JP2009084578A - Propylene-based polymer and production process of same, and material to be coated - Google Patents
Propylene-based polymer and production process of same, and material to be coated Download PDFInfo
- Publication number
- JP2009084578A JP2009084578A JP2008285239A JP2008285239A JP2009084578A JP 2009084578 A JP2009084578 A JP 2009084578A JP 2008285239 A JP2008285239 A JP 2008285239A JP 2008285239 A JP2008285239 A JP 2008285239A JP 2009084578 A JP2009084578 A JP 2009084578A
- Authority
- JP
- Japan
- Prior art keywords
- polymer
- propylene
- hydrocarbon group
- hydroxyl group
- group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 54
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims abstract description 25
- 239000000463 material Substances 0.000 title claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- 150000001336 alkenes Chemical class 0.000 claims abstract description 42
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 37
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 35
- 150000001875 compounds Chemical class 0.000 claims abstract description 26
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 238000002844 melting Methods 0.000 claims abstract description 10
- 230000008018 melting Effects 0.000 claims abstract description 10
- -1 oxy compound Chemical class 0.000 claims description 48
- 150000002430 hydrocarbons Chemical group 0.000 claims description 30
- 229920001155 polypropylene Polymers 0.000 claims description 21
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 19
- 229910052710 silicon Inorganic materials 0.000 claims description 17
- 239000010703 silicon Substances 0.000 claims description 17
- 238000005227 gel permeation chromatography Methods 0.000 claims description 12
- 239000003446 ligand Substances 0.000 claims description 12
- 238000005481 NMR spectroscopy Methods 0.000 claims description 9
- 229910052736 halogen Inorganic materials 0.000 claims description 8
- 150000002367 halogens Chemical class 0.000 claims description 8
- 125000001424 substituent group Chemical group 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 125000000129 anionic group Chemical group 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 238000005259 measurement Methods 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 6
- 230000000737 periodic effect Effects 0.000 claims description 6
- 238000007334 copolymerization reaction Methods 0.000 claims description 3
- 150000002902 organometallic compounds Chemical class 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims 2
- 238000000034 method Methods 0.000 abstract description 17
- 230000008569 process Effects 0.000 abstract description 2
- 229920000098 polyolefin Polymers 0.000 description 23
- 125000004432 carbon atom Chemical group C* 0.000 description 22
- 238000006116 polymerization reaction Methods 0.000 description 19
- 229920005989 resin Polymers 0.000 description 11
- 239000011347 resin Substances 0.000 description 11
- 239000004711 α-olefin Substances 0.000 description 10
- 239000004743 Polypropylene Substances 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical class CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 6
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 5
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 5
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 4
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- VAMFXQBUQXONLZ-UHFFFAOYSA-N n-alpha-eicosene Natural products CCCCCCCCCCCCCCCCCCC=C VAMFXQBUQXONLZ-UHFFFAOYSA-N 0.000 description 4
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadec-1-ene Chemical compound CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 4
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 4
- 239000002685 polymerization catalyst Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- YPVPQMCSLFDIKA-UHFFFAOYSA-N 3-ethylpent-1-ene Chemical class CCC(CC)C=C YPVPQMCSLFDIKA-UHFFFAOYSA-N 0.000 description 3
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical class CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 3
- LDTAOIUHUHHCMU-UHFFFAOYSA-N 3-methylpent-1-ene Chemical class CCC(C)C=C LDTAOIUHUHHCMU-UHFFFAOYSA-N 0.000 description 3
- SUJVAMIXNUAJEY-UHFFFAOYSA-N 4,4-dimethylhex-1-ene Chemical class CCC(C)(C)CC=C SUJVAMIXNUAJEY-UHFFFAOYSA-N 0.000 description 3
- KLCNJIQZXOQYTE-UHFFFAOYSA-N 4,4-dimethylpent-1-ene Chemical class CC(C)(C)CC=C KLCNJIQZXOQYTE-UHFFFAOYSA-N 0.000 description 3
- OPMUAJRVOWSBTP-UHFFFAOYSA-N 4-ethyl-1-hexene Chemical class CCC(CC)CC=C OPMUAJRVOWSBTP-UHFFFAOYSA-N 0.000 description 3
- SUWJESCICIOQHO-UHFFFAOYSA-N 4-methylhex-1-ene Chemical class CCC(C)CC=C SUWJESCICIOQHO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 150000001993 dienes Chemical class 0.000 description 3
- 238000000113 differential scanning calorimetry Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000011256 inorganic filler Substances 0.000 description 3
- 229910003475 inorganic filler Inorganic materials 0.000 description 3
- 239000006247 magnetic powder Substances 0.000 description 3
- 239000012968 metallocene catalyst Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 3
- 229920005992 thermoplastic resin Polymers 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 150000003624 transition metals Chemical group 0.000 description 3
- PRBHEGAFLDMLAL-GQCTYLIASA-N (4e)-hexa-1,4-diene Chemical compound C\C=C\CC=C PRBHEGAFLDMLAL-GQCTYLIASA-N 0.000 description 2
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 2
- PRBHEGAFLDMLAL-UHFFFAOYSA-N 1,5-Hexadiene Natural products CC=CCC=C PRBHEGAFLDMLAL-UHFFFAOYSA-N 0.000 description 2
- XWJBRBSPAODJER-UHFFFAOYSA-N 1,7-octadiene Chemical compound C=CCCCCC=C XWJBRBSPAODJER-UHFFFAOYSA-N 0.000 description 2
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 2
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 2
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 2
- CJSBUWDGPXGFGA-UHFFFAOYSA-N 4-methylpenta-1,3-diene Chemical compound CC(C)=CC=C CJSBUWDGPXGFGA-UHFFFAOYSA-N 0.000 description 2
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- PVEOYINWKBTPIZ-UHFFFAOYSA-N but-3-enoic acid Chemical class OC(=O)CC=C PVEOYINWKBTPIZ-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 125000002843 carboxylic acid group Chemical group 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- MGNZXYYWBUKAII-UHFFFAOYSA-N cyclohexa-1,3-diene Chemical compound C1CC=CC=C1 MGNZXYYWBUKAII-UHFFFAOYSA-N 0.000 description 2
- 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 2
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Chemical class CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 229940069096 dodecene Drugs 0.000 description 2
- LDLDYFCCDKENPD-UHFFFAOYSA-N ethenylcyclohexane Chemical compound C=CC1CCCCC1 LDLDYFCCDKENPD-UHFFFAOYSA-N 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 229910052735 hafnium Inorganic materials 0.000 description 2
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 2
- UIZVMOZAXAMASY-UHFFFAOYSA-N hex-5-en-1-ol Chemical compound OCCCCC=C UIZVMOZAXAMASY-UHFFFAOYSA-N 0.000 description 2
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical compound C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methylcyclopentane Chemical compound CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 2
- JEGNXMUWVCVSSQ-UHFFFAOYSA-N octadec-1-en-1-ol Chemical compound CCCCCCCCCCCCCCCCC=CO JEGNXMUWVCVSSQ-UHFFFAOYSA-N 0.000 description 2
- QYZLKGVUSQXAMU-UHFFFAOYSA-N penta-1,4-diene Chemical compound C=CCC=C QYZLKGVUSQXAMU-UHFFFAOYSA-N 0.000 description 2
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 2
- 150000004291 polyenes Chemical class 0.000 description 2
- 230000037048 polymerization activity Effects 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- XBFJAVXCNXDMBH-UHFFFAOYSA-N tetracyclo[6.2.1.1(3,6).0(2,7)]dodec-4-ene Chemical compound C1C(C23)C=CC1C3C1CC2CC1 XBFJAVXCNXDMBH-UHFFFAOYSA-N 0.000 description 2
- YWWDBCBWQNCYNR-UHFFFAOYSA-N trimethylphosphine Chemical compound CP(C)C YWWDBCBWQNCYNR-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- OJOWICOBYCXEKR-APPZFPTMSA-N (1S,4R)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound CC=C1C[C@@H]2C[C@@H]1C=C2 OJOWICOBYCXEKR-APPZFPTMSA-N 0.000 description 1
- AHAREKHAZNPPMI-AATRIKPKSA-N (3e)-hexa-1,3-diene Chemical compound CC\C=C\C=C AHAREKHAZNPPMI-AATRIKPKSA-N 0.000 description 1
- RYNKSPIWLXKJHG-ZJUUUORDSA-N (3s)-3-[(3s)-oct-1-en-3-yl]oxolane-2,5-dione Chemical compound CCCCC[C@@H](C=C)[C@@H]1CC(=O)OC1=O RYNKSPIWLXKJHG-ZJUUUORDSA-N 0.000 description 1
- HYBLFDUGSBOMPI-BQYQJAHWSA-N (4e)-octa-1,4-diene Chemical compound CCC\C=C\CC=C HYBLFDUGSBOMPI-BQYQJAHWSA-N 0.000 description 1
- HITROERJXNWVOI-SOFGYWHQSA-N (5e)-octa-1,5-diene Chemical compound CC\C=C\CCC=C HITROERJXNWVOI-SOFGYWHQSA-N 0.000 description 1
- RJUCIROUEDJQIB-GQCTYLIASA-N (6e)-octa-1,6-diene Chemical compound C\C=C\CCCC=C RJUCIROUEDJQIB-GQCTYLIASA-N 0.000 description 1
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- IAKOZHOLGAGEJT-UHFFFAOYSA-N 1,1,1-trichloro-2,2-bis(p-methoxyphenyl)-Ethane Chemical compound C1=CC(OC)=CC=C1C(C(Cl)(Cl)Cl)C1=CC=C(OC)C=C1 IAKOZHOLGAGEJT-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
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- HOROZASJKPUNET-UHFFFAOYSA-N 1-chlorodec-5-yne Chemical class CCCCC#CCCCCCl HOROZASJKPUNET-UHFFFAOYSA-N 0.000 description 1
- 229940106006 1-eicosene Drugs 0.000 description 1
- FIKTURVKRGQNQD-UHFFFAOYSA-N 1-eicosene Natural products CCCCCCCCCCCCCCCCCC=CC(O)=O FIKTURVKRGQNQD-UHFFFAOYSA-N 0.000 description 1
- VTPNYMSKBPZSTF-UHFFFAOYSA-N 1-ethenyl-2-ethylbenzene Chemical compound CCC1=CC=CC=C1C=C VTPNYMSKBPZSTF-UHFFFAOYSA-N 0.000 description 1
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- XHUZSRRCICJJCN-UHFFFAOYSA-N 1-ethenyl-3-ethylbenzene Chemical compound CCC1=CC=CC(C=C)=C1 XHUZSRRCICJJCN-UHFFFAOYSA-N 0.000 description 1
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 description 1
- FEEIOCGOXYNQIM-UHFFFAOYSA-N 2,3-di(propan-2-ylidene)bicyclo[2.2.1]hept-5-ene Chemical compound C1C2C=CC1C(=C(C)C)C2=C(C)C FEEIOCGOXYNQIM-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical class COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Chemical class OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- FLYIRERUSAMCDQ-UHFFFAOYSA-N 2-azaniumyl-2-(2-methylphenyl)acetate Chemical class CC1=CC=CC=C1C(N)C(O)=O FLYIRERUSAMCDQ-UHFFFAOYSA-N 0.000 description 1
- IOHAVGDJBFVWGE-UHFFFAOYSA-N 2-ethylidene-3-propan-2-ylidenebicyclo[2.2.1]hept-5-ene Chemical compound C1C2C=CC1C(=CC)C2=C(C)C IOHAVGDJBFVWGE-UHFFFAOYSA-N 0.000 description 1
- SLQMKNPIYMOEGB-UHFFFAOYSA-N 2-methylhexa-1,5-diene Chemical compound CC(=C)CCC=C SLQMKNPIYMOEGB-UHFFFAOYSA-N 0.000 description 1
- AQZWEFBJYQSQEH-UHFFFAOYSA-N 2-methyloxaluminane Chemical compound C[Al]1CCCCO1 AQZWEFBJYQSQEH-UHFFFAOYSA-N 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- XPIQJMUYUKAKNX-VOTSOKGWSA-N 3-[(2e)-octa-2,7-dienyl]oxolane-2,5-dione Chemical compound C=CCCC\C=C\CC1CC(=O)OC1=O XPIQJMUYUKAKNX-VOTSOKGWSA-N 0.000 description 1
- RXUVQQVBBHXRNR-UHFFFAOYSA-N 3-ethylhex-1-en-1-ol Chemical compound CCCC(CC)C=CO RXUVQQVBBHXRNR-UHFFFAOYSA-N 0.000 description 1
- OLGHJTHQWQKJQQ-UHFFFAOYSA-N 3-ethylhex-1-ene Chemical compound CCCC(CC)C=C OLGHJTHQWQKJQQ-UHFFFAOYSA-N 0.000 description 1
- YVQDJVQSDNSPFR-UHFFFAOYSA-N 4,8-dimethyldeca-1,4,8-triene Chemical compound CC=C(C)CCC=C(C)CC=C YVQDJVQSDNSPFR-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- HBPSHRBTXIZBDI-UHFFFAOYSA-N 4-ethylidene-8-methylnona-1,7-diene Chemical compound C=CCC(=CC)CCC=C(C)C HBPSHRBTXIZBDI-UHFFFAOYSA-N 0.000 description 1
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- WTQBISBWKRKLIJ-UHFFFAOYSA-N 5-methylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C)CC1C=C2 WTQBISBWKRKLIJ-UHFFFAOYSA-N 0.000 description 1
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- 125000004429 atom Chemical group 0.000 description 1
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- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical group OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
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- 239000013078 crystal Substances 0.000 description 1
- 239000003484 crystal nucleating agent Substances 0.000 description 1
- HYPABJGVBDSCIT-UPHRSURJSA-N cyclododecene Chemical compound C1CCCCC\C=C/CCCC1 HYPABJGVBDSCIT-UPHRSURJSA-N 0.000 description 1
- ZXIJMRYMVAMXQP-UHFFFAOYSA-N cycloheptene Chemical compound C1CCC=CCC1 ZXIJMRYMVAMXQP-UHFFFAOYSA-N 0.000 description 1
- 125000004210 cyclohexylmethyl group Chemical group [H]C([H])(*)C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
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- 238000000354 decomposition reaction Methods 0.000 description 1
- XUDOZULIAWNMIU-UHFFFAOYSA-N delta-hexenoic acid Chemical class OC(=O)CCCC=C XUDOZULIAWNMIU-UHFFFAOYSA-N 0.000 description 1
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- CQKHFONAFZDDKV-UHFFFAOYSA-N dodec-1-en-1-ol Chemical compound CCCCCCCCCCC=CO CQKHFONAFZDDKV-UHFFFAOYSA-N 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- GCSJLQSCSDMKTP-UHFFFAOYSA-N ethenyl(trimethyl)silane Chemical compound C[Si](C)(C)C=C GCSJLQSCSDMKTP-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000002220 fluorenes Chemical class 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000004820 halides Chemical group 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- PDSKWUZFFRWRCD-UHFFFAOYSA-N hept-6-en-1-amine Chemical compound NCCCCCC=C PDSKWUZFFRWRCD-UHFFFAOYSA-N 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- JHEPBQHNVNUAFL-UHFFFAOYSA-N hex-1-en-1-ol Chemical compound CCCCC=CO JHEPBQHNVNUAFL-UHFFFAOYSA-N 0.000 description 1
- FICBXRYQMBKLJJ-UHFFFAOYSA-N hex-5-en-1-amine Chemical compound NCCCCC=C FICBXRYQMBKLJJ-UHFFFAOYSA-N 0.000 description 1
- GWSURTDMLUFMJH-UHFFFAOYSA-N hexadec-1-en-1-ol Chemical compound CCCCCCCCCCCCCCC=CO GWSURTDMLUFMJH-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- ACJQRYKUUGFHPV-UHFFFAOYSA-N icos-1-en-1-ol Chemical compound CCCCCCCCCCCCCCCCCCC=CO ACJQRYKUUGFHPV-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- UJNZOIKQAUQOCN-UHFFFAOYSA-N methyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(C)C1=CC=CC=C1 UJNZOIKQAUQOCN-UHFFFAOYSA-N 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 description 1
- 125000002868 norbornyl group Chemical group C12(CCC(CC1)C2)* 0.000 description 1
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 1
- MDVPRIBCAFEROC-UHFFFAOYSA-N oct-1-en-1-ol Chemical compound CCCCCCC=CO MDVPRIBCAFEROC-UHFFFAOYSA-N 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- LHTVMBMETNGEAN-UHFFFAOYSA-N pent-1-en-1-ol Chemical compound CCCC=CO LHTVMBMETNGEAN-UHFFFAOYSA-N 0.000 description 1
- LQAVWYMTUMSFBE-UHFFFAOYSA-N pent-4-en-1-ol Chemical compound OCCCC=C LQAVWYMTUMSFBE-UHFFFAOYSA-N 0.000 description 1
- HVAMZGADVCBITI-UHFFFAOYSA-N pent-4-enoic acid Chemical class OC(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- QIIPQYDSKRYMFG-UHFFFAOYSA-N phenyl hydrogen carbonate Chemical group OC(=O)OC1=CC=CC=C1 QIIPQYDSKRYMFG-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920005606 polypropylene copolymer Polymers 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical class O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001981 tert-butyldimethylsilyl group Chemical group [H]C([H])([H])[Si]([H])(C([H])([H])[H])[*]C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- UEIKOIYORDKQGZ-UHFFFAOYSA-N tetradec-1-en-1-ol Chemical compound CCCCCCCCCCCCC=CO UEIKOIYORDKQGZ-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical group CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- RXJKFRMDXUJTEX-UHFFFAOYSA-N triethylphosphine Chemical compound CCP(CC)CC RXJKFRMDXUJTEX-UHFFFAOYSA-N 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- HYWCXWRMUZYRPH-UHFFFAOYSA-N trimethyl(prop-2-enyl)silane Chemical compound C[Si](C)(C)CC=C HYWCXWRMUZYRPH-UHFFFAOYSA-N 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Paints Or Removers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
本発明はプロピレン系重合体、プロピレン系重合体の製造方法、及び塗装性材料に関し、さらに詳しくは、耐熱性に優れ、極性基である水酸基を有するプロピレン系重合、プロピレン系重合体の製造方法、及び塗装性材料体に関する。 The present invention relates to a propylene-based polymer, a method for producing a propylene-based polymer, and a paintable material, and more specifically, a propylene-based polymer having excellent heat resistance and having a polar hydroxyl group, a method for producing a propylene-based polymer, And a paintable material body.
ポリプロピレンは、加工性、耐薬品性、電気的性質、機械的性質などに優れているため、押出成形品、射出成形品、中空成形品、フィルム、シートなどに加工され、各種用途に用いられている。しかしながらポリポリプロピレンは、分子中に極性基を持たない、いわゆる無極性樹脂であるため、金属をはじめ種々の極性物質との親和性に乏しく、極性物質との接着または極性樹脂とのブレンドが困難であった。また、ポリプロピレンからなる成形体の表面は疎水性であり、防曇性、帯電防止性が必要な用途では、低分子量の界面活性剤などを配合する必要があり、界面活性剤のブリードアウトによる表面汚れなどの問題が起こる場合もあった。 Polypropylene is excellent in processability, chemical resistance, electrical properties, mechanical properties, etc., so it is processed into extrusion molded products, injection molded products, hollow molded products, films, sheets, etc. and used in various applications. Yes. However, since polypolypropylene is a so-called nonpolar resin that does not have a polar group in the molecule, it has poor affinity with various polar substances including metals, and adhesion with polar substances or blending with polar resins is difficult. there were. In addition, the surface of the molded body made of polypropylene is hydrophobic, and in applications that require anti-fogging properties and antistatic properties, it is necessary to add a low molecular weight surfactant, etc. In some cases, problems such as contamination occurred.
こうした問題を解決するため、ポリプロピレンに極性基である水酸基を導入することが行なわれてきた。極性化合物（極性オレフィン）を導入する場合、一般的には、ラジカル開始剤の存在下にポリプロピレンと極性オレフィンを反応させる方法が行われているが、このような方法によって得られた極性基含有プロピレン重合体には、ラジカル重合性極性オレフィンの単独重合体や未反応のポリプロピレンが含まれる場合が多く、導入位置も不均一なものである。さらに、ポリマー鎖の架橋反応や分解反応を伴うため、ポリプロピレンの物性が大きく変化する場合が多かった。上記のような架橋・分解反応を伴わずにポリプロピレンに水酸基を導入する方法について、Polymer Journal （第31巻、332頁、1999年）には、末端に不飽和結合を有するポリプロピレンにアルミニウム化合物を付加させた後に酸素で酸化することによりポリプロピレン末端に水酸基を導入する方法が記載されている。しかしこれらの方法では、ポリオレフィン末端の水酸基への変換が効率的に行なわれない。特開２００２−１５５１０９号公報、特開２００２−１４５９４４号公報等には、水酸基含有オレフィン化合物を有機アルミニウム化合物で処理したアルミ変性モノマーをオレフィン重合体の製造に用いて、水酸基含有オレフィン重合体を得る方法が開示されている。しかし、これらの方法では耐熱性に優れたプロピレン系重合体は得られず、また単位触媒あたりの生産性が低いなどの問題がある。Polymer Preprints, Japan（５０巻、１４１０頁、２００１年）では、極性化合物とオレフィンとの共重合も報告されているが、極性化合物のポリマー鎖中への導入量の増加に伴い、ポリマー材料の耐熱性の低下を招き、使用範囲の制限されたプロピレン共重合体しか得られていない。このような課題を克服した水酸基含有プロピレン系重合体を効率良く製造できる方法の開発が望まれている。
本発明者らはこのような従来技術のもと検討した結果、特定の触媒を用いてプロピレン系樹脂を製造すれば、耐熱性に優れ、従来供されていた重合体の課題を克服した新規なプロピレン系重合体が得られることを見出して本発明を完成するに至った。 As a result of investigations based on such conventional techniques, the inventors of the present invention have found that if a propylene-based resin is produced using a specific catalyst, the heat resistance is excellent, and a novel polymer that has overcome the problems of conventional polymers has been overcome. The inventors have found that a propylene-based polymer can be obtained and have completed the present invention.
本発明に係るプロピレン系重合体は、プロピレンと水酸基含有オレフィンから成るオレフィン系重合体であって、下記一般式［１］の構造のメタロセン化合物を含んだ触媒成分から製造され、
(i) 該重合体中の水酸基含有オレフィン量が１０mol%以下であり、(ii) 該重合体のゲルパーミエーションクロマトグラフィ（ＧＰＣ）測定によって得られた重量平均分子量（Ｍｗ）が５０００以上であり、(iii) 重量平均分子量（Ｍｗ）と数平均分子量（Ｍｎ）の比の値（Ｍｗ／Ｍｎ）が、１．０〜３．５の範囲にあり、(iv) 該重合体のＤＳＣで測定した融点（［Ｔｍ］；℃）と核磁気共鳴（ＮＭＲ）で測定した水酸基含有オレフィン量（［−ＯＨ］；mol%）とが、０＜［−ＯＨ］≦３の場合は、下記関係式(Eq-1)を満たし、３＜［−ＯＨ］≦１０の場合は下記関係式(Eq-2)を満たすことを特徴とするプロピレン系重合体。
The propylene polymer according to the present invention is an olefin polymer composed of propylene and a hydroxyl group-containing olefin, which is produced from a catalyst component containing a metallocene compound having a structure represented by the following general formula [1],
(i) The amount of hydroxyl group-containing olefin in the polymer is 10 mol% or less, (ii) the weight average molecular weight (Mw) obtained by gel permeation chromatography (GPC) measurement of the polymer is 5000 or more, (iii) The value (Mw / Mn) of the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is in the range of 1.0 to 3.5, and (iv) measured by DSC of the polymer When the melting point ([Tm]; ° C.) and the amount of hydroxyl group-containing olefin ([—OH]; mol%) measured by nuclear magnetic resonance (NMR) are 0 <[— OH] ≦ 3, A propylene-based polymer satisfying Eq-1) and satisfying the following relational expression (Eq-2) when 3 <[— OH] ≦ 10.
（式[１]中、Ｒ2は炭化水素基、ケイ素含有炭化水素基から選ばれ、Ｒ1、Ｒ3、Ｒ4、Ｒ5、Ｒ6、Ｒ7、Ｒ8、Ｒ9、Ｒ10、Ｒ11、Ｒ12は水素、炭化水素基、ケイ素含有炭化水素基から選ばれ、それぞれ同一でも異なっていてもよく、Ｒ3からＲ10までの隣接した置換基は互いに結合して環を形成してもよく、Ｍは周期表第４族から選ばれた金属であり、Ｙは炭素またはケイ素であり、Ｑはハロゲン、炭化水素基、アニオン配位子または孤立電子対で配位可能な中性配位子から同一または異なる組合せで選んでもよく、ｊは１〜４の整数である。）
(In the formula [1], R 2 is selected from a hydrocarbon group and a silicon-containing hydrocarbon group, and R 1 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 are selected from hydrogen, a hydrocarbon group, and a silicon-containing hydrocarbon group, and may be the same or different, and adjacent substituents from R 3 to R 10 are bonded to each other to form a ring. M is a metal selected from Group 4 of the periodic table, Y is carbon or silicon, Q is neutral capable of coordinating with a halogen, a hydrocarbon group, an anionic ligand or a lone pair of electrons. The ligands may be selected from the same or different combinations, and j is an integer of 1 to 4.)
また本発明のプロピレン系重合体の製造方法は、メタロセン化合物を含んだ触媒成分を用いることを特徴とする製造方法である。 Moreover, the manufacturing method of the propylene-type polymer of this invention is a manufacturing method characterized by using the catalyst component containing the metallocene compound.
本発明で見出されたオレフィン系重合体は、耐熱性などの機械物性に優れ、極性物質との親和性に優れる水酸基含有のプロピレン系重合体として、工業的に極めて利用価値の高いものである。 The olefin polymer found in the present invention is industrially extremely valuable as a hydroxyl group-containing propylene polymer having excellent mechanical properties such as heat resistance and excellent affinity with polar substances. .
以下、本発明に係るプロピレン系重合体について具体的に説明する。
本発明に係るプロピレン系重合体は、プロピレンと水酸基含有オレフィンとの共重合によって得られるプロピレン系重合体である。
The propylene polymer according to the present invention will be specifically described below.
The propylene polymer according to the present invention is a propylene polymer obtained by copolymerization of propylene and a hydroxyl group-containing olefin.
本発明に用いられる水酸基含有オレフィンとしては、水酸基含有のオレフィン系化合物であれば特に制限無く用いられる。水酸基含有オレフィンとして具体的には、例えばビニルアルコール、アリルアルコール、水酸化−1−ブテン、水酸化−1−ペンテン、水酸化−1−ヘキセン、水酸化−1−オクテン、水酸化−1−デセン、水酸化−1−ドデセン、水酸化−1−テトラデセン、水酸化−1−ヘキサデセン、水酸化−1−オクタデセン、水酸化−1−エイコセンなどの炭素原子数２〜２０、好ましくは２〜１０の直鎖状の水酸化α-オレフィン；例えば水酸化−3−メチル−1−ブテン、水酸化−4−メチル−１−ペンテン、水酸化−3−メチル−1−ペンテン、水酸化−3−エチル−1−ペンテン、水酸化−4,4−ジメチル−1−ペンテン、水酸化−4−メチル−1−ヘキセン、水酸化−4,4−ジメチル−1−ヘキセン、水酸化−4−エチル−1−ヘキセン、水酸化−3−エチル−1−ヘキセンなどの好ましくは５〜２０、より好ましくは５〜１０の分岐状の水酸化α-オレフィンが挙げられる。 The hydroxyl group-containing olefin used in the present invention is not particularly limited as long as it is a hydroxyl group-containing olefin compound. Specific examples of the hydroxyl group-containing olefin include vinyl alcohol, allyl alcohol, hydroxyl-1-butene, hydroxyl-1-pentene, hydroxyl-1-hexene, hydroxyl-1-octene, and hydroxyl-1-decene. , Hydroxyl-1-dodecene, hydroxyl-1-tetradecene, hydroxyl-1-hexadecene, hydroxyl-1-octadecene, hydroxyl-1-octadecene, hydroxyl-1-eicosene, etc., having 2 to 20, preferably 2 to 10 carbon atoms Linear hydroxylated α-olefins; for example, hydroxylated 3-methyl-1-butene, hydroxylated 4-methyl-1-pentene, hydroxylated 3-methyl-1-pentene, hydroxylated 3-ethyl -1-pentene, hydroxylated 4,4-dimethyl-1-pentene, hydroxylated 4-methyl-1-hexene, hydroxylated 4,4-dimethyl-1-hexene, hydroxylated 4-ethyl-1 -Hexene, hydroxyl-3-ethyl-1-hexene, etc. Preferably, a branched hydroxylated α-olefin having 5 to 20 and more preferably 5 to 10 is used.
本発明に用いられる水酸基含有オレフィン類は、１種類であっても良く、２種類以上の組み合わせで用いることもできる。 The hydroxyl group-containing olefins used in the present invention may be one kind or a combination of two or more kinds.
本発明に用いられる水酸基含有オレフィンは、該重合体中に１０mol%以下の量で含まれている。好ましくは７mol%以下であり、より好ましくは５mol%以下である。更に好ましくは３mol%以下である。 The hydroxyl group-containing olefin used in the present invention is contained in the polymer in an amount of 10 mol% or less. Preferably it is 7 mol% or less, More preferably, it is 5 mol% or less. More preferably, it is 3 mol% or less.
本発明に係るプロピレン系重合体においては、請求範囲に記載した要件を満たす範囲において、エチレンおよび炭素原子数４〜２０のオレフィンから選ばれる、少なくとも１種以上のオレフィンを含んでいても良い。 The propylene polymer according to the present invention may contain at least one or more olefins selected from ethylene and olefins having 4 to 20 carbon atoms as long as the requirements described in the claims are satisfied.
本発明において用いられる、炭素原子数２〜２０のオレフィンとしては、例えば直鎖状または分岐状のα-オレフィン、環状オレフィン、芳香族ビニル化合物、共役ジエン、非共役ポリエン、官能化ビニル化合物などが挙げられる。 Examples of the olefin having 2 to 20 carbon atoms used in the present invention include linear or branched α-olefin, cyclic olefin, aromatic vinyl compound, conjugated diene, non-conjugated polyene, and functionalized vinyl compound. Can be mentioned.
直鎖状または分岐状のα-オレフィンとして具体的には、例えばエチレン、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、1-ドデセン、1-テトラデセン、1-ヘキサデセン、1-オクタデセン、1-エイコセンなどの炭素原子数２〜２０、好ましくは２〜１０の直鎖状のα-オレフィン；例えば3-メチル-1-ブテン、3-メチル-1-ペンテン、3-エチル-1-ペンテン、4,4-ジメチル-1-ペンテン、4-メチル-1-ヘキセン、4,4-ジメチル-1-ヘキセン、4-エチル-1-ヘキセン、3-エチル-1-ヘキセンなどの好ましくは５〜２０、より好ましくは５〜１０の分岐状のα-オレフィンが挙げられる。 Specific examples of the linear or branched α-olefin include, for example, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1 A linear α-olefin having 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms, such as hexadecene, 1-octadecene, 1-eicosene, etc .; for example, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4,4-dimethyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4-ethyl-1-hexene, 3-ethyl-1- A branched α-olefin such as hexene is preferably 5-20, more preferably 5-10.
環状オレフィンとしては、シクロペンテン、シクロヘプテン、ノルボルネン、5-メチル-2-ノルボルネン、テトラシクロドデセン、ビニルシクロヘキサンなどの炭素原子数３〜２０、好ましくは５〜１５のものが挙げられる。 Examples of the cyclic olefin include those having 3 to 20, preferably 5 to 15 carbon atoms such as cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, vinylcyclohexane and the like.
芳香族ビニル化合物としては、例えばスチレン、およびα-メチルスチレン、o-メチルスチレン、m-メチルスチレン、p-メチルスチレン、o,p-ジメチルスチレン、o-エチルスチレン、m-エチルスチレン、p-エチルスチレンなどのモノまたはポリアルキルスチレンが挙げられる。 Examples of the aromatic vinyl compound include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o, p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene, p- Mono or polyalkyl styrenes such as ethyl styrene are mentioned.
共役ジエンとしては、例えば1,3-ブタジエン、イソプレン、クロロプレン、1,3-ペンタジエン、2,3-ジメチルブタジエン、4-メチル-1,3-ペンタジエン、1,3-ペンタジエン、1,3-ヘキサジエン、1,3-オクタジエンなどの炭素原子数４〜２０、好ましくは４〜１０のものが挙げられる。 Examples of conjugated dienes include 1,3-butadiene, isoprene, chloroprene, 1,3-pentadiene, 2,3-dimethylbutadiene, 4-methyl-1,3-pentadiene, 1,3-pentadiene, 1,3-hexadiene. , 1,3-octadiene and the like having 4 to 20 carbon atoms, preferably 4 to 10 carbon atoms.
非共役ポリエンとしては、例えば1,4-ペンタジエン、1,4-ヘキサジエン、1,5-ヘキサジエン、1,4-オクタジエン、1,5-オクタジエン、1,6-オクタジエン、1,7-オクタジエン、2-メチル-1,5-ヘキサジエン、6-メチル-1,5-ヘプタジエン、7-メチル-1,6-オクタジエン、4-エチリデン-8-メチル-1,7-ノナジエン、4,8-ジメチル-1,4,8-デカトリエン（ＤＭＤＴ）、ジシクロペンタジエン、シクロヘキサジエン、ジシクロオクタジエン、メチレンノルボルネン、5-ビニルノルボルネン、5-エチリデン-2-ノルボルネン、5-メチレン-2-ノルボルネン、5-イソプロピリデン-2-ノルボルネン、6-クロロメチル-5-イソプロペンル-2-ノルボルネン、2,3-ジイソプロピリデン-5-ノルボルネン、2-エチリデン-3-イソプロピリデン-5-ノルボルネン、2-プロペニル-2,2-ノルボルナジエンなどの炭素原子数５〜２０、好ましくは５〜１０のものが挙げられる。 Non-conjugated polyenes include, for example, 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 1,4-octadiene, 1,5-octadiene, 1,6-octadiene, 1,7-octadiene, 2 -Methyl-1,5-hexadiene, 6-methyl-1,5-heptadiene, 7-methyl-1,6-octadiene, 4-ethylidene-8-methyl-1,7-nonadiene, 4,8-dimethyl-1 , 4,8-decatriene (DMDT), dicyclopentadiene, cyclohexadiene, dicyclooctadiene, methylene norbornene, 5-vinyl norbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene -2-norbornene, 6-chloromethyl-5-isopropylene-2-norbornene, 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-propenyl-2,2 -5 carbon atoms such as norbornadiene 20, preferably include the 5 to 10.
官能化ビニル化合物としては、ハロゲン化オレフィン、アクリル酸、プロピオン酸、３−ブテン酸、４−ペンテン酸、５−ヘキセン酸、６−ヘプテン酸、７−オクテン酸、８−ノネン酸、９−デセン酸などの不飽和カルボン酸類、アリルアミン、５−ヘキセンアミン、６−ヘプテンアミンなどの不飽和アミン類、（２，７−オクタジエニル）コハク酸無水物、ペンタプロペニルコハク酸無水物および上記不飽和カルボン酸類にある化合物の例示において、カルボン酸基をカルボン酸無水物基に置き換えた化合物などの不飽和酸無水物類、上記不飽和カルボン酸類にある化合物の例示において、カルボン酸基をカルボン酸ハライド基に置き換えた化合物などの不飽和カルボン酸ハライド類、４−エポキシ−１−ブテン、５−エポキシ−１−ペンテン、６−エポキシ−１−ヘキセン、７−エポキシ−１−ヘプテン、８−エポキシ−１−オクテン、９−エポキシ−１−ノネン、１０−エポキシ−１−デセン、１１−エポキシ−１−ウンデセンなどの不飽和エポキシ化合物類などが挙げられる。 Examples of functionalized vinyl compounds include halogenated olefins, acrylic acid, propionic acid, 3-butenoic acid, 4-pentenoic acid, 5-hexenoic acid, 6-heptenoic acid, 7-octenoic acid, 8-nonenoic acid, and 9-decene. Unsaturated carboxylic acids such as acids, unsaturated amines such as allylamine, 5-hexeneamine, and 6-hepteneamine, (2,7-octadienyl) succinic anhydride, pentapropenyl succinic anhydride, and the above unsaturated carboxylic acids In an example of a compound, unsaturated acid anhydrides such as a compound in which a carboxylic acid group is replaced with a carboxylic acid anhydride group, in an example of a compound in the unsaturated carboxylic acid, the carboxylic acid group is replaced with a carboxylic acid halide group. Unsaturated carboxylic acid halides such as compounds, 4-epoxy-1-butene, 5-epoxy-1-pen 6-epoxy-1-hexene, 7-epoxy-1-heptene, 8-epoxy-1-octene, 9-epoxy-1-nonene, 10-epoxy-1-decene, 11-epoxy-1-undecene, etc. Of unsaturated epoxy compounds.
上記ハロゲン化オレフィンとして具体的には、例えば塩素、臭素、よう素等周期律表第１７族原子を有する、ハロゲン化ビニル、ハロゲン化−1−ブテン、ハロゲン化−1−ペンテン、ハロゲン化−1−ヘキセン、ハロゲン化−1−オクテン、ハロゲン化−1−デセン、ハロゲン化−1−ドデセン、ハロゲン化−1−テトラデセン、ハロゲン化−1−ヘキサデセン、ハロゲン化−1−オクタデセン、ハロゲン化−1−エイコセンなどの炭素原子数２〜２０、好ましくは２〜１０の直鎖状のハロゲン化α-オレフィン；例えばハロゲン化−3−メチル−1−ブテン、ハロゲン化−4−メチル−１−ペンテン、ハロゲン化−3−メチル−1−ペンテン、ハロゲン化−3−エチル−1−ペンテン、ハロゲン化−4,4−ジメチル−1−ペンテン、ハロゲン化−4−メチル−1−ヘキセン、ハロゲン化−4,4−ジメチル−1−ヘキセン、ハロゲン化−4−エチル−1−ヘキセン、ハロゲン化−3−エチル−1−ヘキセンなどの好ましくは５〜２０、より好ましくは５〜１０の分岐状のハロゲン化α-オレフィンが挙げられる。 Specific examples of the halogenated olefin include, for example, vinyl halide, halogenated-1-butene, halogenated-1-pentene, halogenated-1 having a group 17 atom in the periodic table of chlorine, bromine, iodine, etc. -Hexene, halogenated-1-octene, halogenated-1-decene, halogenated-1-dodecene, halogenated-1-tetradecene, halogenated-1-hexadecene, halogenated-1-octadecene, halogenated-1- Straight chain halogenated α-olefins having 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms such as eicosene; for example, halogenated-3-methyl-1-butene, halogenated-4-methyl-1-pentene, halogen -3-methyl-1-pentene, halogenated-3-ethyl-1-pentene, halogenated-4,4-dimethyl-1-pentene, halogenated-4-methyl-1-hexene Halogenated-4,4-dimethyl-1-hexene, halogenated-4-ethyl-1-hexene, halogenated-3-ethyl-1-hexene, etc., preferably 5-20, more preferably 5-10 Examples include branched halogenated α-olefins.
本発明に用いられる上記オレフィン類は、１種類であっても良く、２種類以上の組み合わせで用いることもできる。 The olefins used in the present invention may be one kind or a combination of two or more kinds.
本発明に係るプロピレン系重合体中の、エチレンおよび炭素原子数４〜２０のオレフィンの含量は、特に制限は無いが、４０mol%以下であることが好ましく、より好ましくは２０mol%以下、更に好ましくは１０mol%以下である。 The content of ethylene and the olefin having 4 to 20 carbon atoms in the propylene polymer according to the present invention is not particularly limited, but is preferably 40 mol% or less, more preferably 20 mol% or less, still more preferably. It is 10 mol% or less.
本発明に係るプロピレン系重合体は、例えばＮＭＲ等を用いた測定によって明らかとなるその立体規則性は、アイソタクティシティーが５０％以上、あるいはシンジオタクティシティーが５０％以上のポリオレフィンのいずれであってもよい。 The stereoregularity of the propylene-based polymer according to the present invention, which is clarified by, for example, measurement using NMR or the like, is either a polyolefin having an isotacticity of 50% or more or a syndiotacticity of 50% or more. May be.
本発明に係るオレフィン系重合体の分子量は、ゲルパーミエイションクロマトグラフィー（ＧＰＣ）により求められる重量平均分子量（Ｍｗ）がポリスチレン換算で５，０００以上である。より好ましくは１０，０００〜１０，０００，０００の範囲にである。また重量平均分子量（Ｍｗ）と数平均分子量（Ｍｎ）との割合（Ｍｗ／Ｍｎ）は、１．０〜３．５の範囲である。Ｍｗ／Ｍｎの値が大きいと、該重合体の靭性等の機械物性を発現するのに不利である。該重合体のＭｗ／Ｍｎの値が１．０〜３．５の範囲にあれば、靭性等の機械物性を発現するのに有利であり、工業的に価値がある。該重合体のＭｗ／Ｍｎの値は好ましくは１．０〜３．０の範囲であり、より好ましくは１．０〜２．８の範囲である。 As for the molecular weight of the olefin polymer according to the present invention, the weight average molecular weight (Mw) determined by gel permeation chromatography (GPC) is 5,000 or more in terms of polystyrene. More preferably, it is in the range of 10,000 to 10,000,000. Moreover, the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) is in the range of 1.0 to 3.5. When the value of Mw / Mn is large, it is disadvantageous for expressing mechanical properties such as toughness of the polymer. If the value of Mw / Mn of the polymer is in the range of 1.0 to 3.5, it is advantageous for developing mechanical properties such as toughness and is industrially valuable. The Mw / Mn value of the polymer is preferably in the range of 1.0 to 3.0, more preferably in the range of 1.0 to 2.8.
本発明に係るオレフィン系重合体の、デカン可溶部量の割合は好ましくは３重量％以下である。デカンにより抽出される量が多いと、成型加工性の悪化を招き工業的に不利である。より好ましくは１重量％以下である。 The proportion of the decane soluble part in the olefin polymer according to the present invention is preferably 3% by weight or less. When the amount extracted by decane is large, the moldability is deteriorated, which is industrially disadvantageous. More preferably, it is 1% by weight or less.
本発明において重要なのは、本発明に係るプロピレン系重合体が、該重合体のＤＳＣで測定した融点（［Ｔｍ］；℃）と核磁気共鳴（ＮＭＲ）で測定した水酸基含有オレフィン量（［−ＯＨ］；mol%）が、０＜［−ＯＨ］≦３の場合は、下記関係式(Eq-1)、好ましくは(Eq-1’)を満たし、３＜［−ＯＨ］≦１０の場合は下記関係式(Eq-2)、好ましくは(Eq-2’)を満たすことである。 What is important in the present invention is that the propylene polymer according to the present invention has a melting point ([Tm]; ° C) measured by DSC of the polymer and a hydroxyl group-containing olefin amount ([-OH) measured by nuclear magnetic resonance (NMR). Mol%) satisfying the following relational expression (Eq-1), preferably (Eq-1 ') when 0 <[-OH] ≤3, and when 3 <[-OH] ≤10 The following relational expression (Eq-2), preferably (Eq-2 ′) is satisfied.
オレフィン系重合体の融点が高ければ、該重合体に耐熱性を付与するために有利である。ただし、その融点（Tm）の上限は製法上の制約から通常、１８０℃以下、好ましくは１７０℃以下である。 A high melting point of the olefin polymer is advantageous for imparting heat resistance to the polymer. However, the upper limit of the melting point (Tm) is usually 180 ° C. or lower, preferably 170 ° C. or lower, due to limitations on the production method.
次に、本発明に係るオレフィン系重合体の製造方法について説明する。 Next, the manufacturing method of the olefin polymer which concerns on this invention is demonstrated.
本発明に係るオレフィン系重合体の製造に用いられるオレフィン重合触媒は、従来公知のいずれの触媒であってもよい。従来公知の触媒としては、例えばマグネシウム担持型チタン触媒、メタロセン触媒などが挙げられ、例えば国際公開特許ＷＯ０１／５３３６９、ＷＯ０１／２７１２４、特開平３−１９３７９６あるいは特開平０２−４１３０３中に記載の触媒が好適に用いられる。 The olefin polymerization catalyst used for the production of the olefin polymer according to the present invention may be any conventionally known catalyst. Examples of conventionally known catalysts include magnesium-supported titanium catalysts, metallocene catalysts, and the like. For example, the catalysts described in International Patent Publications WO01 / 53369, WO01 / 27124, JP-A-3-193396, or JP-A-02-41303 are available. Preferably used.
本発明にかかるオレフィン系重合体の製造には、下記一般式［１］で表されるメタロセン化合物を用いたオレフィン重合触媒が用いられる。 In the production of the olefin polymer according to the present invention, an olefin polymerization catalyst using a metallocene compound represented by the following general formula [1] is used.
（式[１]中、Ｒ2は炭化水素基、ケイ素含有炭化水素基から選ばれ、それぞれ同一でも異なっていてもよく、Ｒ1、Ｒ3、Ｒ4、Ｒ5、Ｒ6、Ｒ7、Ｒ8、Ｒ9、Ｒ10、Ｒ11、Ｒ12は水素、炭化水素基、ケイ素含有炭化水素基から選ばれ、それぞれ同一でも異なっていてもよく、Ｒ3からＲ10までの隣接した置換基は互いに結合して環を形成してもよく、Ｍは周期表第４族から選ばれた金属であり、Ｙは炭素またはケイ素であり、Ｑはハロゲン、炭化水素基、アニオン配位子または孤立電子対で配位可能な中性配位子から同一または異なる組合せで選んでもよく、ｊは１〜４の整数である。） (In the formula [1], R 2 is selected from a hydrocarbon group and a silicon-containing hydrocarbon group, and may be the same or different, and R 1 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 are selected from hydrogen, a hydrocarbon group, and a silicon-containing hydrocarbon group, and may be the same or different, and adjacent substituents from R 3 to R 10 May combine with each other to form a ring, M is a metal selected from Group 4 of the periodic table, Y is carbon or silicon, Q is halogen, a hydrocarbon group, an anionic ligand, or an isolated You may choose from the neutral ligand which can be coordinated with an electron pair by the same or different combination, and j is an integer of 1-4.)
本発明において、上記一般式［１］のＲ2は、炭化水素基、ケイ素含有炭化水素基から選ばれる。また上記一般式［１］のＲ1、Ｒ3、Ｒ4、Ｒ5、Ｒ6、Ｒ7、Ｒ8、Ｒ9、Ｒ10、Ｒ11、Ｒ12は水素、炭化水素基、ケイ素含有炭化水素基から選ばれ、それぞれ同一でも異なっていてもよい。 In the present invention, R 2 in the general formula [1] is selected from a hydrocarbon group and a silicon-containing hydrocarbon group. In the above general formula [1], R 1 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 are hydrogen, hydrocarbon group, silicon-containing carbon They are selected from hydrogen groups and may be the same or different.
炭化水素基としては、好ましくは炭素数１〜２０のアルキル基、炭素数７〜２０のアリールアルキル基、炭素数６〜２０のアリール基、または炭素数７〜２０のアルキルアリール基であり、１つ以上の環構造を含んでいてもよい。その具体例としては、メチル、エチル、n-プロピル、イソプロピル、2-メチルプロピル、1,1-ジメチルプロピル、2,2-ジメチルプロピル、1,1-ジエチルプロピル、1-エチル-1-メチルプロピル、1,1,2,2-テトラメチルプロピル、sec-ブチル、tert-ブチル、1,1-ジメチルブチル、1,1,3-トリメチルブチル、ネオペンチル、シクロヘキシルメチル、シクロヘキシル、1-メチル-1-シクロヘキシル、1-アダマンチル、2-アダマンチル、2-メチル-2-アダマンチル、メンチル、ノルボルニル、ベンジル、2-フェニルエチル、1-テトラヒドロナフチル、1-メチル-1-テトラヒドロナフチル、フェニル、ナフチル、トリル等が挙げられる。 The hydrocarbon group is preferably an alkyl group having 1 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an alkylaryl group having 7 to 20 carbon atoms. It may contain more than one ring structure. Specific examples thereof include methyl, ethyl, n-propyl, isopropyl, 2-methylpropyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, 1,1-diethylpropyl, 1-ethyl-1-methylpropyl. 1,1,2,2-tetramethylpropyl, sec-butyl, tert-butyl, 1,1-dimethylbutyl, 1,1,3-trimethylbutyl, neopentyl, cyclohexylmethyl, cyclohexyl, 1-methyl-1- Such as cyclohexyl, 1-adamantyl, 2-adamantyl, 2-methyl-2-adamantyl, menthyl, norbornyl, benzyl, 2-phenylethyl, 1-tetrahydronaphthyl, 1-methyl-1-tetrahydronaphthyl, phenyl, naphthyl, tolyl, etc. Can be mentioned.
ケイ素含有炭化水素基としては、好ましくはケイ素数１〜４、炭素数３〜２０のアルキルまたはアリールシリル基であり、その具体例としては、トリメチルシリル、tert−ブチルジメチルシリル、トリフェニルシリル等が挙げられる。なお、Ｒ2は立体的に嵩高い置換基であることが好ましく、炭素数４以上の置換基であることがより好ましい。 The silicon-containing hydrocarbon group is preferably an alkyl or arylsilyl group having 1 to 4 silicon atoms and 3 to 20 carbon atoms, and specific examples thereof include trimethylsilyl, tert-butyldimethylsilyl, triphenylsilyl and the like. It is done. R 2 is preferably a sterically bulky substituent, and more preferably a substituent having 4 or more carbon atoms.
フルオレン環上のＲ3からＲ10までの隣接した置換基は、互いに結合して環を形成してもよい。そのような置換フルオレニル基として、ベンゾフルオレニル、ジベンゾフルオレニル、オクタヒドロジベンゾフルオレニル、オクタメチルオクタヒドロジベンゾフルオレニル等を挙げることができる。 Adjacent substituents from R 3 to R 10 on the fluorene ring may be bonded to each other to form a ring. Examples of such substituted fluorenyl groups include benzofluorenyl, dibenzofluorenyl, octahydrodibenzofluorenyl, octamethyloctahydrodibenzofluorenyl and the like.
また、フルオレン環上のＲ3からＲ10の置換基は、合成上の容易さから左右対称、すなわちＲ3＝Ｒ10、Ｒ4＝Ｒ9、Ｒ5＝Ｒ8、Ｒ6＝Ｒ7であることが好ましく、無置換フルオレン、3,6-二置換フルオレン、2,7-二置換フルオレンまたは2,3,6,7-四置換フルオレンであることがより好ましい。ここでフルオレン環上の３位、６位、２位、７位はそれぞれＲ5、Ｒ8、Ｒ4、Ｒ9に対応する。 The substituents R 3 to R 10 on the fluorene ring are symmetrical from the viewpoint of ease of synthesis, that is, R 3 = R 10 , R 4 = R 9 , R 5 = R 8 , R 6 = R 7 . Preferably, it is unsubstituted fluorene, 3,6-disubstituted fluorene, 2,7-disubstituted fluorene or 2,3,6,7-tetrasubstituted fluorene. Wherein the 3-position on the fluorene ring, 6-position, 2-position, 7-position each R 5, R 8, corresponding to R 4, R 9.
上記一般式［１］のＲ11とＲ12は、水素、炭化水素基から選ばれ、それぞれ同一でも異なっていてもよい。好ましい炭化水素基の具体例としては、上記と同様のものを挙げることができる。 R 11 and R 12 in the general formula [1] are selected from hydrogen and a hydrocarbon group, and may be the same or different. Specific examples of preferred hydrocarbon groups include the same as those described above.
Ｙは炭素またはケイ素である。一般式［１］の場合は、Ｒ13とＲ14はＹと結合し、架橋部として置換メチレン基または置換シリレン基を構成する。好ましい具体例としては、上記と同様のものを挙げることができる。 Y is carbon or silicon. In the case of the general formula [1], R 13 and R 14 are bonded to Y to form a substituted methylene group or a substituted silylene group as a bridging part. Preferable specific examples include those similar to the above.
本発明において、一般式［１］のＭは、周期表第４族から選ばれる金属であり、Ｍとしてはチタニウム、ジルコニウム、ハフニウムが挙げられる。Ｑはハロゲン、炭素数１〜２０の炭化水素基、アニオン配位子、または孤立電子対で配位可能な中性配位子から同一または異なる組合せで選ばれる。 In the present invention, M in the general formula [1] is a metal selected from Group 4 of the periodic table, and examples of M include titanium, zirconium, and hafnium. Q is selected in the same or different combination from halogen, a hydrocarbon group having 1 to 20 carbon atoms, an anionic ligand, or a neutral ligand capable of coordinating with a lone electron pair.
ハロゲンの具体例としては、フッ素、塩素、臭素、ヨウ素であり、炭化水素基の具体例としては、上記と同様のものを挙げることができる。アニオン配位子の具体例としては、メトキシ、tert−ブトキシ、フェノキシ等のアルコキシ基、アセテート、ベンゾエート等のカルボキシレート基、メシレート、トシレート等のスルホネート基等が挙げられる。孤立電子対で配位可能な中性配位子の具体例としては、トリメチルホスフィン、トリエチルホスフィン、トリフェニルホスフィン、ジフェニルメチルホスフィンなどの有機リン化合物、またはテトラヒドロフラン、ジエチルエーテル、ジオキサン、１、２−ジメトキシエタン等のエーテル類が挙げられる。これらのうち、Ｑは同一でも異なった組み合わせでもよいが、少なくとも一つはハロゲンまたはアルキル基であるのが好ましい。 Specific examples of the halogen include fluorine, chlorine, bromine, and iodine. Specific examples of the hydrocarbon group include the same as those described above. Specific examples of the anionic ligand include alkoxy groups such as methoxy, tert-butoxy and phenoxy, carboxylate groups such as acetate and benzoate, and sulfonate groups such as mesylate and tosylate. Specific examples of the neutral ligand that can coordinate with a lone electron pair include organic phosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, and diphenylmethylphosphine, or tetrahydrofuran, diethyl ether, dioxane, 1,2- And ethers such as dimethoxyethane. Among these, Q may be the same or different combinations, but at least one is preferably a halogen or an alkyl group.
本発明における上記メタロセン化合物の具体例としては、ＷＯ０１／２７１２４中に例示される化合物が好適に挙げられるが、特にこれによって本発明の範囲が限定されるものではない。 Specific examples of the metallocene compound in the present invention include compounds exemplified in WO01 / 27124, but the scope of the present invention is not particularly limited thereby.
また上記のような化合物中のジルコニウムをチタンまたはハフニウムに代えた化合物を挙げることもできる。本発明では、メタロセンのラセミ体が触媒成分として用いられるが、Ｒ型またはＳ型を用いることもできる。このようなメタロセンは、Journal of Organometallic Chem.288(1985)、第63−67頁、ヨーロッパ特許出願公開第0,320,762号明細書に準じて製造することができる。 Moreover, the compound which replaced the zirconium in the above compounds with titanium or hafnium can also be mentioned. In the present invention, a racemic form of metallocene is used as a catalyst component, but R-type or S-type can also be used. Such metallocenes can be produced according to Journal of Organometallic Chem. 288 (1985), pp. 63-67, European Patent Application No. 0,320,762.
本発明の方法にかかるオレフィン系重合体の製造が、メタロセン触媒を用いて行なわれる場合、触媒成分は
（Ａ）上記一般式［１］で表されるメタロセン化合物と、
（Ｂ）(B-1) 有機金属化合物、
(B-2) 有機アルミニウムオキシ化合物、および
(B-3) メタロセン化合物（Ａ）と反応してイオン対を形成する化合物
から選ばれる少なくとも１種の化合物、
さらに必要に応じて、
（Ｃ）微粒子状担体
から構成される、一般に公知の方法で重合触媒として用いることが出来、例えばＷＯ０１／２７１２４記載の方法を採用することが出来る。
When the production of the olefin polymer according to the method of the present invention is performed using a metallocene catalyst, the catalyst component is (A) a metallocene compound represented by the general formula [1],
(B) (B-1) Organometallic compound,
(B-2) an organoaluminum oxy compound, and
(B-3) at least one compound selected from compounds that react with the metallocene compound (A) to form ion pairs;
If necessary,
(C) It can be used as a polymerization catalyst by a generally known method comprising a particulate carrier, and for example, the method described in WO01 / 27124 can be employed.
本発明では、プロピレンと水酸基含有オレフィンとの共重合体は、特開２００２−１５５１０９号公報、特開２０００−２９０３１３号公報、特開平８−１０９２１８号公報、特開２００２−１６７４１２号公報等において開示されている方法によって製造することができる。具体的には、プロピレン；上記例示されるアリルアルコール、4-ペンテン-1-オール、5-ヘキセン-1-オールのような不飽和アルコール類を、既知のチーグラーナッタ触媒やメタロセン触媒を用いて共重合することによって製造することが可能である。 In the present invention, a copolymer of propylene and a hydroxyl group-containing olefin is disclosed in JP 2002-155109 A, JP 2000-290313 A, JP 8-109218 A, JP 2002-167712 A, and the like. It can be manufactured by the method currently being used. Specifically, propylene; unsaturated alcohols such as allyl alcohol, 4-penten-1-ol, and 5-hexen-1-ol exemplified above may be used together using a known Ziegler-Natta catalyst or metallocene catalyst. It can be produced by polymerization.
本発明では、重合は溶解重合、懸濁重合などの液相重合法または気相重合法いずれにおいても実施できる。液相重合法においては、不活性炭化水素溶媒を用いてもよく、具体的には、プロパン、ブタン、ペンタン、ヘキサン、ヘプタン、オクタン、デカン、ドデカン、灯油などの脂肪族炭化水素；シクロペンタン、シクロヘキサン、メチルシクロペンタンなどの脂環族炭化水素；ベンゼン、トルエン、キシレンなどの芳香族炭化水素；エチレンクロリド、クロルベンゼン、ジクロロメタンなどのハロゲン化炭化水素またはこれらの混合物などを挙げることができ、重合に用いる４−メチル−１−ペンテンを含んだオレフィン類自身を溶媒として用いることもできる。 In the present invention, the polymerization can be carried out by either a liquid phase polymerization method such as solution polymerization or suspension polymerization or a gas phase polymerization method. In the liquid phase polymerization method, an inert hydrocarbon solvent may be used. Specifically, aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, Alicyclic hydrocarbons such as cyclohexane and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane, or mixtures thereof. Olefins containing 4-methyl-1-pentene used in the process can be used as a solvent.
重合を行うに際して、成分（Ａ）は、反応容積１リットル当り、通常１０-8〜１０-2モル、好ましくは１０-7〜１０-3モルとなるような量で用いられる。 In carrying out the polymerization, component (A) is usually used in an amount of 10 −8 to 10 −2 mol, preferably 10 −7 to 10 −3 mol, per liter of reaction volume.
成分(B-1) は、成分(B-1) と、成分（Ａ）中の遷移金属原子（Ｍ）とのモル比〔(B-1) ／Ｍ〕が、通常０．０１〜５０００、好ましくは０．０５〜２０００となるような量で用いられる。成分(B-2) は、成分(B-2) 中のアルミニウム原子と、成分（Ａ）中の遷移金属原子（Ｍ）とのモル比〔(B-2) ／Ｍ〕が、通常１０〜５０００、好ましくは２０〜２０００となるような量で用いられる。成分(B-3) は、成分(B-3) と、成分（Ａ）中の遷移金属原子（Ｍ）とのモル比〔(B-3) ／Ｍ〕が、通常１〜１０、好ましくは１〜５となるような量で用いられる。 Component (B-1) has a molar ratio [(B-1) / M] of component (B-1) and transition metal atom (M) in component (A) of usually 0.01 to 5000, Preferably it is used in such an amount that it is 0.05-2000. Component (B-2) has a molar ratio [(B-2) / M] of the aluminum atom in component (B-2) and the transition metal atom (M) in component (A) of usually 10 to 10. The amount used is 5000, preferably 20-2000. Component (B-3) has a molar ratio [(B-3) / M] of component (B-3) to transition metal atom (M) in component (A) of usually 1 to 10, preferably It is used in such an amount as to be 1-5.
また、このようなオレフィン重合触媒を用いたオレフィンの重合温度は、通常−５０〜４００℃、好ましくは１０〜３００℃、より好ましくは１０〜２５０℃の範囲である。重合温度が低すぎると単位触媒あたりの重合活性が低下してしまい、工業的に好ましくない。 Moreover, the polymerization temperature of the olefin using such an olefin polymerization catalyst is -50-400 degreeC normally, Preferably it is 10-300 degreeC, More preferably, it is the range of 10-250 degreeC. If the polymerization temperature is too low, the polymerization activity per unit catalyst is lowered, which is not industrially preferable.
重合圧力は、通常常圧〜１０ＭＰａゲージ圧、好ましくは常圧〜５ＭＰａゲージ圧の条件下であり、重合反応は、回分式、半連続式、連続式のいずれの方法においても行うことができる。さらに重合を反応条件の異なる２段以上に分けて行うことも可能である。 The polymerization pressure is usually from normal pressure to 10 MPa gauge pressure, preferably from normal pressure to 5 MPa gauge pressure, and the polymerization reaction can be carried out in any of batch, semi-continuous and continuous methods. Furthermore, the polymerization can be performed in two or more stages having different reaction conditions.
重合に際して生成ポリマーの分子量や重合活性を制御する目的で水素を添加することができ、その量はオレフィン１ｋｇあたり０．００１〜１００ＮＬ程度が適当である。 In the polymerization, hydrogen can be added for the purpose of controlling the molecular weight and polymerization activity of the produced polymer, and the amount is suitably about 0.001 to 100 NL per kg of olefin.
本発明において、4-メチル-1-ペンテンとともに重合反応に供給されるオレフィンとしては、炭素数２〜２０のオレフィン、特に炭素数２〜１０のα−オレフィンが好ましい。具体的には、エチレン、プロピレン、1-ブテン、1-ペンテン、1-ヘキセン、3-メチル-1-ブテン、3-メチル-1-ペンテン、3-エチル-1-ペンテン、4-メチル-1-ヘキセン、4,4-ジメチル-1-ヘキセン、4,4-ジメチル-1-ペンテン、4-エチル-1-ヘキセン、3-エチル-1-ヘキセン、1-オクテン、1-デセン、1-ドデセン、1-テトラデセン、1-ヘキサデセン、1-オクタデセン、1-エイコセン、ビニルシクロヘキサン、スチレン等が挙げられる。 In the present invention, the olefin supplied to the polymerization reaction together with 4-methyl-1-pentene is preferably an olefin having 2 to 20 carbon atoms, particularly an α-olefin having 2 to 10 carbon atoms. Specifically, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1 -Hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene, vinylcyclohexane, styrene and the like.
また、さらにブタジエン、１，４−ペンタジエン、１，５−ヘキサジエン、１，４−ヘキサジエン等の炭素数４〜２０のジエン、あるいは、ジシクロペンタジエン、ノルボルネン、メチルノルボルネン、テトラシクロドデセン、メチルテトラシクロドデセン等の環状オレフィン、あるいは、アリルトリメチルシラン、ビニルトリメチルシラン等のケイ素含有オレフィン等が挙げられる。 Further, diene having 4 to 20 carbon atoms such as butadiene, 1,4-pentadiene, 1,5-hexadiene, 1,4-hexadiene, or dicyclopentadiene, norbornene, methylnorbornene, tetracyclododecene, methyltetra Examples thereof include cyclic olefins such as cyclododecene, and silicon-containing olefins such as allyltrimethylsilane and vinyltrimethylsilane.
これらの4-メチル-1-ペンテンを含むオレフィンは、単独で重合しても、２種類以上の組み合わせで重合してもよい。このような共重合体として、4-メチル-1-ペンテン単位が８０ないし１００重量％、及びエチレン及び／または他のα−オレフィン単位が２０ないし０重量％からなる共重合体がある。 These olefins containing 4-methyl-1-pentene may be polymerized alone or in combination of two or more. Examples of such copolymers include copolymers comprising 80 to 100% by weight of 4-methyl-1-pentene units and 20 to 0% by weight of ethylene and / or other α-olefin units.
（用途）
本発明に係るプロピレン系重合体は、水酸基を含有するポリオレフィン材料として、塗装性、接着性、印刷性等に優れた材料として用いられる。例えば、自動車外装材、樹脂フィルムとの張り合わせ、表面印刷用樹脂等に用いられる。またアルミニウム等の金属蒸着用フィルム樹脂として、高バリア性を付与した樹脂としても用いられる。さらに、他樹脂とのポリマーアロイ用相溶化剤としても好適に用いられる。その他、カレンダー成形、押出成形、射出成形、ブロー成形、プレス成形、スタンピング成形などの各種成型よって加工することができ、射出成型品、中空容器、フィルムシート、繊維など以外にも、その用途としては制限無く用いることができる。
(Use)
The propylene polymer according to the present invention is used as a material excellent in paintability, adhesiveness, printability and the like as a polyolefin material containing a hydroxyl group. For example, it is used for automobile exterior materials, bonding with resin films, surface printing resins, and the like. Moreover, it is used also as resin which provided high barrier property as film resin for metal vapor deposition, such as aluminum. Further, it is also suitably used as a compatibilizer for polymer alloys with other resins. Besides, it can be processed by various moldings such as calendar molding, extrusion molding, injection molding, blow molding, press molding, stamping molding, etc. In addition to injection molded products, hollow containers, film sheets, fibers, etc. Can be used without limitation.
本発明に係るオレフィン系重合体は、樹脂、ゴム、潤滑油用基材、ワックス、セメントまたはインキ・塗料とを含むオレフィン系重合体組成物であってもよい。 The olefin polymer according to the present invention may be an olefin polymer composition containing a resin, rubber, a base material for lubricating oil, wax, cement, or ink / paint.
本発明に係るオレフィン系重合体は、本発明以外の熱可塑性樹脂とを含んでなる分散体として、水性樹脂分散体、油性樹脂分散体として、好適に用いられる。熱可塑性樹脂の配合量は特に限定されないが、熱可塑性樹脂１００重量部に対し、上記オレフィン系重合体を、通常０.０１〜１５０重量部、必要に応じて充填剤を０.０１〜３００重量部、好ましくはオレフィン系重合体を０.１〜２０重量部、充填剤を０.１〜４０重量部、さらに好ましくはオレフィン系重合体を０.５〜１０重量部、充填剤を０.５〜２０重量部の量で用いることが好ましい。 The olefin polymer according to the present invention is suitably used as an aqueous resin dispersion or an oily resin dispersion as a dispersion comprising a thermoplastic resin other than the present invention. The blending amount of the thermoplastic resin is not particularly limited, but the olefin polymer is usually 0.01 to 150 parts by weight with respect to 100 parts by weight of the thermoplastic resin, and optionally 0.01 to 300 parts by weight of filler. Parts, preferably 0.1 to 20 parts by weight of olefin polymer, 0.1 to 40 parts by weight of filler, more preferably 0.5 to 10 parts by weight of olefin polymer and 0.5 to 5.0 parts of filler. It is preferably used in an amount of ˜20 parts by weight.
本発明に係るオレフィン系重合体は、水酸化マグネシウムなどの無機充填材またはビニルトリメトキシシランなどの架橋剤と併用して用いることができる。必要に応じて本発明の目的を損なわない範囲において、各種の添加剤、例えば軟化剤、安定剤、充填剤、酸化防止剤、結晶核剤などを配合することができる。 The olefin polymer according to the present invention can be used in combination with an inorganic filler such as magnesium hydroxide or a crosslinking agent such as vinyltrimethoxysilane. Various additives such as a softening agent, a stabilizer, a filler, an antioxidant, a crystal nucleating agent, and the like can be blended as long as the object of the present invention is not impaired.
本発明に係るオレフィン系重合体と磁性粉を混練することにより、優れた磁気記録用素材を得ることができる。この場合、オレフィン系重合体と磁性粉との配合比率（オレフィン系ブロック共重合体／磁性粉：重量比）は、９９／１〜１０／９０であることが好ましい。また、これらはプラスチックマグネットとして文房具などに好ましく用いることができる。 By kneading the olefin polymer according to the present invention and magnetic powder, an excellent magnetic recording material can be obtained. In this case, the blending ratio of the olefin polymer and the magnetic powder (olefin block copolymer / magnetic powder: weight ratio) is preferably 99/1 to 10/90. Moreover, these can be preferably used for stationery etc. as a plastic magnet.
本発明では必要に応じて、無機フィラーを添加して使用することもできる。これらの添加量は、接着性樹脂１００重量部に対して、前記オレフィン系ブロック共重合体は通常５〜５０重量部、好ましくは５〜２０重量部であり、無機フィラーは通常１０〜６０重量部、好ましくは２０〜４０重量部であることが望ましい。 In this invention, an inorganic filler can also be added and used as needed. These addition amounts are usually 5 to 50 parts by weight, preferably 5 to 20 parts by weight for the olefin block copolymer, and 10 to 60 parts by weight for the inorganic filler with respect to 100 parts by weight of the adhesive resin. The amount is preferably 20 to 40 parts by weight.
以下に実施例を示し、さらに本発明を説明するが、本発明はこれら実施例に制限されるものではない。 Examples The present invention will be further described with reference to examples, but the present invention is not limited to these examples.
本発明において、重合体の融点（Ｔｍ）は、示差走査熱量測定（ＤＳＣ）によって、２００℃で５分間保持した重合体サンプルを、２０℃まで冷却して５分間保持した後に、１０℃／分で昇温させたときの結晶溶融ピークから算出した。 In the present invention, the melting point (Tm) of the polymer is 10 ° C./min after the polymer sample held at 200 ° C. for 5 minutes is cooled to 20 ° C. and held for 5 minutes by differential scanning calorimetry (DSC). It was calculated from the crystal melting peak when the temperature was raised at.
分子量（Ｍｗ、Ｍｎ）は、ＧＰＣ（ゲルパーミエイションクロマトグラフィー：ポリスチレン換算）により測定した。 The molecular weight (Mw, Mn) was measured by GPC (gel permeation chromatography: in terms of polystyrene).
〔実施例１〕
攪拌器を備え、十分に窒素置換した内容積１０００ｍｌのガラス製重合器に、トルエン（８００ｍｌ）を導入し、プロピレンガス（１００ＮＬ／ｈ）を供給しながら温度を６０℃に保った。トリイソブチルアルミニウム（４４ｍｍｏｌ）と１−ウンデセノール（４０ｍｍｏｌ）を加え１０分間攪拌した後、メチルアルモキサン（ＭＡＯ、アルベマール社製、１０％トルエン溶液）３ｍｍｏｌ［Ａｌ］で活性化されたイソプロピル（３−ｔｅｒｔ−ブチル−５−メチルシクロペンタジエニル）（３，６−ジ−ｔｅｒｔ−ブチルフルオレニル）ジルコニウムジクロライド（０．００３ｍｍｏｌ）を重合器内に加え、温度を６０℃に保ちながら１５分間重合を行った。メタノールを重合器内に導入して重合を終了し、重合液を２Ｌの塩酸含有のメタノール中に注ぎ込み、濾過によりポリマーを回収した。減圧下８０℃で１０時間乾燥し、得られたポリマーは９．２ｇであった。ポリマーはＴｍ＝１１１．０℃、ＧＰＣで測定したＭｗ＝９８，０００、Ｍｎ＝４２，０００であり、Ｍｗ／Ｍｎ＝２．３であった。１Ｈ−ＮＭＲ測定から得られたポリマー中のＯＨ基含量は、４．４１mol%であった。
[Example 1]
Toluene (800 ml) was introduced into a glass polymerization vessel equipped with a stirrer and sufficiently purged with nitrogen and having an internal volume of 1000 ml, and the temperature was kept at 60 ° C. while supplying propylene gas (100 NL / h). After adding triisobutylaluminum (44 mmol) and 1-undecenol (40 mmol) and stirring for 10 minutes, isopropyl (3-tert) activated with 3 mmol [Al] of methylalumoxane (MAO, Albemarle, 10% toluene solution) was added. -Butyl-5-methylcyclopentadienyl) (3,6-di-tert-butylfluorenyl) zirconium dichloride (0.003 mmol) was added into the polymerization vessel and polymerization was carried out for 15 minutes while maintaining the temperature at 60 ° C. went. Methanol was introduced into the polymerization vessel to complete the polymerization, the polymerization solution was poured into 2 L of hydrochloric acid-containing methanol, and the polymer was recovered by filtration. It dried for 10 hours at 80 degreeC under pressure reduction, and the obtained polymer was 9.2g. The polymer had Tm = 111.0 ° C., Mw = 98,000 measured by GPC, Mn = 42,000, and Mw / Mn = 2.3. The OH group content in the polymer obtained from 1H-NMR measurement was 4.41 mol%.
〔比較例１〕
イソプロピル（３−ｔ−ブチル−５−メチルシクロペンタジエニル）（フルオレニル）ジルコニウムジクロリド（５．１ｍｇ）の代わりに、エチレンビス（インデニル）ジルコニウムジクロリド（４．２ｍｇ）を用いた以外は、実施例１と同様に重合を行ない、４０．４ｇのポリマーが得られた。ポリマーはＴｍ＝１１５．４℃、ＧＰＣで測定したＭｗ＝５５，０００、Ｍｎ＝２１，０００であり、Ｍｗ／Ｍｎ＝２．６であった。１Ｈ−ＮＭＲ測定から得られたポリマー中のＯＨ基含量は、２．３０mol%であった。
[Comparative Example 1]
Example except that ethylenebis (indenyl) zirconium dichloride (4.2 mg) was used instead of isopropyl (3-tert-butyl-5-methylcyclopentadienyl) (fluorenyl) zirconium dichloride (5.1 mg). Polymerization was carried out in the same manner as in 1 to obtain 40.4 g of polymer. The polymer had Tm = 115.4 ° C., Mw = 55,000 measured by GPC, Mn = 21,000, and Mw / Mn = 2.6. The OH group content in the polymer obtained from 1H-NMR measurement was 2.30 mol%.
本発明の、水酸基含有プロピレン系重合体は水酸基含有量、融点共に高いという特徴を持つことから、耐熱性が要求される各種の用途に好適に使用される。 Since the hydroxyl group-containing propylene polymer of the present invention is characterized by a high hydroxyl group content and a high melting point, it is suitably used for various applications requiring heat resistance.
Claims (3)
下記一般式［１］の構造のメタロセン化合物を含んだ触媒成分から製造され、
(i) 該重合体中の水酸基含有オレフィン量が１０mol%以下であり、(ii) 該重合体のゲルパーミエーションクロマトグラフィ（ＧＰＣ）測定によって得られた重量平均分子量（Ｍｗ）が５０００以上であり、(iii) 重量平均分子量（Ｍｗ）と数平均分子量（Ｍｎ）の比の値（Ｍｗ／Ｍｎ）が、１．０〜３．５の範囲にあり、(iv) 該重合体のＤＳＣで測定した融点（［Ｔｍ］；℃）と核磁気共鳴（ＮＭＲ）で測定した水酸基含有オレフィン量（［−ＯＨ］；mol%）とが、０＜［−ＯＨ］≦３の場合は、下記関係式(Eq-1)を満たし、３＜［−ＯＨ］≦１０の場合は下記関係式(Eq-2)を満たすことを特徴とするプロピレン系重合体。
（式[１]中、Ｒ2は炭化水素基、ケイ素含有炭化水素基から選ばれ、Ｒ1、Ｒ3、Ｒ4、Ｒ5、Ｒ6、Ｒ7、Ｒ8、Ｒ9、Ｒ10、Ｒ11、Ｒ12は水素、炭化水素基、ケイ素含有炭化水素基から選ばれ、それぞれ同一でも異なっていてもよく、Ｒ3からＲ10までの隣接した置換基は互いに結合して環を形成してもよく、Ｍは周期表第４族から選ばれた金属であり、Ｙは炭素またはケイ素であり、Ｑはハロゲン、炭化水素基、アニオン配位子または孤立電子対で配位可能な中性配位子から同一または異なる組合せで選んでもよく、ｊは１〜４の整数である。） A propylene polymer comprising propylene and a hydroxyl group-containing olefin,
Manufactured from a catalyst component containing a metallocene compound having the structure of the following general formula [1],
(i) The amount of hydroxyl group-containing olefin in the polymer is 10 mol% or less, (ii) the weight average molecular weight (Mw) obtained by gel permeation chromatography (GPC) measurement of the polymer is 5000 or more, (iii) The value (Mw / Mn) of the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is in the range of 1.0 to 3.5, and (iv) measured by DSC of the polymer When the melting point ([Tm]; ° C.) and the amount of hydroxyl group-containing olefin ([—OH]; mol%) measured by nuclear magnetic resonance (NMR) are 0 <[— OH] ≦ 3, A propylene-based polymer satisfying Eq-1) and satisfying the following relational expression (Eq-2) when 3 <[— OH] ≦ 10.
(In the formula [1], R 2 is selected from a hydrocarbon group and a silicon-containing hydrocarbon group, and R 1 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 are selected from hydrogen, a hydrocarbon group, and a silicon-containing hydrocarbon group, and may be the same or different, and adjacent substituents from R 3 to R 10 are bonded to each other to form a ring. M is a metal selected from Group 4 of the periodic table, Y is carbon or silicon, Q is neutral capable of coordinating with a halogen, a hydrocarbon group, an anionic ligand or a lone pair of electrons. The ligands may be selected from the same or different combinations, and j is an integer of 1 to 4.)
（II) 水酸基含有オレフィンと、
（III) 下記（Ａ）及び（Ｂ）を含む触媒成分と、
を順次、又は同時に添加し共重合反応させ、
下記（i)〜(iv)を満たすプロピレン系重合体を製造する方法。
（Ａ）下記一般式［１］で表されるメタロセン化合物。
（式[１]中、Ｒ2は炭化水素基、ケイ素含有炭化水素基から選ばれ、Ｒ1、Ｒ3、Ｒ4、Ｒ5、Ｒ6、Ｒ7、Ｒ8、Ｒ9、Ｒ10、Ｒ11、Ｒ12は水素、炭化水素基、ケイ素含有炭化水素基から選ばれ、それぞれ同一でも異なっていてもよく、Ｒ3からＲ10までの隣接した置換基は互いに結合して環を形成してもよく、Ｍは周期表第４族から選ばれた金属であり、Ｙは炭素またはケイ素であり、Ｑはハロゲン、炭化水素基、アニオン配位子または孤立電子対で配位可能な中性配位子から同一または異なる組合せで選んでもよく、ｊは１〜４の整数である。）
（Ｂ）(B-1) 有機金属化合物、
(B-2) 有機アルミニウムオキシ化合物、および
(B-3) メタロセン化合物（Ａ）と反応してイオン対を形成する化合物、
から選ばれる少なくとも１種の化合物。
(i) 該重合体中の水酸基含有オレフィン量が１０mol%以下であり、
(ii) 該重合体のゲルパーミエーションクロマトグラフィ（ＧＰＣ）測定によって得られた重量平均分子量（Ｍｗ）が５０００以上であり、
(iii) 重量平均分子量（Ｍｗ）と数平均分子量（Ｍｎ）の比の値（Ｍｗ／Ｍｎ）が、１．０〜３．５の範囲にあり、
(iv) 該重合体のＤＳＣで測定した融点（［Ｔｍ］；℃）と核磁気共鳴（ＮＭＲ）で測定した水酸基含有オレフィン量（［−ＯＨ］；mol%）とが、０＜［−ＯＨ］≦３の場合は、下記関係式(Eq-1)を満たし、３＜［−ＯＨ］≦１０の場合は下記関係式(Eq-2)を満たす。
(I) To propylene,
(II) a hydroxyl group-containing olefin;
(III) a catalyst component comprising the following (A) and (B);
Are added sequentially or simultaneously to cause a copolymerization reaction,
A method for producing a propylene-based polymer satisfying the following (i) to (iv).
(A) A metallocene compound represented by the following general formula [1].
(In the formula [1], R 2 is selected from a hydrocarbon group and a silicon-containing hydrocarbon group, and R 1 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 are selected from hydrogen, a hydrocarbon group, and a silicon-containing hydrocarbon group, and may be the same or different, and adjacent substituents from R 3 to R 10 are bonded to each other to form a ring. M is a metal selected from Group 4 of the periodic table, Y is carbon or silicon, Q is neutral capable of coordinating with a halogen, a hydrocarbon group, an anionic ligand or a lone pair of electrons. The ligands may be selected from the same or different combinations, and j is an integer of 1 to 4.)
(B) (B-1) Organometallic compound,
(B-2) an organoaluminum oxy compound, and
(B-3) a compound that reacts with the metallocene compound (A) to form an ion pair,
At least one compound selected from:
(i) the amount of hydroxyl group-containing olefin in the polymer is 10 mol% or less,
(ii) The weight average molecular weight (Mw) obtained by gel permeation chromatography (GPC) measurement of the polymer is 5000 or more,
(iii) The ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) (Mw / Mn) is in the range of 1.0 to 3.5,
(iv) The melting point ([Tm]; ° C.) measured by DSC of the polymer and the amount of hydroxyl group-containing olefin ([—OH]; mol%) measured by nuclear magnetic resonance (NMR) are 0 <[— OH. ] ≦ 3, the following relational expression (Eq-1) is satisfied, and when 3 <[− OH] ≦ 10, the following relational expression (Eq-2) is satisfied.
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| JPH0853516A (en) * | 1994-08-10 | 1996-02-27 | Mitsubishi Chem Corp | Propylene copolymer |
| JP2002145948A (en) * | 2000-11-13 | 2002-05-22 | Mitsui Chemicals Inc | Polar group-containing olefin copolymer and thermoplastic resin composition containing the copolymer |
| JP2002201225A (en) * | 2001-01-05 | 2002-07-19 | Tonen Chem Corp | Random copolymer and its manufacturing method |
| JP2003252930A (en) * | 2001-12-28 | 2003-09-10 | Mitsui Chemicals Inc | Polar group-containing olefin polymer and method for producing the same |
| JP2005105147A (en) * | 2003-09-30 | 2005-04-21 | National Institute Of Advanced Industrial & Technology | Random copolymer and method for producing the same |
| JP2005307113A (en) * | 2004-04-26 | 2005-11-04 | National Institute Of Advanced Industrial & Technology | Polar group-containing copolymer and method for producing the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH0853516A (en) * | 1994-08-10 | 1996-02-27 | Mitsubishi Chem Corp | Propylene copolymer |
| JP2002145948A (en) * | 2000-11-13 | 2002-05-22 | Mitsui Chemicals Inc | Polar group-containing olefin copolymer and thermoplastic resin composition containing the copolymer |
| JP2002201225A (en) * | 2001-01-05 | 2002-07-19 | Tonen Chem Corp | Random copolymer and its manufacturing method |
| JP2003252930A (en) * | 2001-12-28 | 2003-09-10 | Mitsui Chemicals Inc | Polar group-containing olefin polymer and method for producing the same |
| JP2005105147A (en) * | 2003-09-30 | 2005-04-21 | National Institute Of Advanced Industrial & Technology | Random copolymer and method for producing the same |
| JP2005307113A (en) * | 2004-04-26 | 2005-11-04 | National Institute Of Advanced Industrial & Technology | Polar group-containing copolymer and method for producing the same |
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