを合成した。
合成例５（２）で得られた中間体Ｂ−７＿６（８ｇ）をジエチルエーテル（５００ｍｌ）に溶解させ、−７８℃で塩化水素ガスを２５分間バブリングさせた。その後、室温まで昇温し、室温で終夜攪拌を行った。攪拌終了後、溶媒を留去し、Ｂ−７＿ＨＣｌを得た。
（４）リガンドＢ−７の合成
Intermediate B-7_HCl was synthesized according to the above scheme.
Intermediate B-7_6 (8 g) obtained in Synthesis Example 5 (2) was dissolved in diethyl ether (500 ml), and hydrogen chloride gas was bubbled at −78 ° C. for 25 minutes. Then, it heated up to room temperature and stirred overnight at room temperature. After completion of stirring, the solvent was distilled off to obtain B-7_HCl.
(4) Synthesis of ligand B-7
上記のスキームにしたがって、リガンドＢ−７を合成した。
合成例５（３）で得られた中間体Ｂ−７＿ＨＣｌのうち、７．３ｇをジエチルエーテル（５００ｍｌ）に溶解し、−７８℃でアンモニアガスを３０分間バブリングさせた。次いで室温まで徐々に昇温し、室温で終夜攪拌を行った。攪拌終了後、溶媒を留去し、粗Ｂ−７を得た。ここで得られた粗Ｂ−７をジエチルエーテル（１０ｍｌ）に分散させた後、１００ｍｌのｎ−ヘキサンを加えて懸濁洗浄を行った。固体成分を除去した後、溶媒を減圧下に除去し、目的とするリガンドＢ−７を得た。収量：５．２ｇ。
１Ｈ−ＮＭＲ（ＭｅＯＤ，δｐｐｍ）：７．３８−６．６９（ｍ，１０Ｈ），３．７０（ｓ，６Ｈ），１．４３（ｓ，９Ｈ），１．１０（ｓ，９Ｈ）；３１Ｐ−ＮＭＲ（ＭｅＯＤ，δｐｐｍ）：４８．２（ｓ）．
Ligand B-7 was synthesized according to the above scheme.
Of the intermediate B-7_HCl obtained in Synthesis Example 5 (3), 7.3 g was dissolved in diethyl ether (500 ml), and ammonia gas was bubbled at −78 ° C. for 30 minutes. Next, the temperature was gradually raised to room temperature, and the mixture was stirred at room temperature overnight. After completion of the stirring, the solvent was distilled off to obtain crude B-7. The crude B-7 obtained here was dispersed in diethyl ether (10 ml), and then 100 ml of n-hexane was added to perform suspension washing. After removing the solid components, the solvent was removed under reduced pressure to obtain the target ligand B-7. Yield: 5.2g.
1 H-NMR (MeOD, δ ppm): 7.38-6.69 (m, 10H), 3.70 (s, 6H), 1.43 (s, 9H), 1.10 (s, 9H); 31 P-NMR (MeOD, δ ppm): 48.2 (s).
（合成例６）リガンドＢ−８の合成
（１）中間体Ｂ−８＿６の合成
(Synthesis Example 6) Synthesis of Ligand B-8 (1) Synthesis of Intermediate B-8_6
上記のスキームにしたがって、中間体Ｂ−８＿６を合成した。
乾燥ＴＨＦ（３５ｍｌ）に懸濁させた金属マグネシウム（４３２ｍｇ，１８ｍｍｏｌ）に、１，２−ジブロモエタンを３滴加え、５分間攪拌した。次に、１−ブロモ−２−メトキシメチルベンゼン（３．０ｇ，１５ｍｍｏｌ）を加え、室温で終夜攪拌した。固体成分を濾別し、得られた溶液を、別途三塩化リンを２５ｍｌの乾燥ＴＨＦに溶解させた溶液に、−７８℃で１５分かけて滴下した。得られた混合物を室温までゆっくり昇温し、室温で終夜攪拌し、Ｂ−８＿３のＴＨＦ溶液を得た。
次に、合成例５（１）と同様の操作で得られたＢ−７＿５（２．０ｇ，８．０ｍｍｏｌ）を３０ｍｌの乾燥ＴＨＦに溶解させ、ここに、ｎ−ブチルリチウム（２．５ Ｍ，３．２ｍｌ，８．０ｍｍｏｌ）をアルゴン雰囲気下、−５０℃で１５分間かけて滴下した。同温度で３０分間攪拌した後、室温まで徐々に昇温し、室温で２時間反応を行った。ここに、上記で得られたＢ−８＿３のＴＨＦ溶液を０℃で１５分間かけて滴下し、滴下終了後、室温まで徐々に昇温し、室温で終夜攪拌を行った。攪拌終了後、飽和塩化アンモニウム水溶液を加え、酢酸エチルで抽出操作を行った後、有機層を硫酸ナトリウム上で乾燥した。無機塩を濾別した後、減圧下に濃縮し、石油エーテル／酢酸エチル（２０／１）を溶媒として、得られた残渣をシリカゲルカラムで精製し、目的とするＢ−８＿６を得た（収量：１．１ｇ）。
同様の操作を繰り返し、最終的にＢ−８＿６を７．２ｇ得た。
（２）中間体Ｂ−８＿ＨＣｌの合成
Intermediate B-8_6 was synthesized according to the above scheme.
Three drops of 1,2-dibromoethane were added to metallic magnesium (432 mg, 18 mmol) suspended in dry THF (35 ml) and stirred for 5 minutes. Next, 1-bromo-2-methoxymethylbenzene (3.0 g, 15 mmol) was added and stirred overnight at room temperature. The solid component was separated by filtration, and the obtained solution was added dropwise at −78 ° C. over 15 minutes to a solution obtained by separately dissolving phosphorus trichloride in 25 ml of dry THF. The resulting mixture was slowly warmed to room temperature and stirred overnight at room temperature to obtain a THF solution of B-8_3.
Next, B-7_5 (2.0 g, 8.0 mmol) obtained by the same operation as in Synthesis Example 5 (1) was dissolved in 30 ml of dry THF, and then n-butyllithium (2.5 M , 3.2 ml, 8.0 mmol) was added dropwise over 15 minutes at −50 ° C. under an argon atmosphere. After stirring at the same temperature for 30 minutes, the temperature was gradually raised to room temperature, and the reaction was performed at room temperature for 2 hours. Here, the THF solution of B-8_3 obtained above was added dropwise at 0 ° C. over 15 minutes. After completion of the dropwise addition, the temperature was gradually raised to room temperature and stirred at room temperature overnight. After completion of the stirring, a saturated aqueous solution of ammonium chloride was added, extraction was performed with ethyl acetate, and the organic layer was dried over sodium sulfate. The inorganic salt was filtered off and concentrated under reduced pressure, and the resulting residue was purified with a silica gel column using petroleum ether / ethyl acetate (20/1) as a solvent to obtain the desired B-8_6 (yield). : 1.1 g).
The same operation was repeated, and finally 7.2 g of B-8_6 was obtained.
(2) Synthesis of intermediate B-8_HCl
上記のスキームにしたがって、中間体Ｂ−８＿ＨＣｌを合成した。
合成例６（１）で得られたＢ−８＿６（７．２ｇ）を２００ｍｌのジエチルエーテルに溶解させ、−７８℃で塩化水素ガスを１０分間バブリングさせた。その後、反応混合物を室温までゆっくり昇温し、室温で３時間攪拌した。攪拌終了後、溶媒を減圧下に留去し、粗Ｂ−８＿ＨＣｌを得た。
（３）リガンドＢ−８の合成
Intermediate B-8_HCl was synthesized according to the above scheme.
B-8_6 (7.2 g) obtained in Synthesis Example 6 (1) was dissolved in 200 ml of diethyl ether, and hydrogen chloride gas was bubbled at −78 ° C. for 10 minutes. The reaction mixture was then slowly warmed to room temperature and stirred at room temperature for 3 hours. After completion of the stirring, the solvent was distilled off under reduced pressure to obtain crude B-8_HCl.
(3) Synthesis of ligand B-8
上記のスキームにしたがって、リガンドＢ−８を合成した。
合成例６（２）で得られた粗Ｂ−８＿ＨＣｌを２００ｍｌのジエチルエーテルに溶解させ、−７８℃でアンモニアガスを３０分間バブリングさせた。その後、反応混合物を室温までゆっくり昇温し、室温で終夜攪拌した。攪拌終了後、溶媒を減圧下に除去し、粗Ｂ−８を得た。ここで得られた粗Ｂ−８をジエチルエーテル（１０ｍｌ）に分散させた後、１００ ｍｌのｎ−ヘキサンを加えて懸濁洗浄を行った。固体成分を除去した後、溶媒を減圧下に除去し、目的とするリガンドＢ−８を得た。収量：５．５ｇ。
１Ｈ−ＮＭＲ（ＭｅＯＤ，δｐｐｍ）：７．５０−６．６５（ｍ，１０Ｈ），４．５３（ｄ，２Ｈ），４．５１（ｄ，２Ｈ），３．２０（ｓ，６Ｈ），１．４１（ｓ，９Ｈ），１．０８（ｓ，９Ｈ）；３１Ｐ−ＮＭＲ（ＭｅＯＤ，δｐｐｍ）：４７．６（ｓ）．
Ligand B-8 was synthesized according to the above scheme.
Crude B-8_HCl obtained in Synthesis Example 6 (2) was dissolved in 200 ml of diethyl ether, and ammonia gas was bubbled at −78 ° C. for 30 minutes. The reaction mixture was then slowly warmed to room temperature and stirred at room temperature overnight. After completion of the stirring, the solvent was removed under reduced pressure to obtain crude B-8. The crude B-8 obtained here was dispersed in diethyl ether (10 ml), and then 100 ml of n-hexane was added for suspension washing. After removing the solid components, the solvent was removed under reduced pressure to obtain the target ligand B-8. Yield: 5.5g.
1 H-NMR (MeOD, δ ppm): 7.50-6.65 (m, 10H), 4.53 (d, 2H), 4.51 (d, 2H), 3.20 (s, 6H), 1.41 (s, 9H), 1.08 (s, 9H); 31 P-NMR (MeOD, δ ppm): 47.6 (s).
（合成例７）リガンドＢ−１０の合成
（１）中間体Ｂ−１０＿３の合成
Synthesis Example 7 Synthesis of Ligand B-10 (1) Synthesis of Intermediate B-10_3
上記のスキームにしたがって、中間体Ｂ−１０＿３を合成した。
室温、アルゴン雰囲気下、１−ブロモ−２−ジメチルアミノメチルベンゼン（２５ｇ，１１７ｍｍｏｌ）と金属マグネシウム（３．４ｇ，１４０ｍｍｏｌ）を、乾燥ＴＨＦ（１５０ｍｌ）に加え、１，２−ジブロモエタンを数滴加えた。その後引き続き１．５時間攪拌した。金属マグネシウムは大部分溶解し、固体残渣を濾過により分離し濾液を得た。別途、三塩化リン（８．０ｇ，５８．５ｍｍｏｌ）を乾燥ＴＨＦ（１００ｍｌ）に溶解させた溶液を準備し、先に得られた濾液を−７８℃でゆっくり加え、得られた混合液を−３０℃で２時間攪拌した。中間体Ｂ−１０＿３の白色スラリーが得られ、特に精製することなく次の反応に使用した。
（２）中間体Ｂ−１０＿６の合成
アルゴン雰囲気下、合成例５（１）と同様の操作で得られたＢ−７＿５（１４．６ｇ，５８．５ｍｍｏｌ）を乾燥ＴＨＦ（１５０ｍｌ）に溶解させ、ｎ−ブチルリチウム（２６．９ｍｌ，２．５Ｍ，ｎ−ヘキサン溶液）を−５０℃で滴下した。混合物を同温度で０．５時間攪拌し、その後、室温まで徐々に昇温し、さらに室温で２時間攪拌した。得られた反応混合物を、合成例７（１）で得られたＢ−１０＿３のスラリーに、−７８℃でゆっくり加えた。その後室温まで徐々に昇温し、室温で終夜攪拌した。攪拌終了後、水（１００ｍｌ）を加えた後、酢酸エチル（２００ｍｌ×３）で抽出操作を行った。有機層を集め硫酸ナトリウム上で乾燥し、無機塩を濾別した後、減圧下に濃縮し、残渣をカラムにて精製し、Ｂ−１０＿６（８ｇ）を得た。同様の操作を行い、最終的にＢ−１０＿６を１１．５ｇ得た。
（３）中間体Ｂ−１０＿７の合成
合成例７（２）で得られた中間体Ｂ−１０＿６（１１．５ｇ）を酢酸エチル（５０ｍｌ）に溶解させ、飽和塩化水素酢酸エチル溶液（１５０ｍｌ）を−２０℃で加えた。得られた反応混合物を−２０℃で１時間攪拌し、その後徐々に室温まで昇温し、室温でさらに１．５時間攪拌した。その後、減圧下に溶媒および揮発分を除去し、中間体Ｂ−１０＿７を灰色がかった白色固体として得た。収量：１１．６ｇ。
（４）リガンドＢ−１０の合成
合成例７（３）で得られた中間体Ｂ−１０＿７（１１．６ｇ）を水（１００ｍｌ）に溶解させ、飽和炭酸水素ナトリウム水溶液（１５０ｍｌ）を加え、室温で１．５時間攪拌した。その後、酢酸エチル（２００ｍｌ×３）で抽出操作を行い、無機塩を濾別した後、減圧下に溶媒を留去して濃縮し、残渣をメタノール（１０ｍｌ×５）で洗浄し、目的とするリガンドＢ−１０を６．８ｇ得た。
１Ｈ−ＮＭＲ（ＭｅＯＤ，δｐｐｍ）：７．４０−６．８０（ｍ，１０Ｈ），３．８１（ｍ，２Ｈ），３．３１（ｍ，２Ｈ），２．１５（ｄ，１２Ｈ），１．４０（ｓ，９Ｈ），１．１１（ｓ，９Ｈ）；３１Ｐ−ＮＭＲ（ＭｅＯＤ，δｐｐｍ）：４５．３０（ｓ）．
Intermediate B-10_3 was synthesized according to the above scheme.
1-Bromo-2-dimethylaminomethylbenzene (25 g, 117 mmol) and metallic magnesium (3.4 g, 140 mmol) were added to dry THF (150 ml) at room temperature under an argon atmosphere, and several drops of 1,2-dibromoethane were added. added. Subsequently, the mixture was stirred for 1.5 hours. Most of the magnesium metal was dissolved, and the solid residue was separated by filtration to obtain a filtrate. Separately, a solution in which phosphorus trichloride (8.0 g, 58.5 mmol) was dissolved in dry THF (100 ml) was prepared, the filtrate obtained earlier was slowly added at −78 ° C., and the resulting mixture was − The mixture was stirred at 30 ° C. for 2 hours. A white slurry of Intermediate B-10_3 was obtained and used in the next reaction without further purification.
(2) Synthesis of Intermediate B-10_6 Under an argon atmosphere, B-7_5 (14.6 g, 58.5 mmol) obtained by the same operation as in Synthesis Example 5 (1) was dissolved in dry THF (150 ml). n-Butyllithium (26.9 ml, 2.5 M, n-hexane solution) was added dropwise at −50 ° C. The mixture was stirred at the same temperature for 0.5 hour, then gradually warmed to room temperature, and further stirred at room temperature for 2 hours. The obtained reaction mixture was slowly added at −78 ° C. to the slurry of B-10_3 obtained in Synthesis Example 7 (1). Thereafter, the temperature was gradually raised to room temperature, and the mixture was stirred at room temperature overnight. After completion of the stirring, water (100 ml) was added, followed by extraction with ethyl acetate (200 ml × 3). The organic layer was collected and dried over sodium sulfate, and the inorganic salt was filtered off and concentrated under reduced pressure. The residue was purified by a column to obtain B-10_6 (8 g). The same operation was performed to finally obtain 11.5 g of B-10_6.
(3) Synthesis of Intermediate B-10_7 Intermediate B-10_6 (11.5 g) obtained in Synthesis Example 7 (2) was dissolved in ethyl acetate (50 ml), and a saturated hydrogen chloride ethyl acetate solution (150 ml) was added. Added at -20 ° C. The resulting reaction mixture was stirred at −20 ° C. for 1 hour, then gradually warmed to room temperature, and further stirred at room temperature for 1.5 hours. Thereafter, the solvent and volatile components were removed under reduced pressure to obtain Intermediate B-10_7 as an off-white solid. Yield: 11.6 g.
(4) Synthesis of Ligand B-10 Intermediate B-10_7 (11.6 g) obtained in Synthesis Example 7 (3) was dissolved in water (100 ml), saturated aqueous sodium hydrogen carbonate solution (150 ml) was added, and room temperature For 1.5 hours. Thereafter, extraction with ethyl acetate (200 ml × 3) was performed, the inorganic salt was filtered off, the solvent was distilled off under reduced pressure, and the residue was washed with methanol (10 ml × 5). 6.8 g of ligand B-10 was obtained.
1 H-NMR (MeOD, δ ppm): 7.40-6.80 (m, 10H), 3.81 (m, 2H), 3.31 (m, 2H), 2.15 (d, 12H), 1.40 (s, 9H), 1.11 (s, 9H); 31 P-NMR (MeOD, δ ppm): 45.30 (s).
（実施例１〜５）
（１）エチレンとアクリル酸エステルの共重合
合成例２で得られた錯体をトルエンに溶解させ、濃度を１６μｍｏｌ／ｍｌに調整した。次に、破裂板式触媒フィーダーを備えた内容積２リッターの誘導攪拌式オートクレーブ内を精製窒素で置換し、該触媒フィーダー内に上記記載の錯体トルエン溶液を５ｍｌ仕込んだ。次いで、所定量の精製トルエンおよびコモノマーを精製窒素雰囲気下にオートクレーブ内に導入した。攪拌しながら、オートクレーブを重合温度まで昇温した後、精製エチレンで破裂板を割って触媒をフィードし、ただちにオートクレーブ内圧を所定圧力に調整して重合を開始した。引き続き攪拌しながらオートクレーブ内圧を所定圧力に保持しながら１時間重合を行った。重合終了後、オートクレーブを室温まで冷却し、エタノール（２５ｍｌ）をオートクレーブ内に導入した。得られたポリマーがトルエン不溶の固体である場合には、濾過によりポリマーと溶媒を分離した。濾過では分離が不十分な場合には、以下のようにしてポリマーを回収した。エタノール（１，０００ｍｌ）を用いてポリマーを再沈させ、沈殿したポリマーを濾過し、得られた固形ポリマーをエタノール（２００ｍｌ）に分散させ、ここに１Ｎ−塩酸（１００ｍｌ）を加えて２０分攪拌し、ポリマーを濾過した。得られた固形ポリマーをエタノール（２００ｍｌ）に分散させて５分攪拌し、再び濾過を行った。この操作をさらに２回行い、最終的にポリマーを回収した。上記いずれかの手法で溶媒から分離したポリマーは、６０℃で３時間減圧乾燥した。
仕込んだコモノマーの種類と量については、表１に記載した。なお、コモノマーは、Ａｌｄｒｉｃｈ社製のＡｌｄｒｉｃｈ Ｉｎｈｉｂｉｔｏｒ Ｒｅｍｏｖｅｒを充填したカラムを用いて、精製窒素雰囲気下、室温で精製した後に使用した。また、重合に用いたトルエン量、重合温度、重合中のオートクレーブ内圧についても、表１に記載した。表１において、ｔＢＡはアクリル酸ｔブチルを、ｎＢＡはアクリル酸ｎブチルを示す。また、活性Ｖｐは、共重合に用いた錯体１ｍｏｌあたり、重合時間１時間あたりの共重合体収量（ｋｇ）を表す。
(Examples 1-5)
(1) Copolymerization of ethylene and acrylate ester The complex obtained in Synthesis Example 2 was dissolved in toluene, and the concentration was adjusted to 16 μmol / ml. Next, the inside of a 2 liter induction stirring autoclave equipped with a rupturable plate type catalyst feeder was replaced with purified nitrogen, and 5 ml of the complex toluene solution described above was charged into the catalyst feeder. A predetermined amount of purified toluene and comonomer were then introduced into the autoclave under a purified nitrogen atmosphere. The temperature of the autoclave was raised to the polymerization temperature while stirring, and then the catalyst was fed by breaking the rupturable plate with purified ethylene. Immediately, the autoclave internal pressure was adjusted to a predetermined pressure to initiate polymerization. Then, polymerization was carried out for 1 hour while maintaining the internal pressure of the autoclave at a predetermined pressure while stirring. After completion of the polymerization, the autoclave was cooled to room temperature, and ethanol (25 ml) was introduced into the autoclave. When the obtained polymer was a toluene-insoluble solid, the polymer and the solvent were separated by filtration. When separation was insufficient by filtration, the polymer was recovered as follows. The polymer was reprecipitated using ethanol (1,000 ml), the precipitated polymer was filtered, the obtained solid polymer was dispersed in ethanol (200 ml), 1N hydrochloric acid (100 ml) was added thereto, and the mixture was stirred for 20 minutes. And the polymer was filtered. The obtained solid polymer was dispersed in ethanol (200 ml), stirred for 5 minutes, and filtered again. This operation was performed twice more, and finally the polymer was recovered. The polymer separated from the solvent by any one of the above methods was dried under reduced pressure at 60 ° C. for 3 hours.
The types and amounts of comonomer charged are shown in Table 1. The comonomer was used after purification at room temperature in a purified nitrogen atmosphere using a column packed with Aldrich Inhibitor Remover manufactured by Aldrich. Table 1 also shows the amount of toluene used for the polymerization, the polymerization temperature, and the autoclave internal pressure during the polymerization. In Table 1, tBA represents tbutyl acrylate, and nBA represents nbutyl acrylate. Moreover, active Vp represents the copolymer yield (kg) per 1 hour of polymerization time per 1 mol of complexes used for copolymerization.
（２）エチレン・アクリル酸エステル共重合体の分析
実施例１〜４で得られたエチレン・アクリル酸ｔブチル共重合体の１３Ｃ−ＮＭＲスペクトル分析結果を表２に示す。なお、表２において、各部分構造の量は、主鎖炭素１０００個あたりの数である。また、Ｅｔ末端はエチル末端、Ｖｙ末端はビニル末端、Ｍｅ分岐はメチル分岐、主鎖ｔＢＡは、末端以外の主鎖に共重合されているアクリル酸ｔブチルを、末端ｔＢＡは主鎖末端に存在するアクリル酸ｔブチル由来の末端基を示す。Ｅ体、Ｚ体は、それぞれ前記した部分構造（ＩＶ）および（Ｖ）に対応する。
(2) Analysis of ethylene / acrylic acid ester copolymer Table 2 shows the results of 13 C-NMR spectrum analysis of the ethylene / acrylic acid tbutyl copolymer obtained in Examples 1 to 4. In Table 2, the amount of each partial structure is the number per 1000 main chain carbons. Et end is ethyl end, Vy end is vinyl end, Me branch is methyl branch, main chain tBA is tbutyl acrylate copolymerized with main chain other than end, and end tBA is at main chain end. An end group derived from t-butyl acrylate is shown. E body and Z body correspond to the partial structures (IV) and (V) described above, respectively.
また、実施例５で得られたエチレン・アクリル酸ｎブチル共重合体の１３Ｃ−ＮＭＲスペクトル分析結果を表３に示す。なお、表３において、各部分構造の量は主鎖炭素１０００個あたりの数である。また、Ｅｔ末端はエチル末端、Ｖｙ末端はビニル末端、Ｍｅ分岐はメチル分岐、主鎖ｎＢＡは、末端以外の主鎖に共重合されているアクリル酸ｎブチルを、末端ｎＢＡは主鎖末端に存在するアクリル酸ｎブチル由来の末端基を示す。Ｅ体、Ｚ体は、それぞれ前記した部分構造（Ｖ）および（ＩＶ）に対応する。 Table 3 shows the results of 13 C-NMR spectrum analysis of the ethylene / n-butyl acrylate copolymer obtained in Example 5. In Table 3, the amount of each partial structure is the number per 1000 main chain carbons. Et end is ethyl end, Vy end is vinyl end, Me branch is methyl branch, main chain nBA is nbutyl acrylate copolymerized with main chain other than end, and terminal nBA is present at main chain end. An end group derived from n-butyl acrylate is shown. E body and Z body respectively correspond to the partial structures (V) and (IV) described above.
実施例１〜５で得られたポリマーのＤＳＣによる分析結果、ならびに、１３Ｃ−ＮＭＲスペクトルの解析から得られた共重合体中のコモノマー含量（アクリル酸エステル含量）を表４に示す。なお、実施例１〜５で用いられたコモノマーは、表１に前記した通りである。 Table 4 shows the results of DSC analysis of the polymers obtained in Examples 1 to 5 and the comonomer content (acrylate content) in the copolymer obtained from the analysis of 13 C-NMR spectrum. The comonomers used in Examples 1 to 5 are as described above in Table 1.
実施例１〜５で得られたポリマーのＧＰＣによる分析結果を表５に示す。 Table 5 shows the results of GPC analysis of the polymers obtained in Examples 1-5.
（比較例１）
実施例１において、重合系にトリイソブチルアルミニウム（ＴＩＢＡ）を、ＴＩＢＡ／Ｎｉ＝３（ｍ．ｒ．）で共存させた以外は、実施例１と同様にしてエチレンとアクリル酸エステルの共重合を行った。重合活性はほとんどなく、生成ポリマーは痕跡量であった。
(Comparative Example 1)
In Example 1, copolymerization of ethylene and an acrylate was carried out in the same manner as in Example 1 except that triisobutylaluminum (TIBA) was allowed to coexist in the polymerization system at TIBA / Ni = 3 (mr). went. There was almost no polymerization activity, and the produced polymer was a trace amount.
（比較例２）
実施例１において、重合系にメチルアルミノキサン（ＭＡＯ）を、Ａｌ／Ｎｉ＝１００（ｍ．ｒ．）となるように共存させた以外は、実施例１と同様にしてエチレンとアクリル酸エステルの共重合を行った。重合活性はまったく発現せず、ポリマーは得られなかった。
(Comparative Example 2)
In Example 1, a copolymer of ethylene and an acrylate ester was used in the same manner as in Example 1 except that methylaluminoxane (MAO) was allowed to coexist in the polymerization system so that Al / Ni = 100 (mr). Polymerization was performed. No polymerization activity was expressed, and no polymer was obtained.
（実施例６）
実施例１を繰り返して、エチレンとアクリル酸エステルの共重合を行った。得られたポリマーを改良型ソックスレー抽出器を用いて、沸騰アセトンにて抽出を行った。沸騰アセトン抽出成分は、０．５重量％であった。なお、該沸騰アセトン抽出分をＩＲで分析したところ、ポリエチレン由来のシグナルが観測された。
(Example 6)
Example 1 was repeated to copolymerize ethylene and an acrylate ester. The obtained polymer was extracted with boiling acetone using an improved Soxhlet extractor. The boiling acetone extraction component was 0.5% by weight. When the boiling acetone extract was analyzed by IR, a signal derived from polyethylene was observed.
（実施例７〜１０）
錯体として、合成例１または３で得られた錯体１または錯体３を用いた以外は、実施例１と同様にして、エチレンとアクリル酸エステルの共重合を行った。なお、採用した重合条件については、表６に示す。表６において、ｔＢＡはアクリル酸ｔブチルを、ｎＢＡはアクリル酸ｎブチルを、ＭＡはアクリル酸メチルを示す。また、活性Ｖｐは、共重合に用いた錯体１ｍｏｌあたり、重合時間１時間あたりの共重合体収量（ｋｇ）を表す。
実施例７〜１０において、得られた共重合体をＩＲにて測定したところ、コモノマーとして用いたアクリル酸エステルのカルボニル基由来のシグナルが明瞭に観測された。実施例８〜１０について、ＤＳＣ測定を行った結果を表７に示す。なお、表７において、ｎ／ａは未測定であることを示す。また、実施例８で得られた共重合体について、ＧＰＣ測定を行ったところ、Ｍｗ＝１６００、Ｍｎ＝１１００，Ｍｗ／Ｍｎ＝１．５であった。
(Examples 7 to 10)
Copolymerization of ethylene and an acrylate ester was carried out in the same manner as in Example 1 except that Complex 1 or Complex 3 obtained in Synthesis Example 1 or 3 was used as the complex. The polymerization conditions employed are shown in Table 6. In Table 6, tBA represents tbutyl acrylate, nBA represents nbutyl acrylate, and MA represents methyl acrylate. Moreover, active Vp represents the copolymer yield (kg) per 1 hour of polymerization time per 1 mol of complexes used for copolymerization.
In Examples 7-10, when the obtained copolymer was measured by IR, the signal derived from the carbonyl group of the acrylic ester used as a comonomer was clearly observed. Table 7 shows the results of DSC measurement for Examples 8 to 10. In Table 7, n / a indicates unmeasured. Moreover, when the GPC measurement was performed about the copolymer obtained in Example 8, they were Mw = 1600, Mn = 1100, Mw / Mn = 1.5.
（比較例３）
錯体として、合成例２で得られた錯体２を使用し、トルエン仕込み量＝４９０ｍｌ、内圧＝３（ＭＰａ）、重合温度＝８０（℃）の条件で、エチレンと酢酸ビニルの共重合を試みた。酢酸ビニルの仕込み量は４．５ｍｌであった。その他の条件については、実施例１と同様にして重合を行った。重合活性＝７（ｋｇ／ｍｏｌ／ｈ）で重合体が得られたが、得られた重合体をＩＲにて分析したところ、コモノマーとして用いた酢酸ビニル由来のカルボニル基にもとづくシグナルは痕跡程度にしか観測されなかった。
(Comparative Example 3)
The complex 2 obtained in Synthesis Example 2 was used as the complex, and copolymerization of ethylene and vinyl acetate was attempted under the conditions of toluene charge = 490 ml, internal pressure = 3 (MPa), and polymerization temperature = 80 (° C.). . The amount of vinyl acetate charged was 4.5 ml. Regarding other conditions, polymerization was carried out in the same manner as in Example 1. A polymer was obtained with a polymerization activity of 7 (kg / mol / h). When the obtained polymer was analyzed by IR, the signal based on the carbonyl group derived from vinyl acetate used as a comonomer was about a trace. Only observed.
（比較例４）
錯体として、合成例２で得られた錯体２を使用し、トルエン仕込み量＝４９０ｍｌ、内圧＝３（ＭＰａ）、重合温度＝８０（℃）の条件で、エチレンとビニルエチルエーテルの共重合を試みた。ビニルエチルエーテルの仕込み量は５ｍｌであった。その他の条件については、実施例１と同様にして重合を行った。重合活性＝２７３（ｋｇ／ｍｏｌ／ｈ）で重合体が得られたが、得られた重合体をＩＲにて分析したところ、コモノマーとして用いたビニルエチルエーテル由来のエーテル基にもとづくシグナルは痕跡程度にしか観測されなかった。
(Comparative Example 4)
The complex 2 obtained in Synthesis Example 2 was used as the complex, and the copolymerization of ethylene and vinyl ethyl ether was attempted under the conditions of toluene charge = 490 ml, internal pressure = 3 (MPa), and polymerization temperature = 80 (° C.). It was. The amount of vinyl ethyl ether charged was 5 ml. Regarding other conditions, polymerization was carried out in the same manner as in Example 1. A polymer was obtained with a polymerization activity of 273 (kg / mol / h). When the obtained polymer was analyzed by IR, the signal based on the ether group derived from vinyl ethyl ether used as a comonomer was about a trace. It was observed only in
（実施例１１〜１４）
錯体として、合成例４で得られた錯体４を用いた以外は、実施例１と同様にして、エチレンとアクリル酸エステルの共重合を行った。なお、採用した重合条件については、表８に示す。表８において、ｔＢＡはアクリル酸ｔブチルを、ｎＢＡはアクリル酸ｎブチル示す。また、活性Ｖｐは、共重合に用いた錯体１ｍｏｌあたり、重合時間１時間あたりの共重合体収量（ｋｇ）を表す。
(Examples 11-14)
As a complex, copolymerization of ethylene and an acrylate ester was performed in the same manner as in Example 1 except that the complex 4 obtained in Synthesis Example 4 was used. The employed polymerization conditions are shown in Table 8. In Table 8, tBA represents tbutyl acrylate and nBA represents nbutyl acrylate. Moreover, active Vp represents the copolymer yield (kg) per 1 hour of polymerization time per 1 mol of complexes used for copolymerization.
実施例１１〜１４において、得られた共重合体をＩＲにて測定したところ、コモノマーとして用いたアクリル酸エステルのカルボニル基由来のシグナルが７２０〜７３０ｃｍ−１および１７２０〜１７３０ｃｍ−１付近に明瞭に観測された。また、実施例１１〜１４についてＤＳＣ測定を行った結果を表９に示す。表９において、ｎ／ａは未測定であることを示す。表８においては、主要ピークのＴｍおよびＴｃを示したが、実施例１１では、他に１２４．７℃、１２０．６℃にＴｍピークが観測された。同様に、実施例１２では、他に１１０．８℃のＴｍピークおよび１０６．６℃のＴｃピーク、実施例１５では、他に１１０．１℃のＴｍピークが観測された。 In Examples 11-14, when the obtained copolymer was measured by IR, the signals derived from the carbonyl group of the acrylate ester used as a comonomer were clearly around 720-730 cm −1 and 1720-1730 cm −1. Observed. In addition, Table 9 shows the results of DSC measurement for Examples 11-14. In Table 9, n / a indicates that it has not been measured. In Table 8, Tm and Tc of the main peaks are shown, but in Example 11, Tm peaks were observed at 124.7 ° C. and 120.6 ° C. in addition. Similarly, in Example 12, another Tm peak of 110.8 ° C. and a Tc peak of 106.6 ° C. were observed, and in Example 15, another Tm peak of 110.1 ° C. was observed.
実施例１１で得られた共重合体を１３Ｃ−ＮＭＲで分析したところ、コモノマーであるｔＢＡの含量は０．８ｍｏｌ％であった。内訳は、主鎖中に存在しているものが０．４６ｍｏｌ％であり、末端に存在しているものが０．３６ｍｏｌ％であった。なお、ｔＢＡ由来の末端構造は、前記した部分構造（ＩＶ）で示されるものであった。該共重合体には、主鎖１０００カーボン中０．６個のメチル分岐があったが、他の炭化水素分岐はなかった。
実施例１１および１２で得られた共重合体についてＧＰＣ測定を行ったところ、実施例１１についてはＭｗ＝３３７０、Ｍｎ＝２１００、Ｍｗ／Ｍｎ＝１．６、実施例１２についてはＭｗ＝５１５００、Ｍｎ＝２５００、Ｍｗ／Ｍｎ＝２０．６であった。
When the copolymer obtained in Example 11 was analyzed by 13 C-NMR, the content of tBA as a comonomer was 0.8 mol%. The breakdown was 0.46 mol% present in the main chain and 0.36 mol% present at the terminal. The terminal structure derived from tBA was shown by the partial structure (IV) described above. The copolymer had 0.6 methyl branches in 1000 carbon backbones, but no other hydrocarbon branches.
When GPC measurement was performed on the copolymers obtained in Examples 11 and 12, Mw = 3370, Mn = 2100, Mw / Mn = 1.6 for Example 11, and Mw = 51500 for Example 12. Mn = 2500 and Mw / Mn = 20.6.
（実施例１５〜２９）
Ｂ−７を用いたエチレンとアクリル酸エステルの共重合
（１）Ｂ−７錯体の形成
以下の操作は、すべて高純度アルゴン雰囲気下で行った。
初めに４ｍｌのスクリューキャップ付きバイアル瓶に、合成例５で得られたＢ−７（１０．７ｍｇ）を秤り取った。次に、Ｎｉ（ＣＯＤ）２（２０ｍｇ）を８ｍｌのバイアル瓶に秤り取り、トルエン（７．２２ｍｌ）に溶解させ、１０ｍＭのＮｉ（ＣＯＤ）２トルエン溶液を調製した。得られた溶液は、黄色透明であった。ここで得られたＮｉ（ＣＯＤ）２トルエン溶液（２．３６ｍｌ）をＢ−７を有するバイアル瓶に加え、スクリューキャップで密閉した後、３０秒間振って攪拌し、溶液を得た。その後、溶液の色が次第に暗黄色から赤色に変化し、沈殿は見られなかった。室温で３時間静置した後、得られた溶液０．５ｍｌを２ｍｌのバイアル瓶に分取し、トルエン（１．５ｍｌ）で希釈し、（Ｂ−７）（ＣＯＤ）Ｎｉ錯体の２．５ｍＭ溶液を得た。
（２）エチレンとアクリル酸エステルの共重合
内容積約１０ｍｌの攪拌翼ならびに内筒付きオートクレーブに、乾燥トルエン（４．２ ｍｌ）および所定量のアクリル酸エステルを仕込んだ。攪拌しながらオートクレーブを所定温度に昇温した後、エチレンをオートクレーブに供給し、温度と圧力が所定の条件になるように調整した。調整終了後、上記（１）で得られた錯体溶液を所定量供給し、共重合を開始させた。所定時間重合させた後、一酸化炭素を吹き込んだ。未反応ガスを除去した後、内筒を取り出し、減圧下に溶媒および未反応コモノマーを除去し、恒量になるまで乾燥を行った。
共重合条件については、表１０に記載した。なお、コモノマーは、Ａｌｄｒｉｃｈ社製のＡｌｄｒｉｃｈ Ｉｎｈｉｂｉｔｏｒ Ｒｅｍｏｖｅｒを充填したカラムを用いて、高純度アルゴン雰囲気下、室温で精製した後に使用した。表１０において、ｔＢＡはアクリル酸ｔブチルを示す。また、活性Ｖｐは、共重合に用いた錯体１ｍｏｌあたり、重合時間１時間あたりの共重合体収量（ｋｇ）を表す。得られた共重合体のＤＳＣ測定結果およびＧＰＣ測定結果については、それぞれ表１１、表１２に示した。
(Examples 15 to 29)
Copolymerization of ethylene and acrylic acid ester using B-7 (1) Formation of B-7 complex The following operations were all performed in a high purity argon atmosphere.
First, B-7 (10.7 mg) obtained in Synthesis Example 5 was weighed into a 4 ml vial with a screw cap. Next, Ni (COD) 2 (20 mg) was weighed into an 8 ml vial and dissolved in toluene (7.22 ml) to prepare a 10 mM Ni (COD) 2 toluene solution. The resulting solution was yellow and transparent. The Ni (COD) 2 toluene solution (2.36 ml) obtained here was added to the vial containing B-7, sealed with a screw cap, and then shaken for 30 seconds to obtain a solution. Thereafter, the color of the solution gradually changed from dark yellow to red, and no precipitation was observed. After standing at room temperature for 3 hours, 0.5 ml of the resulting solution was dispensed into a 2 ml vial, diluted with toluene (1.5 ml), and 2.5 mM of (B-7) (COD) Ni complex. A solution was obtained.
(2) Copolymerization of ethylene and acrylic ester Dry toluene (4.2 ml) and a predetermined amount of acrylic ester were charged into a stirring blade having an internal volume of about 10 ml and an autoclave with an inner cylinder. The temperature of the autoclave was raised to a predetermined temperature while stirring, and then ethylene was supplied to the autoclave so that the temperature and pressure were adjusted to predetermined conditions. After completion of the adjustment, a predetermined amount of the complex solution obtained in (1) was supplied to start copolymerization. After polymerization for a predetermined time, carbon monoxide was blown. After removing the unreacted gas, the inner cylinder was taken out, and the solvent and unreacted comonomer were removed under reduced pressure, followed by drying until a constant weight was obtained.
The copolymerization conditions are shown in Table 10. The comonomer was used after purification at room temperature in a high-purity argon atmosphere using a column packed with Aldrich Inhibitor Remover manufactured by Aldrich. In Table 10, tBA represents tbutyl acrylate. Moreover, active Vp represents the copolymer yield (kg) per 1 hour of polymerization time per 1 mol of complexes used for copolymerization. The DSC measurement results and GPC measurement results of the obtained copolymer are shown in Tables 11 and 12, respectively.
（比較例５〜１０）
Ｂ−７を用いたエチレンの重合
実施例１５〜２９で得られた（Ｂ−７）（ＣＯＤ）Ｎｉ錯体溶液を用い、コモノマーを用いなかった以外は、実施例１５〜２９と同様にして、エチレンの重合を行った。結果は表１７〜１９に示した。
(Comparative Examples 5 to 10)
Polymerization of ethylene using B-7 Except that the (B-7) (COD) Ni complex solution obtained in Examples 15 to 29 was used and no comonomer was used, the same as in Examples 15 to 29, Ethylene was polymerized. The results are shown in Tables 17-19.
（実施例３０〜３５）
Ｂ−８を用いたエチレンとアクリル酸エステルの共重合
（１）Ｂ−８錯体の形成
合成例６で得られたＢ−８（１１．４ ｍｇ）を用いた以外は、実施例１５〜２９と同様にして、（Ｂ−８）（ＣＯＤ）Ｎｉ錯体の２．５ｍＭ溶液を得た。
（２）エチレンとアクリル酸エステルの共重合
上記（Ｂ−８）（ＣＯＤ）Ｎｉ錯体溶液を用いた以外は、実施例１５〜２９と同様にして、エチレンとアクリル酸エステルの共重合を行った。重合条件および活性については表１３に、得られた共重合体のＤＳＣ測定結果およびＧＰＣ測定結果については、それぞれ表１４〜１５に示した。
(Examples 30 to 35)
Copolymerization of ethylene and acrylic acid ester using B-8 (1) Formation of B-8 complex Examples 15 to 29 except that B-8 (11.4 mg) obtained in Synthesis Example 6 was used. In the same manner as above, a 2.5 mM solution of (B-8) (COD) Ni complex was obtained.
(2) Copolymerization of ethylene and acrylate ester Copolymerization of ethylene and acrylate ester was conducted in the same manner as in Examples 15 to 29 except that the (B-8) (COD) Ni complex solution was used. . The polymerization conditions and activities are shown in Table 13, and the DSC measurement results and GPC measurement results of the obtained copolymers are shown in Tables 14 to 15, respectively.
（比較例１１〜１２）
Ｂ−８を用いたエチレンの重合
実施例３０〜３５で得られた（Ｂ−８）（ＣＯＤ）Ｎｉ錯体溶液を用い、コモノマーを用いなかった以外は、実施例１５〜２９と同様にして、エチレンの重合を行った。結果は表１７〜１９に示した。
(Comparative Examples 11-12)
Polymerization of ethylene with B-8 Except that the (B-8) (COD) Ni complex solution obtained in Examples 30 to 35 was used and no comonomer was used, the same as in Examples 15 to 29, Ethylene was polymerized. The results are shown in Tables 17-19.
（実施例３６〜４７）
Ｂ−１０を用いたエチレンとアクリル酸エステルの共重合
（１）Ｂ−１０錯体の形成
合成例７で得られたＢ−１０（１３．１ｍｇ）を用いた以外は、実施例１５〜２９と同様にして、（Ｂ−１０）（ＣＯＤ）Ｎｉ錯体の２．５ｍＭ溶液を得た。
（２）エチレンとアクリル酸エステルの共重合
上記（Ｂ−１０）（ＣＯＤ）Ｎｉ錯体溶液を用いた以外は、実施例１５〜２９と同様にして、エチレンとアクリル酸エステルの共重合を行った。重合条件および活性については表１６に示した。
(Examples 36 to 47)
Copolymerization of ethylene and acrylic acid ester using B-10 (1) Formation of B-10 complex Examples 15 to 29 except that B-10 (13.1 mg) obtained in Synthesis Example 7 was used. Similarly, a 2.5 mM solution of (B-10) (COD) Ni complex was obtained.
(2) Copolymerization of ethylene and acrylate ester Copolymerization of ethylene and acrylate ester was carried out in the same manner as in Examples 15 to 29 except that the above (B-10) (COD) Ni complex solution was used. . The polymerization conditions and activity are shown in Table 16.
（比較例１３〜１６）
Ｂ−１０を用いたエチレンの重合
実施例３６〜４７で得られた（Ｂ−１０）（ＣＯＤ）Ｎｉ錯体溶液を用い、コモノマーを用いなかった以外は、実施例１５〜２９と同様にして、エチレンの重合を行った。結果は表１７〜１９に示した。
(Comparative Examples 13 to 16)
Polymerization of ethylene using B-10 Except that the (B-10) (COD) Ni complex solution obtained in Examples 36 to 47 was used and no comonomer was used, the same as in Examples 15 to 29, Ethylene was polymerized. The results are shown in Tables 17-19.
本発明のα−オレフィン・（メタ）アクリル酸エステル共重合体は、機械的・熱的物性に優れ、有用な成形体として応用可能である。また、該共重合体の製造工程において、非晶質重合体の副生量がきわめて少ないため、こうした副生物を目的とする共重合体から除去する工程が不要であり、さらに、希少かつ高価なパラジウムの代わりに、ニッケルを金属中心とした触媒を使用することができ、工業的にきわめて有用である。 The α-olefin / (meth) acrylic acid ester copolymer of the present invention is excellent in mechanical and thermal properties and can be applied as a useful molded article. In addition, in the production process of the copolymer, the amount of by-product of the amorphous polymer is extremely small, so a step of removing such by-products from the target copolymer is unnecessary, and furthermore, it is rare and expensive. Instead of palladium, a nickel-centered catalyst can be used, which is very useful industrially.
Claims (6)
−ＣＨ＝Ｃ（Ｒ８）ＣＯ２（Ｒ９） ・・・（Ｄ）
（式（Ｄ）において、Ｒ８は水素または炭素数１〜１０の炭化水素基であり、分岐、環、および／または不飽和結合を有していてもよい。Ｒ９は炭素数１〜３０の炭化水素基であり、分岐、環、および／または不飽和結合を有していてもよい。さらに、Ｒ９内の任意の位置にヘテロ原子を含有していてもよい。） (A) α-olefin and (b) (meth) acrylic acid ester, the main chain terminal is an ethyl group, a vinyl group, and (meth) acrylic acid used for copolymerization as component (b) It consists of a group represented by the general formula (D) derived from an ester, and the carbon-carbon double bond in the general formula (D) is composed of two types of geometric isomer structures of Z-form and E-form. An α-olefin / (meth) acrylic acid ester copolymer.
-CH = C (R 8) CO 2 (R 9) ··· (D)
(In Formula (D), R 8 is hydrogen or a hydrocarbon group having 1 to 10 carbon atoms, and may have a branch, a ring, and / or an unsaturated bond. R 9 has 1 to 30 carbon atoms. And may have a branched, ring, and / or unsaturated bond, and may contain a hetero atom at any position within R 9. )
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| JP2010260913A (en) * | 2009-04-30 | 2010-11-18 | Japan Polypropylene Corp | NEW METAL COMPLEX-CONTAINING POLYMERIZATION CATALYST COMPONENT AND METHOD FOR PRODUCING alpha-OLEFIN POLYMER OR alpha-OLEFIN-(METH)ACRYLATE COPOLYMER USING THE SAME |
| JPWO2010050256A1 (en) * | 2008-10-30 | 2012-03-29 | 日本ポリプロ株式会社 | Novel metal complex, method for producing α-olefin polymer using the same, and method for producing α-olefin and (meth) acrylic acid ester copolymer |
| JP2013209349A (en) * | 2012-03-30 | 2013-10-10 | Japan Polyethylene Corp | METAL COMPLEX AND METHOD FOR PRODUCING α-OLEFIN AND (METH)ACRYLIC ACID ESTER COPOLYMER USING THE SAME |
| JP2013209350A (en) * | 2012-03-30 | 2013-10-10 | Japan Polyethylene Corp | METAL COMPLEX AND METHOD FOR PRODUCING α-OLEFIN AND (METH)ACRYLIC ACID ESTER COPOLYMER USING THE SAME |
| JP2016017134A (en) * | 2014-07-08 | 2016-02-01 | 日本ポリエチレン株式会社 | Olefin polymerization catalyst and olefin polymer production method |
| JP2016029170A (en) * | 2014-07-24 | 2016-03-03 | 日本ポリエチレン株式会社 | Olefin polymerization catalyst and method for producing olefin polymer |
| CN109320558A (en) * | 2018-09-10 | 2019-02-12 | 天津大学 | Preparation method of naphthol skeleton phenol-phosphine neutral nickel catalyst and application of catalyst in preparation of ethylene/vinyl polar monomer copolymer |
| JP2019112520A (en) * | 2017-12-22 | 2019-07-11 | 国立大学法人 東京大学 | Method for producing catalyst for olefin polymerization and polar group-containing olefinic polymer |
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