JP2010222464A - Method for producing polymer - Google Patents
Method for producing polymer Download PDFInfo
- Publication number
- JP2010222464A JP2010222464A JP2009070869A JP2009070869A JP2010222464A JP 2010222464 A JP2010222464 A JP 2010222464A JP 2009070869 A JP2009070869 A JP 2009070869A JP 2009070869 A JP2009070869 A JP 2009070869A JP 2010222464 A JP2010222464 A JP 2010222464A
- Authority
- JP
- Japan
- Prior art keywords
- polymer
- olefin
- meth
- monomer
- copolymer
- 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 126
- 238000004519 manufacturing process Methods 0.000 title claims description 24
- 239000000178 monomer Substances 0.000 claims abstract description 41
- 229920000098 polyolefin Polymers 0.000 claims abstract description 40
- 150000002736 metal compounds Chemical class 0.000 claims abstract description 21
- 239000012190 activator Substances 0.000 claims abstract description 16
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 15
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 6
- 230000000737 periodic effect Effects 0.000 claims abstract description 5
- 229920001577 copolymer Polymers 0.000 claims description 40
- -1 monoolefin compound Chemical class 0.000 claims description 38
- 150000001875 compounds Chemical class 0.000 claims description 32
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 claims description 31
- 239000004711 α-olefin Substances 0.000 claims description 27
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 18
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical group CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 11
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 11
- 229920005604 random copolymer Polymers 0.000 claims description 11
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 10
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 10
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052794 bromium Inorganic materials 0.000 claims description 6
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 5
- JRNVZBWKYDBUCA-UHFFFAOYSA-N N-chlorosuccinimide Chemical compound ClN1C(=O)CCC1=O JRNVZBWKYDBUCA-UHFFFAOYSA-N 0.000 claims description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 125000002950 monocyclic group Chemical group 0.000 claims description 4
- 125000003367 polycyclic group Chemical group 0.000 claims description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 3
- 238000004581 coalescence Methods 0.000 claims description 3
- VRLDVERQJMEPIF-UHFFFAOYSA-N dbdmh Chemical compound CC1(C)N(Br)C(=O)N(Br)C1=O VRLDVERQJMEPIF-UHFFFAOYSA-N 0.000 claims description 3
- 229920001519 homopolymer Polymers 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- HHBCEKAWSILOOP-UHFFFAOYSA-N 1,3-dibromo-1,3,5-triazinane-2,4,6-trione Chemical compound BrN1C(=O)NC(=O)N(Br)C1=O HHBCEKAWSILOOP-UHFFFAOYSA-N 0.000 claims description 2
- GJNCXCPHNRATIQ-UHFFFAOYSA-N 1-bromoazepan-2-one Chemical compound BrN1CCCCCC1=O GJNCXCPHNRATIQ-UHFFFAOYSA-N 0.000 claims description 2
- ZJEQUGWMBSKCCM-UHFFFAOYSA-N 1-bromopiperidine-2,6-dione Chemical compound BrN1C(=O)CCCC1=O ZJEQUGWMBSKCCM-UHFFFAOYSA-N 0.000 claims description 2
- MARXMDRWROUXMD-UHFFFAOYSA-N 2-bromoisoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(Br)C(=O)C2=C1 MARXMDRWROUXMD-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 239000005749 Copper compound Substances 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- 239000004793 Polystyrene Substances 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 125000004429 atom Chemical group 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 150000001880 copper compounds Chemical class 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
- 229910052702 rhenium Inorganic materials 0.000 claims description 2
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 239000010948 rhodium Substances 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 150000003949 imides Chemical group 0.000 claims 1
- 150000002894 organic compounds Chemical class 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 80
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 63
- 229910052757 nitrogen Inorganic materials 0.000 description 41
- 238000003756 stirring Methods 0.000 description 31
- 238000006116 polymerization reaction Methods 0.000 description 29
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 26
- 230000005587 bubbling Effects 0.000 description 26
- 150000003254 radicals Chemical class 0.000 description 25
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 23
- 239000000243 solution Substances 0.000 description 23
- 238000004458 analytical method Methods 0.000 description 22
- 238000005160 1H NMR spectroscopy Methods 0.000 description 21
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 description 21
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 18
- 239000000203 mixture Substances 0.000 description 18
- 239000002904 solvent Substances 0.000 description 17
- 239000011521 glass Substances 0.000 description 16
- 229920001155 polypropylene Polymers 0.000 description 16
- 239000004743 Polypropylene Substances 0.000 description 14
- 238000001816 cooling Methods 0.000 description 13
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 13
- 239000004926 polymethyl methacrylate Substances 0.000 description 13
- 229920002939 poly(N,N-dimethylacrylamides) Polymers 0.000 description 12
- 239000002002 slurry Substances 0.000 description 10
- 239000006228 supernatant Substances 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 8
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 7
- 238000010526 radical polymerization reaction Methods 0.000 description 7
- 239000000725 suspension Substances 0.000 description 7
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 6
- 239000011976 maleic acid Substances 0.000 description 6
- 229920002189 poly(glycerol 1-O-monomethacrylate) polymer Polymers 0.000 description 6
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 6
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 5
- 150000001336 alkenes Chemical class 0.000 description 5
- 239000000470 constituent Substances 0.000 description 5
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 5
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 5
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 4
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 4
- 150000001721 carbon Chemical group 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 229920001567 vinyl ester resin Polymers 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 3
- 229910021591 Copper(I) chloride Inorganic materials 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
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 3
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 description 3
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 3
- 150000002148 esters Chemical class 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
- 229920000768 polyamine Polymers 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 238000010557 suspension polymerization reaction Methods 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 2
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 2
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Chemical group CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- LQZMLBORDGWNPD-UHFFFAOYSA-N N-iodosuccinimide Chemical compound IN1C(=O)CCC1=O LQZMLBORDGWNPD-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
- 238000012662 bulk polymerization Methods 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 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
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- OTTZHAVKAVGASB-UHFFFAOYSA-N hept-2-ene Chemical compound CCCCC=CC OTTZHAVKAVGASB-UHFFFAOYSA-N 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- FSQQTNAZHBEJLS-UPHRSURJSA-N maleamic acid Chemical compound NC(=O)\C=C/C(O)=O FSQQTNAZHBEJLS-UPHRSURJSA-N 0.000 description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- DWFKOMDBEKIATP-UHFFFAOYSA-N n'-[2-[2-(dimethylamino)ethyl-methylamino]ethyl]-n,n,n'-trimethylethane-1,2-diamine Chemical compound CN(C)CCN(C)CCN(C)CCN(C)C DWFKOMDBEKIATP-UHFFFAOYSA-N 0.000 description 2
- VAMFXQBUQXONLZ-UHFFFAOYSA-N n-alpha-eicosene Natural products CCCCCCCCCCCCCCCCCCC=C VAMFXQBUQXONLZ-UHFFFAOYSA-N 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadec-1-ene Chemical compound CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000007870 radical polymerization initiator Substances 0.000 description 2
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Abstract
Description
本発明は、オレフィン系重合体セグメントとラジカル重合体セグメントとが化学結合した重合体の製造方法に関する。 The present invention relates to a method for producing a polymer in which an olefin polymer segment and a radical polymer segment are chemically bonded.
オレフィン系重合体セグメントとラジカル重合体セグメントとが化学結合した重合体の製造方法として、アルキルホウ素含有ポリオレフィンのホウ素含有基を過酸化物に変換して、メチルメタクリレートなどのモノマーをラジカル重合させることにより、ブロックポリマーを製造する方法が開示されている(例えば特許文献1を参照)。また、オレフィンと極性基含有モノマーとの共重合体中の極性基、あるいは不飽和結合の変性により得られた極性基含有オレフィン系重合体中の極性基を、ラジカル重合開始剤に変換して、メチルメタクリレートなどの極性基含有モノマーをラジカル重合する方法が開示されている(特許文献2や3を参照)。 As a method for producing a polymer in which an olefin polymer segment and a radical polymer segment are chemically bonded, a boron-containing group of an alkylboron-containing polyolefin is converted into a peroxide, and a monomer such as methyl methacrylate is radically polymerized. A method for producing a block polymer is disclosed (for example, see Patent Document 1). Moreover, the polar group in the copolymer of the olefin and the polar group-containing monomer or the polar group in the polar group-containing olefin polymer obtained by modification of the unsaturated bond is converted into a radical polymerization initiator, A method of radical polymerization of a polar group-containing monomer such as methyl methacrylate is disclosed (see Patent Documents 2 and 3).
近年では、オレフィン系重合体を直接ハロゲン化して得られるハロゲン変性重合体を利用してラジカル重合を行うことにより、オレフィン系重合体セグメントとラジカル重合体セグメントとが化学結合した重合体を製造する方法が報告されている(特許文献4を参照)。 In recent years, a method of producing a polymer in which an olefin polymer segment and a radical polymer segment are chemically bonded by performing radical polymerization using a halogen-modified polymer obtained by directly halogenating an olefin polymer. Has been reported (see Patent Document 4).
従来のいずれの製造方法でも、分子内に重合開始点を導入したオレフィン系重合体をマクロ開始剤として用いるため、ラジカル重合を実施する前に、オレフィン系重合体へ官能基を導入するプロセスと、さらにはポリマーを分離・精製するなどのプロセスが必要であった。 In any of the conventional production methods, since an olefin polymer having a polymerization initiation point introduced into the molecule is used as a macroinitiator, a process of introducing a functional group into the olefin polymer before carrying out radical polymerization, Furthermore, a process such as separation and purification of the polymer was necessary.
本発明は、上記の従来技術に鑑みてなされたものであり、より簡便な方法でオレフィン系重合体セグメントとラジカル重合体セグメントとが化学結合した重合体を製造する方法を提供することを目的とする。具体的には、マクロ開始剤である「分子内に重合開始点を導入したオレフィン系重合体」の製造プロセスを簡略化することで、オレフィン系重合体セグメントとラジカル重合体セグメントとが化学結合した重合体を、工業的に有利な方法で製造することを目的とする。 The present invention has been made in view of the above prior art, and aims to provide a method for producing a polymer in which an olefin polymer segment and a radical polymer segment are chemically bonded by a simpler method. To do. Specifically, the olefin polymer segment and the radical polymer segment were chemically bonded by simplifying the manufacturing process of the macroinitiator “olefin polymer with a polymerization initiation point introduced into the molecule”. The object is to produce the polymer in an industrially advantageous manner.
本発明者らは、該課題を解決すべく鋭意検討を進めた結果、特定の活性化剤を用いてオレフィン系重合体を活性化させて、ラジカル重合性単量体を重合することにより、上記課題を解決しうることを見出して本発明に至った。 As a result of diligent studies to solve the problem, the present inventors activated the olefin polymer using a specific activator and polymerized a radical polymerizable monomer, thereby The inventors have found that the problems can be solved and have reached the present invention.
すなわち本発明は、オレフィン系重合体セグメントとラジカル重合体セグメントとが化学結合した重合体の製造方法であって、ハロゲン元素を含まないオレフィン系重合体(A)と、周期律表第3族〜第11族から選ばれる遷移金属元素を含む金属化合物(B)と、分子内にハロゲン−ハロゲン結合または窒素−ハロゲン結合を有する活性化剤(C)との存在下で、ラジカル重合性単量体を重合させる工程を含むことを特徴とする。 That is, the present invention is a method for producing a polymer in which an olefin polymer segment and a radical polymer segment are chemically bonded, and includes an olefin polymer (A) not containing a halogen element, a group 3 of the periodic table, A radical polymerizable monomer in the presence of a metal compound (B) containing a transition metal element selected from Group 11 and an activator (C) having a halogen-halogen bond or a nitrogen-halogen bond in the molecule. And a step of polymerizing.
本発明は、オレフィン系重合体セグメントとラジカル重合体セグメントとが化学結合した重合体の製造方法の改良を提供する。本発明の方法によれば、工業的に広く製造されているポリエチレンやポリプロピレンなどのオレフィン系重合体を原料にして、一段階反応で、目的とするオレフィン系重合体セグメントとラジカル重合体セグメントとが化学結合した重合体を製造することが可能である。そのため、従来技術と比較して製造工程を大幅に簡素化することができ、製造コストやエネルギー消費の面で非常に有利である。 The present invention provides an improved method for producing a polymer in which an olefin polymer segment and a radical polymer segment are chemically bonded. According to the method of the present invention, an olefin polymer such as polyethylene or polypropylene, which is widely produced industrially, is used as a raw material, and the desired olefin polymer segment and radical polymer segment are obtained in a one-step reaction. It is possible to produce chemically bonded polymers. Therefore, the manufacturing process can be greatly simplified as compared with the prior art, which is very advantageous in terms of manufacturing cost and energy consumption.
以下、本発明の重合体の製造方法について具体的に説明する。
本発明は、オレフィン系重合体セグメントとラジカル重合体セグメントとが化学結合した重合体を製造する方法である。ハロゲン元素を含まないオレフィン系重合体(A)、周期律表第3族〜第11族から選ばれる遷移金属元素を含む金属化合物(B)、および分子内にハロゲン−ハロゲン結合または窒素−ハロゲン結合を有する活性化剤(C)の存在下で、ラジカル重合性単量体を重合させることを特徴とする。
Hereafter, the manufacturing method of the polymer of this invention is demonstrated concretely.
The present invention is a method for producing a polymer in which an olefin polymer segment and a radical polymer segment are chemically bonded. Olefin polymer containing no halogen element (A), metal compound (B) containing a transition metal element selected from Group 3 to Group 11 of the periodic table, and halogen-halogen bond or nitrogen-halogen bond in the molecule It is characterized by polymerizing a radically polymerizable monomer in the presence of an activator (C) having
本発明に用いられる、ハロゲン元素を含まないオレフィン系重合体(A)は、炭素−炭素二重結合を一つだけ有するモノオレフィン化合物、あるいは芳香環を有するモノオレフィン化合物から構成される重合体であることが好ましい。炭素−炭素二重結合を複数有する化合物(例えば、ヘキサジエンやオクタジエンなどの直鎖状ジエン化合物、ジビニルベンゼンなどのスチレン系ジエン化合物、ビニルノルボルネンやエチリデンノルボルネンなどの環状ジオレフィン化合物など)の重合体、またはそれを共重合成分とする共重合体は、ラジカル重合性単量体を重合させる段階で、ジエン化合物に由来する不飽和結合同士が架橋してゲル化するため好ましくない場合がある。 The olefin polymer (A) containing no halogen element used in the present invention is a polymer composed of a monoolefin compound having only one carbon-carbon double bond or a monoolefin compound having an aromatic ring. Preferably there is. A polymer of a compound having a plurality of carbon-carbon double bonds (for example, a linear diene compound such as hexadiene or octadiene, a styrene diene compound such as divinylbenzene, a cyclic diolefin compound such as vinyl norbornene or ethylidene norbornene), Or the copolymer which uses it as a copolymerization component may be unpreferable since the unsaturated bond derived from a diene compound bridge | crosslinks and gelatinizes in the step which superposes | polymerizes a radically polymerizable monomer.
したがって本発明に用いられるオレフィン系重合体(A)は、例えば、下記(A1)〜(A5)からなる群から選ばれる重合体が挙げられる。これらは2種以上組み合わせて用いられてもよい。
(A1):CH2=CH−CXH2X+1(xは0または正の整数)で示されるα−オレフィン化合物の単独重合体または共重合体。
(A2):CH2=CH−CXH2X+1(xは0または正の整数)で示されるα−オレフィン化合物と芳香環を有するモノオレフィン化合物との共重合体。
(A3):CH2=CH−CXH2X+1(xは0または正の整数)で示されるα−オレフィン化合物と下記一般式(1)で表される環状モノオレフィン化合物との共重合体。
(A4):CH2=CH−CXH2X+1(xは0または正の整数)で示されるα−オレフィン化合物と不飽和カルボン酸またはその誘導体とのランダム共重合体。
(A5):前記重合体(A1)〜(A4)のいずれかを、不飽和カルボン酸またはその誘導体により変性したもの。
Accordingly, examples of the olefin polymer (A) used in the present invention include polymers selected from the group consisting of the following (A1) to (A5). Two or more of these may be used in combination.
(A1): A homopolymer or copolymer of an α-olefin compound represented by CH 2 ═CH—C X H 2X + 1 (x is 0 or a positive integer).
(A2): A copolymer of an α-olefin compound represented by CH 2 ═CH—C X H 2X + 1 (x is 0 or a positive integer) and a monoolefin compound having an aromatic ring.
(A3): Co-weight of an α-olefin compound represented by CH 2 ═CH—C X H 2X + 1 (x is 0 or a positive integer) and a cyclic monoolefin compound represented by the following general formula (1) Coalescence.
(A4): A random copolymer of an α-olefin compound represented by CH 2 ═CH—C X H 2X + 1 (x is 0 or a positive integer) and an unsaturated carboxylic acid or a derivative thereof.
(A5): A polymer obtained by modifying any of the polymers (A1) to (A4) with an unsaturated carboxylic acid or a derivative thereof.
重合体(A1)について:
本発明で用いられる重合体(A1)は、CH2=CH−CXH2X+1(xは0または正の整数)で示されるα−オレフィン化合物の単独重合体または共重合体である。
About polymer (A1):
The polymer (A1) used in the present invention is a homopolymer or copolymer of an α-olefin compound represented by CH 2 ═CH—C X H 2X + 1 (x is 0 or a positive integer).
重合体(A1)の構成モノマーである、CH2=CH−CXH2X+1(xは0または正の整数)で示されるα−オレフィン化合物の具体例には、エチレン、プロピレン、1-ブテン、1-ペンテン、3-メチル-1-ブテン、1-ヘキセン、4-メチル-1-ペンテン、3-メチル-1-ペンテン、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数が4〜20の直鎖状または分岐状のα−オレフィンが含まれる。これらの例示オレフィン類の中では、エチレン、プロピレン、1-ブテン、1-ヘキセン、4-メチル-1-ペンテン、1-オクテンから選ばれる少なくとも1種のオレフィンを使用することが好ましく、より好ましくはエチレン、プロピレン、1-ブテンである。 Specific examples of the α-olefin compound represented by CH 2 ═CH—C X H 2X + 1 (x is 0 or a positive integer), which is a constituent monomer of the polymer (A1), include ethylene, propylene, 1 − Butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, Linear or branched α-olefins having 4 to 20 carbon atoms such as 1-hexadecene, 1-octadecene, 1-eicosene and the like are included. Among these exemplified olefins, it is preferable to use at least one olefin selected from ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene and 1-octene, more preferably Ethylene, propylene and 1-butene.
重合体(A1)は、上記α−オレフィン化合物を単独重合または共重合して得られるものであればよく、特に制限はない。重合体(A1)の好ましい具体例には、低密度ポリエチレン、中密度ポリエチレン、高密度ポリエチレン、直鎖状低密度ポリエチレン、超高分子量ポリエチレンなどのエチレン系重合体;プロピレンホモポリマー、プロピレンランダムコポリマー、プロピレンブロックコポリマーなどのプロピレン系重合体;ポリブテン、ポリ(4-メチル-1-ペンテン)、ポリ(1-ヘキセン)、エチレン−プロピレン共重合体、エチレン−ブテン共重合体、エチレン−ヘキセン共重合体、エチレン−オクテン共重合体、エチレン−(4-メチル-1-ペンテン)共重合体、プロピレン−ブテン共重合体、プロピレン−(4-メチル-1-ペンテン)共重合体、プロピレン−ヘキセン共重合体、プロピレン−オクテン共重合体などが含まれる。なかでも、エチレン系重合体、プロピレン系重合体、エチレン−プロピレン共重合体、エチレン−ブテン共重合体がより好ましい。 The polymer (A1) is not particularly limited as long as it is obtained by homopolymerization or copolymerization of the α-olefin compound. Preferred specific examples of the polymer (A1) include ethylene polymers such as low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, and ultrahigh molecular weight polyethylene; propylene homopolymer, propylene random copolymer, Propylene polymers such as propylene block copolymer; polybutene, poly (4-methyl-1-pentene), poly (1-hexene), ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-hexene copolymer , Ethylene-octene copolymer, ethylene- (4-methyl-1-pentene) copolymer, propylene-butene copolymer, propylene- (4-methyl-1-pentene) copolymer, propylene-hexene copolymer Polymers, propylene-octene copolymers and the like are included. Of these, ethylene polymers, propylene polymers, ethylene-propylene copolymers, and ethylene-butene copolymers are more preferable.
重合体(A2)について:
本発明で用いられる重合体(A2)は、CH2=CH−CXH2X+1(xは0または正の整数)で示されるα−オレフィン化合物と芳香環を有するモノオレフィン化合物との共重合体である。
About polymer (A2):
The polymer (A2) used in the present invention is a copolymer of an α-olefin compound represented by CH 2 ═CH—C X H 2X + 1 (x is 0 or a positive integer) and a monoolefin compound having an aromatic ring. It is a polymer.
共重合体(A2)の構成モノマーである、CH2=CH−CXH2X+1(xは0または正の整数)で示されるα−オレフィン化合物の具体例には、上記(A1)の項で記載したα−オレフィン化合物が含まれる。一方、芳香環を有するモノオレフィン化合物の具体例には、スチレン、ビニルトルエン、α−メチルスチレン等のスチレン系化合物やビニルピリジンなどが含まれる。 Specific examples of the α-olefin compound represented by CH 2 ═CH—C X H 2X + 1 (x is 0 or a positive integer), which is a constituent monomer of the copolymer (A2), include the above (A1). The α-olefin compound described in the item is included. On the other hand, specific examples of the monoolefin compound having an aromatic ring include styrene compounds such as styrene, vinyltoluene, and α-methylstyrene, vinylpyridine, and the like.
共重合体(A2)は、上記α−オレフィン化合物と芳香環を有するモノオレフィン化合物とを共重合して得られるものであればよく、特に制限はない。共重合体(A2)の好ましい例には、エチレン−スチレン共重合体、プロピレン−スチレン共重合体、エチレン−プロピレン−スチレン三元共重合体、エチレン−ブテン−スチレン三元共重合体などが含まれる。共重合体(A2)中に含まれるα−オレフィン化合物に由来するユニットの含量は、オレフィン系重合体としての性質を保持するために50モル%以上が好ましく、より好ましくは60モル%以上である。 The copolymer (A2) is not particularly limited as long as it is obtained by copolymerizing the α-olefin compound and a monoolefin compound having an aromatic ring. Preferred examples of the copolymer (A2) include an ethylene-styrene copolymer, a propylene-styrene copolymer, an ethylene-propylene-styrene terpolymer, an ethylene-butene-styrene terpolymer. It is. The content of the unit derived from the α-olefin compound contained in the copolymer (A2) is preferably 50 mol% or more, more preferably 60 mol% or more in order to maintain the properties as an olefin polymer. .
共重合体(A3)について:
共重合体(A3)は、CH2=CH−CXH2X+1(xは0または正の整数)で示されるα−オレフィン化合物と下記一般式(1)で表される環状モノオレフィン化合物との共重合体である。
Regarding copolymer (A3):
The copolymer (A3) is composed of an α-olefin compound represented by CH 2 ═CH—C X H 2X + 1 (x is 0 or a positive integer) and a cyclic monoolefin compound represented by the following general formula (1) And a copolymer.
共重合体(A3)の構成モノマーであるCH2=CH−CXH2X+1(xは0または正の整数)で示されるα−オレフィン化合物の例には、上記(A1)の項で記載したα−オレフィン化合物が含まれる。 Examples of the α-olefin compound represented by CH 2 ═CH—C X H 2X + 1 (x is 0 or a positive integer), which is a constituent monomer of the copolymer (A3), include those in the section (A1) above. The described α-olefin compounds are included.
共重合体(A3)の構成モノマーである環状モノオレフィン化合物を示す一般式(1)において、nは0または1であり、mは0または正の整数であり、qは0または1であり、qが1の場合には、RaおよびRbは、それぞれ独立に、下記の原子または炭化水素基を表し、qが0の場合には、それぞれの結合手が結合して5員環を形成する。 In the general formula (1) showing the cyclic monoolefin compound that is a constituent monomer of the copolymer (A3), n is 0 or 1, m is 0 or a positive integer, q is 0 or 1, When q is 1, R a and R b each independently represent the following atom or hydrocarbon group, and when q is 0, each bond is bonded to form a 5-membered ring. To do.
一般式(1)におけるR1〜R18ならびにRaおよびRbが示す炭化水素基は、通常、炭素原子数1〜20のアルキル基、または炭素原子数3〜15のシクロアルキル基などである。より具体的に、アルキル基の例には、メチル基、エチル基、プロピル基、アミル基、ヘキシル基、オクチル基、デシル基、ドデシル基およびオクタデシル基などが含まれ;シクロアルキル基の例には、シクロヘキシル基が含まれる。 The hydrocarbon group represented by R 1 to R 18 and R a and R b in the general formula (1) is usually an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 3 to 15 carbon atoms. . More specifically, examples of alkyl groups include methyl, ethyl, propyl, amyl, hexyl, octyl, decyl, dodecyl and octadecyl groups; examples of cycloalkyl groups A cyclohexyl group.
さらに、一般式(1)におけるR15とR16とが、R17とR18とが、R15とR17とが、R16とR18とが、R15とR18とが、あるいはR16とR17とがそれぞれ結合して(互いに共同して)、単環または多環を形成していてもよい。ここで形成される単環または多環の具体例が以下に示されるが、特に限定されない。 Furthermore, R 15 and R 16 in the general formula (1) are R 17 and R 18 , R 15 and R 17 are R 16 and R 18 , R 15 and R 18 are R or R 16 and R 17 may be bonded to each other (in cooperation with each other) to form a monocyclic or polycyclic ring. Specific examples of the monocyclic or polycyclic ring formed here are shown below, but are not particularly limited.
上記単環または多環の例示において、1の番号を付した炭素原子は、上記一般式(1)においてR15およびR16が結合している炭素原子を表し;2の番号を付した炭素原子は、上記一般式(1)においてR17およびR18が結合している炭素原子を表す。 In the monocyclic or polycyclic examples, the carbon atom numbered 1 represents the carbon atom to which R 15 and R 16 are bonded in the general formula (1); the carbon atom numbered 2 Represents a carbon atom to which R 17 and R 18 are bonded in the general formula (1).
上記一般式(1)で表される環状オレフィンの具体例には、ビシクロ[2.2.1]ヘプト-2-エン誘導体、トリシクロ[4.3.0.12,5]-3-デセン誘導体、トリシクロ[4.3.0.12,5]-3-ウンデセン誘導体、テトラシクロ[4.4.0.12,5.17,10]-3-ドデセン誘導体、ペンタシクロ[7.4.0.12,5.19,12.08,13]-3-ペンタデセン誘導体、ペンタシクロ[6.5.1.13,6.02,7.09,13]-4-ペンタデセン誘導体、ペンタシクロ[8.4.0.12,3.19,12.08,13]-3-ヘキサデセン誘導体、ペンタシクロ[6.6.1.13,6.02,7.09,14]-4-ヘキサデセン誘導体、ペンタシクロペンタデカジエン誘導体、ヘキサシクロ[6.6.1.13,6.110,13.02,7.09,14]-4-ヘプタデセン誘導体、ヘプタシクロ[8.7.0.13,6.110,17.112,15.02,7.011,16 ]-4-エイコセン誘導体、ヘプタシクロ-5-エイコセン誘導体、ヘプタシクロ[8.8.0.14,7.111,18.113,16.03,8.012,17]-5-ヘンエイコセン誘導体、オクタシクロ[8.8.0.12,9.14,7.111,18.113,16.03,8.012,17]-5-ドコセン誘導体、ノナシクロ[10.9.1.14,7.113,20.115,18.03,8.02,10.012,21.014,19]-5-ペンタコセン誘導体、ノナシクロ[10.10.1.15,8.114,21.116,19.02,11.04,9.013,22.015,20]-5-ヘキサコセン誘導体などが含まれる。 Specific examples of the cyclic olefin represented by the general formula (1) include a bicyclo [2.2.1] hept-2-ene derivative, a tricyclo [4.3.0.1 2,5 ] -3-decene derivative, and a tricyclo [4.3. 0.1 2,5] -3-undecene derivatives, tetracyclo [4.4.0.1 2,5 .1 7,10] -3-dodecene derivatives, pentacyclo [7.4.0.1 2,5 .1 9,12 .0 8,13] 3-pentadecene derivatives, pentacyclo [6.5.1.1 3,6 .0 2,7 .0 9,13] -4- pentadecene derivatives, pentacyclo [8.4.0.1 2,3 .1 9,12 .0 8,13] 3-hexadecene derivative, pentacyclo [6.6.1.1 3,6 .0 2,7 .0 9,14] -4- hexadecene derivatives, penta cyclopentadiene decadiene derivative, hexacyclo [6.6.1.1 3,6 .1 10, 13.0 2,7 .0 9,14] -4-heptadecene derivatives, heptacyclo [8.7.0.1 3,6 .1 10,17 .1 12,15 .0 2,7 .0 11,16] -4- Eicosene derivatives, heptacyclo-5-eicosene derivatives, heptacyclo 8.8.0.1 4,7 .1 11,18 .1 13,16 .0 3,8 .0 12,17] -5- heneicosene derivatives, octacyclo [8.8.0.1 2,9 .1 4,7 .1 11, 18.1 13,16 .0 3,8 .0 12,17] -5-docosene derivatives, Nonashikuro [10.9.1.1 4,7 .1 13,20 .1 15,18 .0 3,8 .0 2, 10.0 12,21 .0 14,19] -5-pentacosene derivatives, Nonashikuro [10.10.1.1 5,8 .1 14,21 .1 16,19 .0 2,11 .0 4,9 .0 13, 22.0 15,20] -5-hexacosenoic derivatives, and the like.
一般式(1)で表される環状モノオレフィン化合物は、シクロペンタジエンと対応する構造を有するオレフィン類とを、ディールス・アルダー反応させることによって製造することができる。これらの環状オレフィンは、単独であるいは2種以上組み合わせて用いることができる。 The cyclic monoolefin compound represented by the general formula (1) can be produced by subjecting cyclopentadiene and an olefin having a corresponding structure to Diels-Alder reaction. These cyclic olefins can be used alone or in combination of two or more.
一般式(1)で表される環状モノオレフィン化合物から誘導される構成単位は、下記一般式(2)で示される。
式(2)において、n、m、q、R1〜R18ならびにRaおよびRbは、式(1)と同じ意味である。 In the formula (2), n, m, q, R 1 to R 18, R a and R b have the same meaning as in the formula (1).
共重合体(A3)は、上記α−オレフィン化合物と一般式(1)で表される環状モノオレフィン化合物とを共重合して得られるものであればよく、特に制限はない。好ましくはエチレンとビシクロ[2.2.1]ヘプト-2-エンとの共重合体、またはエチレンとテトラシクロ[4.4.0.12,5.17,10]-3-ドデセンとの共重合体などである。 The copolymer (A3) is not particularly limited as long as it is obtained by copolymerizing the α-olefin compound and the cyclic monoolefin compound represented by the general formula (1). Preferably is ethylene and bicyclo [2.2.1] copolymers of hept-2-ene, or ethylene and tetracyclo [4.4.0.1 2,5 .1 7,10] -3- dodecene, copolymers .
共重合体(A3)中に含まれるα−オレフィン化合物に由来するユニットの含量は、オレフィン系重合体としての性質を保持するために50モル%以上が好ましく、より好ましくは60モル%以上である。 The content of the unit derived from the α-olefin compound contained in the copolymer (A3) is preferably 50 mol% or more, more preferably 60 mol% or more in order to maintain the properties as an olefin polymer. .
ランダム共重合体(A4)について:
ランダム共重合体(A4)は、CH2=CH−CXH2X+1(xは0または正の整数)で示されるα−オレフィン化合物と、不飽和カルボン酸またはその誘導体とのランダム共重合体である。
About the random copolymer (A4):
The random copolymer (A4) is a random copolymer of an α-olefin compound represented by CH 2 ═CH—C X H 2X + 1 (x is 0 or a positive integer) and an unsaturated carboxylic acid or a derivative thereof. It is a coalescence.
ランダム共重合体(A4)の構成モノマーである、CH2=CH−CXH2X+1(xは0または正の整数)で示されるα−オレフィン化合物の例には、上記(A1)の項で記載したα−オレフィン化合物が含まれる。 Examples of the α-olefin compound represented by CH 2 ═CH—C X H 2X + 1 (x is 0 or a positive integer), which is a constituent monomer of the random copolymer (A4), include the above-mentioned item (A1). The described α-olefin compounds are included.
一方、不飽和カルボン酸またはその誘導体の例には、不飽和モノカルボン酸およびその誘導体、不飽和ジカルボン酸およびその誘導体、ならびにビニルエステル類が含まれる。より具体的には、(メタ)アクリル酸、(メタ)アクリル酸エステル、(メタ)アクリル酸アミド、マレイン酸、マレイン酸無水物、マレイン酸エステル、マレイン酸アミド、マレイン酸イミド、酢酸ビニルや酪酸ビニルなどの脂肪族ビニルエステル類などが挙げられる。 On the other hand, examples of unsaturated carboxylic acids or derivatives thereof include unsaturated monocarboxylic acids and derivatives thereof, unsaturated dicarboxylic acids and derivatives thereof, and vinyl esters. More specifically, (meth) acrylic acid, (meth) acrylic acid ester, (meth) acrylic acid amide, maleic acid, maleic anhydride, maleic acid ester, maleic acid amide, maleic acid imide, vinyl acetate and butyric acid Examples thereof include aliphatic vinyl esters such as vinyl.
ランダム共重合体(A4)は、上記α−オレフィン化合物と不飽和カルボン酸またはその誘導体とのランダム共重合体であればよく、特に制限はない。ランダム共重合体(A4)の好ましい例には、エチレン−(メタ)アクリル酸共重合体、エチレン−(メタ)アクリル酸エステル共重合体、エチレン−無水マレイン酸共重合体、エチレン−酢酸ビニル共重合体などが含まれる。 The random copolymer (A4) is not particularly limited as long as it is a random copolymer of the α-olefin compound and the unsaturated carboxylic acid or derivative thereof. Preferred examples of the random copolymer (A4) include an ethylene- (meth) acrylic acid copolymer, an ethylene- (meth) acrylic acid ester copolymer, an ethylene-maleic anhydride copolymer, and an ethylene-vinyl acetate copolymer. Polymers and the like are included.
ランダム共重合体(A4)中に含まれるα−オレフィン化合物に由来するユニットの含量は、オレフィン系重合体としての性質を保持するために50モル%以上が好ましく、より好ましくは60モル%以上である。 The content of the unit derived from the α-olefin compound contained in the random copolymer (A4) is preferably 50 mol% or more, more preferably 60 mol% or more in order to maintain the properties as an olefin polymer. is there.
重合体(A5)について:
重合体(A5)は、前記重合体(A1)〜(A4)のいずれかを、不飽和カルボン酸またはその誘導体により変性したものである。
About polymer (A5):
The polymer (A5) is obtained by modifying any of the polymers (A1) to (A4) with an unsaturated carboxylic acid or a derivative thereof.
前記重合体(A1)〜(A4)のいずれかを変性するための不飽和カルボン酸またはその誘導体の具体例には、マレイン酸、マレイン酸無水物、マレイン酸エステル、マレイン酸アミド、マレイン酸イミドなどが含まれる。これらのうち、好ましくはマレイン酸無水物である。 Specific examples of the unsaturated carboxylic acid or its derivative for modifying any of the polymers (A1) to (A4) include maleic acid, maleic anhydride, maleic ester, maleic amide, maleic imide Etc. are included. Of these, maleic anhydride is preferred.
前記重合体(A1)〜(A4)で表される重合体のいずれかを、不飽和カルボン酸またはその誘導体により変性する方法としては、有機過酸化物などのラジカル発生剤の存在下に、あるいは紫外線や放射線の存在下に、不飽和カルボン酸またはその誘導体を前記重合体(A1)〜(A4)と反応させる方法などが含まれる。 As a method of modifying any of the polymers represented by the polymers (A1) to (A4) with an unsaturated carboxylic acid or a derivative thereof, in the presence of a radical generator such as an organic peroxide, or Examples include a method in which an unsaturated carboxylic acid or a derivative thereof is reacted with the polymers (A1) to (A4) in the presence of ultraviolet rays or radiation.
前記重合体(A1)〜(A5)を製造する条件や方法については特に制限はないが、例えばチーグラー・ナッタ触媒やメタロセン触媒、ポストメタロセン触媒などのような公知の遷移金属触媒を用いた配位アニオン重合や、高圧下あるいは放射線照射下でのラジカル重合などの方法を用いることができる。また、上記方法で製造したオレフィン系重合体を、熱やラジカルで分解したものを用いることもできる。 The conditions and method for producing the polymers (A1) to (A5) are not particularly limited. For example, coordination using a known transition metal catalyst such as a Ziegler-Natta catalyst, a metallocene catalyst, or a postmetallocene catalyst. Methods such as anionic polymerization and radical polymerization under high pressure or irradiation can be used. Moreover, what decomposed | disassembled the olefin type polymer manufactured by the said method with the heat | fever or a radical can also be used.
本発明で用いられるオレフィン系重合体(A)は、ゲルパーミエーションクロマトグラフィー(GPC)により測定したポリスチレン換算の重量平均分子量が1×103〜1×107であり、好ましくは5×103〜1×106であり、より好ましくは1×104〜5×105である。 The olefin polymer (A) used in the present invention has a polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography (GPC) of 1 × 10 3 to 1 × 10 7 , preferably 5 × 10 3. ˜1 × 10 6 , more preferably 1 × 10 4 to 5 × 10 5 .
本発明ではラジカル重合性単量体を重合させるが、この重合反応は、周期律表第3族〜第11族から選ばれる遷移金属元素を含む金属化合物(B)を触媒として行われる。金属化合物(B)は、好ましくは、チタン、ジルコニウム、モリブデン、レニウム、鉄、ルテニウム、ロジウム、コバルト、ニッケル、パラジウム、銅から選ばれる金属を含む化合物であり;さらに好ましくは、0価の銅、1価の銅、2価のルテニウム、2価の鉄、または2価のニッケルの錯体などであり、なかでも銅錯体が好ましい。 In the present invention, a radically polymerizable monomer is polymerized, and this polymerization reaction is performed using a metal compound (B) containing a transition metal element selected from Group 3 to Group 11 of the periodic table as a catalyst. The metal compound (B) is preferably a compound containing a metal selected from titanium, zirconium, molybdenum, rhenium, iron, ruthenium, rhodium, cobalt, nickel, palladium, copper; more preferably, zero-valent copper, Examples of the complex include monovalent copper, divalent ruthenium, divalent iron, and divalent nickel. Of these, a copper complex is preferable.
金属化合物(B)である1価の銅化合物の具体例には、塩化第一銅、臭化第一銅、ヨウ化第一銅、シアン化第一銅、酸化第一銅、過塩素酸第一銅などが含まれる。 Specific examples of the monovalent copper compound which is the metal compound (B) include cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, cuprous oxide, perchloric acid One cup etc. are included.
また、2価の塩化ルテニウムのトリストリフェニルホスフィン錯体(RuCl2(PPh3)3)も、金属化合物(B)として好適である。金属化合物(B)をルテニウム化合物として用いる場合は、活性化剤としてアルミニウムアルコキシド類を組み合わせて用いる。
さらに、2価の鉄のビストリフェニルホスフィン錯体(FeCl2(PPh3)2)、2価のニッケルのビストリフェニルホスフィン錯体(NiCl2(PPh3)2)、および2価のニッケルのビストリブチルホスフィン錯体(NiBr2(PBu3)2)も金属化合物(B)として好適であり、触媒として作用する。
A tristriphenylphosphine complex of divalent ruthenium chloride (RuCl 2 (PPh 3 ) 3 ) is also suitable as the metal compound (B). When using a metal compound (B) as a ruthenium compound, an aluminum alkoxide is used in combination as an activator.
Further, a divalent iron bistriphenylphosphine complex (FeCl 2 (PPh 3 ) 2 ), a divalent nickel bistriphenylphosphine complex (NiCl 2 (PPh 3 ) 2 ), and a divalent nickel bistributylphosphine complex (NiBr 2 (PBu 3 ) 2 ) is also suitable as the metal compound (B) and acts as a catalyst.
金属化合物(B)の触媒活性を高めるために、金属化合物(B)の配位子となる化合物を組み合わせて用いてもよい。配位子となる化合物の例には、2,2'-ビピリジルもしくはその誘導体;1,10-フェナントロリンもしくはその誘導体;またはテトラメチルエチレンジアミン、ペンタメチルジエチレントリアミン、ヘキサメチルトリエチレンテトラミンもしくはヘキサメチルトリス(2−アミノエチル)アミンなどのポリアミンなどが含まれる。このうち、好ましくはペンタメチルジエチレントリアミンやヘキサメチルトリエチレンテトラミンである。 In order to enhance the catalytic activity of the metal compound (B), a compound that becomes a ligand of the metal compound (B) may be used in combination. Examples of the ligand compound include 2,2′-bipyridyl or a derivative thereof; 1,10-phenanthroline or a derivative thereof; or tetramethylethylenediamine, pentamethyldiethylenetriamine, hexamethyltriethylenetetramine, or hexamethyltris (2 -Polyamines such as -aminoethyl) amine. Of these, pentamethyldiethylenetriamine and hexamethyltriethylenetetramine are preferable.
これらのポリアミンの使用量が少なすぎると、金属化合物(B)の溶媒またはモノマーへの溶解性が低くなるため触媒活性が極端に低下するもしくは持続しない場合があり;多すぎると、得られるポリマー中に残留して着色や臭いの原因となる場合がある。そのため、ポリアミンの使用量は、金属化合物(B)に対して通常0.1〜1,000等量の範囲であり、好ましくは1〜800等量、より好ましくは10〜300等量の範囲である。 If the amount of these polyamines used is too small, the solubility of the metal compound (B) in the solvent or monomer may be low, so that the catalytic activity may be extremely reduced or not sustained; Residues may cause coloring and odor. Therefore, the usage-amount of polyamine is the range of 0.1-1,000 equivalent normally with respect to a metal compound (B), Preferably it is 1-800 equivalent, More preferably, it is the range of 10-300 equivalent. is there.
本発明におけるラジカル重合性単量体の重合反応は、活性化剤(C)の存在下で行われる。活性化剤(C)は、光照射下や高温条件下でホモ解裂してラジカル種を生成し、オレフィン系重合体(A)を攻撃して、オレフィン系重合体(A)をマクロラジカルとする。マクロラジカルとなったオレフィン系重合体(A)を開始剤として、系内に存在する金属化合物(B)の触媒作用によりラジカル重合性単量体が重合すると考えられる。 The polymerization reaction of the radically polymerizable monomer in the present invention is performed in the presence of an activator (C). The activator (C) is homo-cleavable under light irradiation or high temperature conditions to generate radical species, attack the olefin polymer (A), and turn the olefin polymer (A) into a macro radical. To do. It is considered that the radical polymerizable monomer is polymerized by the catalytic action of the metal compound (B) present in the system using the olefin polymer (A) that has become a macro radical as an initiator.
また、活性化剤(C)のホモ解裂で生じたハロゲンラジカルとの反応により、金属化合物(B)の酸化種が生成する。金属化合物(B)の酸化種がラジカル重合を制御することで、目的とするオレフィン系重合体セグメントとラジカル重合体セグメントとが化学結合した重合体が効率よく製造されると考えられる。 In addition, oxidized species of the metal compound (B) are generated by a reaction with a halogen radical generated by homo-cleavage of the activator (C). It is considered that the polymer in which the target olefin polymer segment and the radical polymer segment are chemically bonded is efficiently produced by controlling the radical polymerization by the oxidizing species of the metal compound (B).
本発明で用いられる活性化剤(C)は、分子内にハロゲン−ハロゲン結合または窒素−ハロゲン結合を有することが好ましく、活性化剤(C)の具体例には塩素、臭素、ヨウ素、N-クロロスクシンイミド、N-ブロモスクシンイミド、N-ヨードスクシンイミド、N-ブロモカプロラクタム、N-ブロモフタルイミド、1,3-ジブロモ-5,5-ジメチルヒダントイン、N-クロログルタルイミド、N-ブロモグルタルイミド、N,N'-ジブロモイソシアヌル酸などが含まれる。好ましくは臭素、およびN-ブロモスクシンイミド、1,3-ジブロモ-5,5-ジメチルヒダントインなどのN-Br結合を有する化合物である。 The activator (C) used in the present invention preferably has a halogen-halogen bond or a nitrogen-halogen bond in the molecule. Specific examples of the activator (C) include chlorine, bromine, iodine, N- Chlorosuccinimide, N-bromosuccinimide, N-iodosuccinimide, N-bromocaprolactam, N-bromophthalimide, 1,3-dibromo-5,5-dimethylhydantoin, N-chloroglutarimide, N-bromoglutarimide, N, N'-dibromoisocyanuric acid and the like are included. Preferred are bromine and compounds having an N-Br bond such as N-bromosuccinimide and 1,3-dibromo-5,5-dimethylhydantoin.
本発明で用いられるラジカル重合性単量体は、例えば、(メタ)アクリル酸系単量体、スチレン系単量体、(メタ)アクリルアミド系単量体、マレイン酸系単量体、マレイミド系単量体、ビニルエステル系単量体などでありうる。 Examples of the radical polymerizable monomer used in the present invention include a (meth) acrylic acid monomer, a styrene monomer, a (meth) acrylamide monomer, a maleic acid monomer, and a maleimide monomer. It may be a monomer, a vinyl ester monomer or the like.
(メタ)アクリル酸系単量体の具体例には、(メタ)アクリル酸、(メタ)アクリル酸カリウム、(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-tert-ブチル、(メタ)アクリル酸-n-ペンチル、(メタ)アクリル酸-n-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-n-ヘプチル、(メタ)アクリル酸-n-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-2-メトキシエチル、(メタ)アクリル酸-3-メトキシブチル、(メタ)アクリル酸-2-ヒドロキシエチル、(メタ)アクリル酸-2-ヒドロキシプロピル、(メタ)アクリル酸ステアリル、(メタ)アクリル酸グリシジル、(メタ)アクリル酸2-アミノエチル、(メタ)アクリル酸2-(ジメチルアミノ)エチル、γ-(メタクリロイルオキシプロピル)トリメトキシシラン、(メタ)アクリル酸のエチレンオキサイド付加物、(メタ)アクリル酸トリフルオロメチルメチル、(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2-パーフルオロエチルエチル、(メタ)アクリル酸2-パーフルオロエチル-2-パーフルオロブチルエチル、(メタ)アクリル酸2-パーフルオロエチル、(メタ)アクリル酸パーフルオロメチル、(メタ)アクリル酸ジパーフルオロメチルメチル、(メタ)アクリル酸2-パーフルオロメチル-2-パーフルオロエチルメチル、(メタ)アクリル酸2-パーフルオロヘキシルエチル、(メタ)アクリル酸2-パーフルオロデシルエチル、(メタ)アクリル酸2-パーフルオロヘキサデシルエチルなどが含まれる。 Specific examples of (meth) acrylic acid monomers include (meth) acrylic acid, potassium (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylic acid-n- Propyl, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, (meth) acryl Acid-n-hexyl, cyclohexyl (meth) acrylate, (meth) acrylic acid-n-heptyl, (meth) acrylic acid-n-octyl, (meth) acrylic acid-2-ethylhexyl, (meth) acrylate nonyl, Decyl (meth) acrylate, dodecyl (meth) acrylate, phenyl (meth) acrylate, toluyl (meth) acrylate, benzyl (meth) acrylate, (meth) 2-methoxyethyl acrylate, 3-methoxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, stearyl (meth) acrylate, (meth ) Glycidyl acrylate, 2-aminoethyl (meth) acrylate, 2- (dimethylamino) ethyl (meth) acrylate, γ- (methacryloyloxypropyl) trimethoxysilane, ethylene oxide adduct of (meth) acrylic acid, (Meth) acrylic acid trifluoromethyl methyl, (meth) acrylic acid 2-trifluoromethyl ethyl, (meth) acrylic acid 2-perfluoroethyl ethyl, (meth) acrylic acid 2-perfluoroethyl-2-perfluorobutyl Ethyl, 2-perfluoroethyl (meth) acrylate, perfluoromethe (meth) acrylate Chill, diperfluoromethylmethyl (meth) acrylate, 2-perfluoromethyl-2-perfluoroethylmethyl (meth) acrylate, 2-perfluorohexylethyl (meth) acrylate, 2- (meth) acrylic acid 2- Examples include perfluorodecylethyl and 2-perfluorohexadecylethyl (meth) acrylate.
スチレン系単量体の具体例には、スチレン、ビニルトルエン、α−メチルスチレン、クロロスチレン、スチレンスルホン酸およびその塩などが含まれる。 Specific examples of the styrenic monomer include styrene, vinyl toluene, α-methyl styrene, chlorostyrene, styrene sulfonic acid and salts thereof.
(メタ)アクリルアミド系単量体の具体例には、(メタ)アクリロニトリル、(メタ)アクリルアミド、N−メチル(メタ)アクリルアミド、N-エチル(メタ)アクリルアミド、N-プロピル(メタ)アクリルアミド、N-イソプロピル(メタ)アクリルアミド、N-ブチル(メタ)アクリルアミド、N,N-ジメチル(メタ)アクリルアミドなどが含まれる。 Specific examples of (meth) acrylamide monomers include (meth) acrylonitrile, (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N- Isopropyl (meth) acrylamide, N-butyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide and the like are included.
マレイン酸系単量体の具体例には、無水マレイン酸、マレイン酸、マレイン酸のモノアルキルエステル及びジアルキルエステルなどが含まれる。 Specific examples of the maleic monomer include maleic anhydride, maleic acid, maleic acid monoalkyl ester and dialkyl ester, and the like.
マレイミド系単量体の例には、マレイミド、メチルマレイミド、エチルマレイミド、プロピルマレイミド、ブチルマレイミド、ヘキシルマレイミド、オクチルマレイミド、ドデシルマレイミド、ステアリルマレイミド、フェニルマレイミド、シクロヘキシルマレイミドなどが含まれる。 Examples of the maleimide monomer include maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide and the like.
ビニルエステル系単量体の例には、酢酸ビニル、プロピオン酸ビニル、ピバリン酸ビニル、安息香酸ビニル、桂皮酸ビニルなどが含まれる。 Examples of vinyl ester monomers include vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, vinyl cinnamate and the like.
これらのうち、本発明で用いられるラジカル重合性単量体は、好ましくは(メタ)アクリル酸系単量体、スチレン系単量体、(メタ)アクリロニトリルである。これらの化合物は、単独で、または2種類以上を組み合わせて使用しても構わない。 Of these, the radical polymerizable monomer used in the present invention is preferably a (meth) acrylic acid monomer, a styrene monomer, or (meth) acrylonitrile. These compounds may be used alone or in combination of two or more.
本発明において、ラジカル重合性単量体を重合する方法は特に限定されず、塊状重合、溶液重合、懸濁重合、乳化重合、塊状・懸濁重合などを適用することができる。 In the present invention, the method for polymerizing the radical polymerizable monomer is not particularly limited, and bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, bulk / suspension polymerization, and the like can be applied.
本発明の重合反応は、溶媒中で行うことができる。使用できる溶媒は、反応を阻害しないものであれば何れでもよく限定されない。溶媒の具体例には、ベンゼン、トルエンおよびキシレン等の芳香族炭化水素系溶媒;ペンタン、ヘキサン、ヘプタン、オクタン、ノナンおよびデカン等の脂肪族炭化水素系溶媒;シクロヘキサン、メチルシクロヘキサンおよびデカヒドロナフタレンのような脂環族炭化水素系溶媒;クロロベンゼン、ブロモベンゼン、ジクロロベンゼン、トリクロロベンゼン、塩化メチレン、クロロホルム、四塩化炭素およびテトラクロロエチレン等のハロゲン化炭化水素系溶媒;メタノール、エタノール、n-プロパノール、iso-プロパノール、n-ブタノール、sec-ブタノールおよびtert-ブタノール等のアルコール系溶媒;アセトン、メチルエチルケトンおよびメチルイソブチルケトン等のケトン系溶媒;酢酸エチルおよびジメチルフタレート等のエステル系溶媒;ジメチルエーテル、ジエチルエーテル、ジ-n-アミルエーテル、テトラヒドロフランおよびジオキシアニソールのようなエーテル系溶媒などが含まれる。また、本発明の重合反応は、水を溶媒とする懸濁重合、乳化重合であってもよい。これらの溶媒は、単独でもまたは2種以上を混合して使用してもよい。また、これらの溶媒の使用によって、反応液が均一相となることが好ましいが、不均一な複数の相となっても構わない。 The polymerization reaction of the present invention can be carried out in a solvent. Any solvent may be used as long as it does not inhibit the reaction. Specific examples of the solvent include aromatic hydrocarbon solvents such as benzene, toluene and xylene; aliphatic hydrocarbon solvents such as pentane, hexane, heptane, octane, nonane and decane; cyclohexane, methylcyclohexane and decahydronaphthalene. Such alicyclic hydrocarbon solvents; halogenated hydrocarbon solvents such as chlorobenzene, bromobenzene, dichlorobenzene, trichlorobenzene, methylene chloride, chloroform, carbon tetrachloride and tetrachloroethylene; methanol, ethanol, n-propanol, iso- Alcohol solvents such as propanol, n-butanol, sec-butanol and tert-butanol; ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; ester solvents such as ethyl acetate and dimethyl phthalate Dimethyl ether, diethyl ether, di -n- amyl ether, and the like ether solvents such as tetrahydrofuran and dioxy anisole. The polymerization reaction of the present invention may be suspension polymerization or emulsion polymerization using water as a solvent. These solvents may be used alone or in admixture of two or more. Moreover, it is preferable that the reaction liquid becomes a homogeneous phase by using these solvents, but a plurality of non-uniform phases may be used.
本発明の重合反応の反応温度は、ラジカル重合反応が進行する温度であればよく、所望する重合体の重合度、使用するラジカル重合開始剤、および溶媒の種類や量によって設定される。反応温度は、例えば、通常−100℃〜250℃であり、好ましくは−50℃〜180℃であり、更に好ましくは0℃〜160℃である。重合反応は、場合によって、減圧、常圧または加圧条件下の何れで行ってもよい。上記重合反応は、窒素やアルゴン等の不活性ガス雰囲気下で行うことが好ましい。 The reaction temperature of the polymerization reaction of the present invention may be any temperature at which the radical polymerization reaction proceeds, and is set according to the desired degree of polymerization of the polymer, the radical polymerization initiator used, and the type and amount of the solvent. The reaction temperature is, for example, usually −100 ° C. to 250 ° C., preferably −50 ° C. to 180 ° C., more preferably 0 ° C. to 160 ° C. In some cases, the polymerization reaction may be performed under reduced pressure, normal pressure, or pressurized conditions. The polymerization reaction is preferably performed in an inert gas atmosphere such as nitrogen or argon.
本発明の重合反応における各成分の添加順序は特に限定されないが、好ましくは、オレフィン系重合体(A)を溶媒中に溶解あるいは懸濁させ;これに活性化剤(C)を添加し;次いで金属化合物(B)とラジカル重合性単量体を添加して、所定の重合温度で重合する方法がある。また、重合体(A)や金属化合物(B)、活性化剤(C)、ラジカル重合性単量体の種類や性状に応じてこれらの順序を入れ替えたり、一部をあらかじめプレミックスして用いたりすることも可能である。 The order of addition of each component in the polymerization reaction of the present invention is not particularly limited. Preferably, the olefin polymer (A) is dissolved or suspended in a solvent; the activator (C) is added thereto; There is a method in which a metal compound (B) and a radical polymerizable monomer are added and polymerized at a predetermined polymerization temperature. Also, the order of these may be changed according to the type and properties of the polymer (A), the metal compound (B), the activator (C), and the radical polymerizable monomer, or a part thereof may be premixed in advance. It is also possible to do.
本発明の製造方法により得られる重合体(オレフィン系重合体セグメントとラジカル重合体セグメントとが化学結合した重合体)は、精製・単離されることが好ましい。精製・単離は、例えば、重合に用いた溶媒や未反応のモノマーを留去したり、貧溶媒による再沈殿するなどして、公知の方法を用いて行われる。さらに、得られた重合体を、ソックスレー抽出装置を用いて、アセトンやTHFなどの極性溶媒で処理することで、副生したホモラジカル重合体を除去することが可能である。 The polymer obtained by the production method of the present invention (a polymer in which an olefin polymer segment and a radical polymer segment are chemically bonded) is preferably purified and isolated. Purification / isolation is performed using a known method, for example, by distilling off the solvent or unreacted monomer used for the polymerization or reprecipitation with a poor solvent. Furthermore, by treating the obtained polymer with a polar solvent such as acetone or THF using a Soxhlet extraction apparatus, it is possible to remove the by-product homoradical polymer.
以下、実施例に基づいて本発明をさらに具体的に説明するが、本発明はこれら実施例に限定されるものではない。 EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples.
本実施例中の各物性の測定は以下のように行なった。
(i)分子量および分子量分布の測定
GPC(ゲルパーミエーションクロマトグラフィー)を使用して、以下の条件で測定した。
測定装置:allianceGPC2000(Waters社製)
解析装置:Empowerプロフェッショナル(Waters社製)
カラム:TSKgel GMH6HT×2+TSKgel GMH6HTL×2
カラム温度:140℃
移動相:o−ジクロロベンゼン(ODCB)
検出器:示差屈折率計
流速:1mL/min
試料濃度:30mg/20mL−ODCB
注入量:500μL
カラム較正:単分散ポリスチレン(東ソー社製)
The physical properties in this example were measured as follows.
(i) Measurement of molecular weight and molecular weight distribution GPC (gel permeation chromatography) was used and measured under the following conditions.
Measuring device: alliance GPC2000 (manufactured by Waters)
Analysis device: Empower Professional (manufactured by Waters)
Column: TSKgel GMH6HT x 2 + TSKgel GMH6HTL x 2
Column temperature: 140 ° C
Mobile phase: o-dichlorobenzene (ODCB)
Detector: differential refractometer flow rate: 1 mL / min
Sample concentration: 30 mg / 20 mL-ODCB
Injection volume: 500 μL
Column calibration: monodisperse polystyrene (manufactured by Tosoh Corporation)
(ii)ポリマーの組成分析
1H−NMRを使用して以下の条件で測定した。
測定装置:JNMGSX−400型核磁気共鳴装置(日本電子製)
試料管:5mmφ
測定溶媒:o−ジクロロベンゼン−d4
測定温度:120℃
測定幅:8000Hz
パルス幅:7.7μs(45°)
パルス間隔:6.0s
測定回数:〜8000回
(ii) Polymer composition analysis
Measurement was performed under the following conditions using 1 H-NMR.
Measuring device: JNMGSX-400 nuclear magnetic resonance apparatus (manufactured by JEOL)
Sample tube: 5mmφ
Measuring solvent: o-dichlorobenzene-d4
Measurement temperature: 120 ° C
Measurement width: 8000Hz
Pulse width: 7.7 μs (45 °)
Pulse interval: 6.0s
Number of measurements: ~ 8000 times
[実施例1]
充分に窒素置換した内容積500mLのガラス製反応器に、粒子状ポリプロピレン(PP)(Mn=34,500)30gと、酢酸ブチル200mLを入れ、攪拌下100℃で2時間窒素バブリングを行い、スラリーを得た。得られたスラリーに、N−ブロモスクシンイミド(NBS)1.2gを加えて、100℃で2時間撹拌した後、メタクリル酸メチル(MMA)100mLを加えて1時間窒素バブリングを行った。さらにこのスラリーに、銅粉末114mg、N,N,N',N'',N''-ペンタメチルジエチレントリアミン(PMDETA)0.75mLを加えた後、100℃で3時間重合を行った。冷却後、スラリーをアセトン1.5L中に注いで撹拌し、グラスフィルターでろ過した。さらにフィルター上のポリマーをアセトンおよびメタノールで洗浄した後、減圧乾燥して33.6gの淡黄色粒子状ポリマーを得た。
[Example 1]
A glass reactor with an internal volume of 500 mL that has been sufficiently purged with nitrogen is charged with 30 g of particulate polypropylene (PP) (Mn = 34,500) and 200 mL of butyl acetate, and is subjected to nitrogen bubbling at 100 ° C. for 2 hours with stirring to produce a slurry. Got. After adding 1.2 g of N-bromosuccinimide (NBS) to the obtained slurry and stirring at 100 ° C. for 2 hours, 100 mL of methyl methacrylate (MMA) was added and nitrogen bubbling was performed for 1 hour. Furthermore, after adding 114 mg of copper powder and 0.75 mL of N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine (PMDETA) to this slurry, polymerization was carried out at 100 ° C. for 3 hours. After cooling, the slurry was poured into 1.5 L of acetone, stirred, and filtered through a glass filter. Further, the polymer on the filter was washed with acetone and methanol, and then dried under reduced pressure to obtain 33.6 g of a pale yellow particulate polymer.
1H−NMR分析により、得られたポリマー中にはPP成分とPMMA成分とが含まれており、その組成比はPP/PMMA=90/10(wt%)であった。結果を表1に示す。 According to 1 H-NMR analysis, the obtained polymer contained a PP component and a PMMA component, and the composition ratio was PP / PMMA = 90/10 (wt%). The results are shown in Table 1.
[実施例2]
充分に窒素置換した内容積500mLのガラス製反応器に、実施例1と同じ粒子状PP30gと酢酸ブチル200mLを入れ、攪拌下100℃で2時間窒素バブリングを行った。このスラリーにNBS1.2gを加えて100℃で2時間撹拌した後、スチレン(St)160mL、アクリロニトリル(AN)40mLを加えて1時間窒素バブリングを行った。このスラリーに、銅粉末318mg、PMDETA2.09mLを加えた後、100℃で3時間重合を行った。冷却後メタノール150mLを加え、スラリーをグラスフィルターでろ過した。さらにフィルター上のポリマーをアセトンおよびメタノールで洗浄した後、減圧乾燥して31.7gの白色粒子状ポリマーを得た。
[Example 2]
30 g of the same particulate PP as in Example 1 and 200 mL of butyl acetate were placed in a glass reactor having an internal volume of 500 mL sufficiently purged with nitrogen, and nitrogen bubbling was performed at 100 ° C. for 2 hours with stirring. After adding 1.2 g of NBS to this slurry and stirring at 100 ° C. for 2 hours, 160 mL of styrene (St) and 40 mL of acrylonitrile (AN) were added and nitrogen bubbling was performed for 1 hour. After adding 318 mg of copper powder and 2.09 mL of PMDETA to this slurry, polymerization was performed at 100 ° C. for 3 hours. After cooling, 150 mL of methanol was added, and the slurry was filtered through a glass filter. Further, the polymer on the filter was washed with acetone and methanol and then dried under reduced pressure to obtain 31.7 g of a white particulate polymer.
1H−NMR分析により、得られたポリマー中にはPP成分とスチレン−アクリロニトリル共重合体(AS)成分が含まれており、その組成比はPP/St−AN=95/5(wt%)であった。結果を表1に示す。 According to 1 H-NMR analysis, the obtained polymer contains a PP component and a styrene-acrylonitrile copolymer (AS) component, and the composition ratio is PP / St-AN = 95/5 (wt%). Met. The results are shown in Table 1.
[実施例3]
充分に窒素置換した内容積500mLのガラス製反応器に、実施例1と同じ粒子状PP15gとクロロベンゼン200mLを入れ、攪拌下100℃で2時間窒素バブリングを行った。このスラリーにNBS1.2gを加えて100℃で2時間撹拌した後、MMA100mLを加えて1時間窒素バブリングを行った。このスラリーに、銅粉末114mg、PMDETA0.75mLを加えた後、100℃で3時間重合を行った。冷却後、スラリーをアセトン1.5L中に注いで撹拌し、グラスフィルターでろ過した。さらにフィルター上のポリマーをアセトンおよびメタノールで洗浄した後、減圧乾燥して35.0gの淡黄色粒子状ポリマーを得た。
[Example 3]
Into a glass reactor having an internal volume of 500 mL sufficiently purged with nitrogen, 15 g of the same particulate PP as in Example 1 and 200 mL of chlorobenzene were placed, and nitrogen bubbling was performed at 100 ° C. for 2 hours with stirring. NBS 1.2g was added to this slurry, and it stirred at 100 degreeC for 2 hours, Then, MMA100mL was added and nitrogen bubbling was performed for 1 hour. To this slurry, 114 mg of copper powder and 0.75 mL of PMDETA were added, followed by polymerization at 100 ° C. for 3 hours. After cooling, the slurry was poured into 1.5 L of acetone, stirred, and filtered through a glass filter. Further, the polymer on the filter was washed with acetone and methanol and then dried under reduced pressure to obtain 35.0 g of a light yellow particulate polymer.
1H−NMR分析により、得られたポリマー中にはPP成分とPMMA成分が含まれており、その組成比はPP/PMMA=43/57(wt%)であった。結果を表1に示す。 According to 1 H-NMR analysis, the obtained polymer contained a PP component and a PMMA component, and the composition ratio was PP / PMMA = 43/57 (wt%). The results are shown in Table 1.
[実施例4]
溶媒をアニソールにした以外は、実施例3と同様にして、16.6gの白色粒子状ポリマーを得た。1H−NMR分析により、得られたポリマー中にはPP成分とPMMA成分が含まれており、その組成比はPP/PMMA=91/9(wt%)であった。結果を表1に示す。
[Example 4]
16.6 g of white particulate polymer was obtained in the same manner as in Example 3 except that the solvent was anisole. According to 1 H-NMR analysis, the obtained polymer contained a PP component and a PMMA component, and the composition ratio was PP / PMMA = 91/9 (wt%). The results are shown in Table 1.
[比較例1]
NBSを添加しなかった以外は実施例3と同様にして、14.8gの白色粒子状ポリマーを得た。1H−NMR分析からは、得られたポリマー中にMMA成分は検出されなかった。結果を表1に示す。
[Comparative Example 1]
14.8 g of white particulate polymer was obtained in the same manner as in Example 3 except that NBS was not added. From 1 H-NMR analysis, no MMA component was detected in the obtained polymer. The results are shown in Table 1.
[比較例2]
銅粉末およびPMDETAを加えなかった以外は実施例3と同様にして、14.9gの白色粒子状ポリマーを得た。1H−NMR分析からは、得られたポリマー中にMMA成分は検出されなかった。結果を表1に示す。
[Comparative Example 2]
14.9 g of white particulate polymer was obtained in the same manner as in Example 3 except that copper powder and PMDETA were not added. From 1 H-NMR analysis, no MMA component was detected in the obtained polymer. The results are shown in Table 1.
[実施例5]
充分に窒素置換した内容積500mLのガラス製反応器に、エチレン−プロピレン共重合体(EPR;Mn=51,900)15gと、クロロベンゼン200mLを入れ、攪拌下100℃で2時間窒素バブリングを行った。この溶液に臭素0.15mLを加えて、100℃で2時間撹拌した後、メタクリル酸ドデシル(DMA)90mLを加えて1時間窒素バブリングを行った。この溶液に、臭化銅(I)215mg、PMDETA3.13mLを加えた後、80℃で4時間重合を行った。冷却後、反応溶液をメタノール1.5L中に注いで撹拌し、上澄みを取り除いた。再びメタノール1.5Lを加えて撹拌後、沈降したゴム状ポリマーを120℃で減圧乾燥して18.2gの褐色ゴム状ポリマーを得た。
[Example 5]
Into a glass reactor with an internal volume of 500 mL sufficiently purged with nitrogen, 15 g of ethylene-propylene copolymer (EPR; Mn = 51,900) and 200 mL of chlorobenzene were placed, and nitrogen bubbling was performed at 100 ° C. for 2 hours with stirring. . After adding 0.15 mL of bromine to this solution and stirring at 100 ° C. for 2 hours, 90 mL of dodecyl methacrylate (DMA) was added and nitrogen bubbling was performed for 1 hour. To this solution, 215 mg of copper (I) bromide and 3.13 mL of PMDETA were added, followed by polymerization at 80 ° C. for 4 hours. After cooling, the reaction solution was poured into 1.5 L of methanol and stirred, and the supernatant was removed. After adding 1.5 L of methanol again and stirring, the precipitated rubber-like polymer was dried under reduced pressure at 120 ° C. to obtain 18.2 g of a brown rubber-like polymer.
1H−NMR分析により、得られたポリマー中にはEPR成分とPDMA成分が含まれており、その組成比はEPR/PDMA=82/18(wt%)であった。結果を表2に示す。 According to 1 H-NMR analysis, the obtained polymer contained an EPR component and a PDMA component, and the composition ratio was EPR / PDMA = 82/18 (wt%). The results are shown in Table 2.
[実施例6]
臭化銅(I)とPMDETAの仕込み量を表2に示すように変更した以外は、実施例5と同様の操作により、25.6gの褐色ゴム状ポリマーを得た。1H−NMR分析より、得られたポリマー中にはEPR成分とPDMA成分が含まれており、その組成比はEPR/PDMA=59/41(wt%)であった。結果を表2に示す。
[Example 6]
25.6 g of a brown rubbery polymer was obtained in the same manner as in Example 5 except that the amounts of copper (I) bromide and PMDETA were changed as shown in Table 2. From the 1 H-NMR analysis, the obtained polymer contained an EPR component and a PDMA component, and the composition ratio was EPR / PDMA = 59/41 (wt%). The results are shown in Table 2.
[実施例7]
活性化剤を、臭素からNBS0.6gに変更した以外は、実施例6と同様の操作により、37.0gの褐色ゴム状ポリマーを得た。1H−NMR分析より、得られたポリマー中にはEPR成分とPDMA成分が含まれており、その組成比はEPR/PDMA=41/59(wt%)であった。結果を表2に示す。
[Example 7]
37.0 g of a brown rubbery polymer was obtained in the same manner as in Example 6 except that the activator was changed from bromine to NBS 0.6 g. From the 1 H-NMR analysis, the obtained polymer contained an EPR component and a PDMA component, and the composition ratio was EPR / PDMA = 41/59 (wt%). The results are shown in Table 2.
[実施例8]
充分に窒素置換した内容積500mLのガラス製反応器に、実施例5と同様のEPR15gと酢酸ブチル200mLを入れ、攪拌下110℃で2時間窒素バブリングを行った。この懸濁液にNBS0.6gを加えて110℃で2時間撹拌した後、DMA100mLを加えて1時間窒素バブリングを行った。この懸濁液に、銅粉末381mg、PMDETA2.51mLを加えた後、110℃で4時間重合を行った。冷却後、反応溶液をメタノール1.5L中に注いで撹拌し、上澄みを取り除いた。再びメタノール1.5Lを加えて撹拌後、沈降したゴム状ポリマーを120℃で減圧乾燥して56.3gの褐色ゴム状ポリマーを得た。
[Example 8]
Into a glass reactor having an internal volume of 500 mL sufficiently purged with nitrogen, 15 g of EPR as in Example 5 and 200 mL of butyl acetate were placed, and nitrogen bubbling was performed at 110 ° C. for 2 hours with stirring. NBS 0.6g was added to this suspension, and after stirring at 110 degreeC for 2 hours, DMA100mL was added and nitrogen bubbling was performed for 1 hour. After adding 381 mg of copper powder and 2.51 mL of PMDETA to this suspension, polymerization was performed at 110 ° C. for 4 hours. After cooling, the reaction solution was poured into 1.5 L of methanol and stirred, and the supernatant was removed. After adding 1.5 L of methanol again and stirring, the precipitated rubber-like polymer was dried under reduced pressure at 120 ° C. to obtain 56.3 g of a brown rubber-like polymer.
1H−NMR分析より、得られたポリマー中にはEPR成分とPDMA成分が含まれており、その組成比はEPR/PDMA=27/73(wt%)であった。結果を表2に示す。 From the 1 H-NMR analysis, the obtained polymer contained an EPR component and a PDMA component, and the composition ratio was EPR / PDMA = 27/73 (wt%). The results are shown in Table 2.
[実施例9〜13]
銅粉末とPMDETAの仕込み量を表2に示すように変更した以外は実施例8と同様の操作により、メタクリル酸ドデシルの重合を行った。結果を表2に示す。
[Examples 9 to 13]
Polymerization of dodecyl methacrylate was carried out in the same manner as in Example 8 except that the amounts of copper powder and PMDETA were changed as shown in Table 2. The results are shown in Table 2.
[実施例14]
充分に窒素置換した内容積500mLのガラス製反応器に、実施例5と同様のEPR15gと酢酸ブチル200mLを入れ、攪拌下100℃で2時間窒素バブリングを行った。この懸濁液にNBS0.6gを加えて100℃で2時間撹拌した後、DMA100mLを加えて1時間窒素バブリングを行った。この懸濁液に、銅粉末95mg、PMDETA0.63mLを加えた後、100℃で4時間重合を行った。冷却後、反応溶液をメタノール1.5L中に注いで撹拌し、上澄みを取り除いた。再びメタノール1.5Lを加えて撹拌後、沈降したゴム状ポリマーを120℃で減圧乾燥して58.1gの褐色ゴム状ポリマーを得た。
[Example 14]
A glass reactor having an internal volume of 500 mL sufficiently purged with nitrogen was charged with 15 g of EPR as in Example 5 and 200 mL of butyl acetate, and subjected to nitrogen bubbling at 100 ° C. for 2 hours with stirring. NBS 0.6g was added to this suspension, and it stirred at 100 degreeC for 2 hours, Then, DMA100mL was added and nitrogen bubbling was performed for 1 hour. After adding 95 mg of copper powder and 0.63 mL of PMDETA to this suspension, polymerization was performed at 100 ° C. for 4 hours. After cooling, the reaction solution was poured into 1.5 L of methanol and stirred, and the supernatant was removed. After adding 1.5 L of methanol again and stirring, the precipitated rubber-like polymer was dried under reduced pressure at 120 ° C. to obtain 58.1 g of a brown rubber-like polymer.
1H−NMR分析より、得られたポリマー中にはEPR成分とPDMA成分が含まれており、その組成比はEPR/PDMA=26/74(wt%)であった。結果を表2に示す。 From the 1 H-NMR analysis, the obtained polymer contained an EPR component and a PDMA component, and the composition ratio was EPR / PDMA = 26/74 (wt%). The results are shown in Table 2.
[実施例15]
充分に窒素置換した内容積500mLのガラス製反応器に、実施例5と同様のEPR15gとクロロベンゼン200mLを入れ、攪拌下100℃で2時間窒素バブリングを行った。この溶液にNBS0.6gを加えて100℃で2時間撹拌した後、DMA100mLを加えて1時間窒素バブリングを行った。この溶液に、銅粉末95mg、PMDETA0.63mLを加えた後、100℃で4時間重合を行った。冷却後、反応溶液をメタノール1.5L中に注いで撹拌し、上澄みを取り除いた。再びメタノール1.5Lを加えて撹拌後、沈降したゴム状ポリマーを120℃で減圧乾燥して59.6gの褐色ゴム状ポリマーを得た。
[Example 15]
Into a glass reactor having an internal volume of 500 mL sufficiently purged with nitrogen, 15 g of EPR as in Example 5 and 200 mL of chlorobenzene were placed, and nitrogen bubbling was performed at 100 ° C. for 2 hours with stirring. NBS 0.6g was added to this solution, and it stirred at 100 degreeC for 2 hours, Then, DMA100mL was added and nitrogen bubbling was performed for 1 hour. After adding 95 mg of copper powder and 0.63 mL of PMDETA to this solution, polymerization was performed at 100 ° C. for 4 hours. After cooling, the reaction solution was poured into 1.5 L of methanol and stirred, and the supernatant was removed. After adding 1.5 L of methanol again and stirring, the precipitated rubber-like polymer was dried under reduced pressure at 120 ° C. to obtain 59.6 g of a brown rubber-like polymer.
1H−NMR分析より、得られたポリマー中にはEPR成分とPDMA成分が含まれており、その組成比はEPR/PDMA=25/75(wt%)であった。結果を表2に示す。 From the 1 H-NMR analysis, the obtained polymer contained an EPR component and a PDMA component, and the composition ratio was EPR / PDMA = 25/75 (wt%). The results are shown in Table 2.
[実施例16]
充分に窒素置換した内容積1Lのガラス製反応器に、エチレン−ブテン共重合体(EBR;Mn=82,000)50gと酢酸ブチル700mLを入れ、攪拌下110℃で2時間窒素バブリングを行った。この懸濁液にNBS1.25gを加えて110℃で2時間撹拌した後、MMA50mL、メタクリル酸グリシジル(GMA)7mLを加えて1時間窒素バブリングを行った。この懸濁液に、銅粉末199mg、PMDETA1.30mLを加えた後、110℃で2時間重合を行った。冷却後、懸濁液をアセトン1.5L中に注いで撹拌し、上澄みを取り除いた。再びアセトン1.5Lを加えて撹拌後、沈降したゴム状ポリマーを120℃で減圧乾燥して64.0gの褐色ゴム状ポリマーを得た。
[Example 16]
Into a glass reactor having an internal volume of 1 L that was sufficiently purged with nitrogen, 50 g of ethylene-butene copolymer (EBR; Mn = 82,000) and 700 mL of butyl acetate were placed, and nitrogen bubbling was performed at 110 ° C. for 2 hours with stirring. . After adding 1.25g of NBS to this suspension and stirring at 110 degreeC for 2 hours, 50 mL of MMA and 7 mL of glycidyl methacrylate (GMA) were added, and nitrogen bubbling was performed for 1 hour. After adding 199 mg of copper powder and 1.30 mL of PMDETA to this suspension, polymerization was carried out at 110 ° C. for 2 hours. After cooling, the suspension was poured into 1.5 L of acetone and stirred, and the supernatant was removed. After adding 1.5 L of acetone again and stirring, the precipitated rubber-like polymer was dried under reduced pressure at 120 ° C. to obtain 64.0 g of a brown rubber-like polymer.
1H−NMR分析より、得られたポリマー中にはEBR成分とMMA−GMA共重合体成分が含まれており、その組成比はEBR/MMA−GMA=78/22(wt%)であった。結果を表3に示す。 From the 1 H-NMR analysis, the obtained polymer contained an EBR component and an MMA-GMA copolymer component, and the composition ratio was EBR / MMA-GMA = 78/22 (wt%). . The results are shown in Table 3.
[実施例17〜19]
NBS、銅粉末、PMDETA、GMAの仕込み量および重合時間を表3に示すように変更した以外は、実施例16と同様の操作により、MMAとGMAとの共重合を行った。結果を表3に示す。
[Examples 17 to 19]
MMA and GMA were copolymerized in the same manner as in Example 16 except that the amount of NBS, copper powder, PMDETA, and GMA and the polymerization time were changed as shown in Table 3. The results are shown in Table 3.
[実施例20]
充分に窒素置換した内容積1Lのガラス製反応器に、実施例16と同様のEBR50gとクロロベンゼン700mLを入れ、攪拌下110℃で2時間窒素バブリングを行った。この溶液にNBS1.25gを加えて110℃で2時間撹拌した後、GMA30mLを加えて1時間窒素バブリングを行った。この溶液に、銅粉末199mg、PMDETA1.30mLを加えた後、110℃で1時間重合を行った。冷却後、反応溶液をアセトン1.5L中に注いで撹拌し、上澄みを取り除いた。再びアセトン1.5Lを加えて撹拌後、沈降したゴム状ポリマーを120℃で減圧乾燥して51.6gの褐色ゴム状ポリマーを得た。
[Example 20]
50 g of EBR and 700 mL of chlorobenzene as in Example 16 were placed in a 1 L glass reactor sufficiently purged with nitrogen, and nitrogen bubbling was performed at 110 ° C. for 2 hours with stirring. NBS 1.25g was added to this solution, and it stirred at 110 degreeC for 2 hours, Then, GMA30mL was added and nitrogen bubbling was performed for 1 hour. After adding 199 mg of copper powder and 1.30 mL of PMDETA to this solution, polymerization was performed at 110 ° C. for 1 hour. After cooling, the reaction solution was poured into 1.5 L of acetone and stirred, and the supernatant was removed. After adding 1.5 L of acetone again and stirring, the precipitated rubber-like polymer was dried under reduced pressure at 120 ° C. to obtain 51.6 g of a brown rubber-like polymer.
1H−NMR分析より、得られたポリマー中にはEBR成分とPGMA成分が含まれており、その組成比はEBR/PGMA=97/3(wt%)であった。結果を表3に示す。 From the 1 H-NMR analysis, the obtained polymer contained an EBR component and a PGMA component, and the composition ratio was EBR / PGMA = 97/3 (wt%). The results are shown in Table 3.
[実施例21]
充分に窒素置換した内容積2Lのガラス製反応器に、エチレン−ブテン共重合体(EBR;Mn=131,000)90gとクロロベンゼン1200mLを入れ、攪拌下100℃で2時間窒素バブリングを行った。この溶液にNBS1.8gを加えて100℃で2時間撹拌した後、MMA600mLを加えて1時間窒素バブリングを行った。この溶液に、銅粉末286mg、PMDETA1.88mLを加えた後、100℃で2時間重合を行った。冷却後、溶液をメタノール1.5L中に注いで撹拌し、上澄みを取り除いた。再びメタノール1.5Lを加えて撹拌後、沈降したゴム状ポリマーを120℃で減圧乾燥して91.2gの褐色ゴム状ポリマーを得た。
[Example 21]
90 g of ethylene-butene copolymer (EBR; Mn = 131,000) and 1200 mL of chlorobenzene were placed in a 2 L glass reactor sufficiently purged with nitrogen, and nitrogen bubbling was performed at 100 ° C. for 2 hours with stirring. After adding NBS1.8g to this solution and stirring at 100 degreeC for 2 hours, MMA600mL was added and nitrogen bubbling was performed for 1 hour. After adding 286 mg of copper powder and 1.88 mL of PMDETA to this solution, polymerization was performed at 100 ° C. for 2 hours. After cooling, the solution was poured into 1.5 L of methanol and stirred, and the supernatant was removed. After adding 1.5 L of methanol again and stirring, the precipitated rubber-like polymer was dried under reduced pressure at 120 ° C. to obtain 91.2 g of a brown rubber-like polymer.
1H−NMR分析より、得られたポリマー中にはEBR成分とPMMA成分が含まれており、その組成比はEBR/PMMA=99/1(wt%)であった。結果を表3に示す。 From the 1 H-NMR analysis, the obtained polymer contained an EBR component and a PMMA component, and the composition ratio was EBR / PMMA = 99/1 (wt%). The results are shown in Table 3.
[実施例22]
充分に窒素置換した内容積2Lのガラス製反応器に、実施例21で用いたものと同様のEBR90gとクロロベンゼン1200mLを入れ、攪拌下100℃で2時間窒素バブリングを行った。この溶液にNBS1.8gを加えて100℃で2時間撹拌した後、MMA600mLを加えて1時間窒素バブリングを行った。この溶液に、塩化銅(I)1.60g、PMDETA3.38mLを加えた後、100℃で1時間重合を行った。冷却後、溶液をメタノール1.5L中に注いで撹拌し、上澄みを取り除いた。再びメタノール1.5Lを加えて撹拌後、沈降したゴム状ポリマーを120℃で減圧乾燥して133.7gの褐色ゴム状ポリマーを得た。
[Example 22]
90 g of EBR and 1200 mL of chlorobenzene similar to those used in Example 21 were placed in a 2 L glass reactor sufficiently purged with nitrogen, and nitrogen bubbling was performed at 100 ° C. for 2 hours with stirring. After adding NBS1.8g to this solution and stirring at 100 degreeC for 2 hours, MMA600mL was added and nitrogen bubbling was performed for 1 hour. To this solution, 1.60 g of copper (I) chloride and 3.38 mL of PMDETA were added, followed by polymerization at 100 ° C. for 1 hour. After cooling, the solution was poured into 1.5 L of methanol and stirred, and the supernatant was removed. After adding 1.5 L of methanol again and stirring, the precipitated rubber-like polymer was dried under reduced pressure at 120 ° C. to obtain 133.7 g of a brown rubber-like polymer.
1H−NMR分析より、得られたポリマー中にはEBR成分とPMMA成分が含まれており、その組成比はEBR/PMMA=67/33(wt%)であった。結果を表3に示す。 From the 1 H-NMR analysis, the obtained polymer contained an EBR component and a PMMA component, and the composition ratio was EBR / PMMA = 67/33 (wt%). The results are shown in Table 3.
[実施例23]
重合時間を3時間にした以外は実施例22と同様の操作で233.3gの褐色ポリマーを得た。1H−NMR分析より、得られたポリマー中にはEBR成分とPMMA成分が含まれており、その組成比はEBR/PMMA=39/61(wt%)であった。結果を表3に示す。
[Example 23]
Except for setting the polymerization time to 3 hours, 233.3 g of a brown polymer was obtained in the same manner as in Example 22. From the 1H-NMR analysis, the obtained polymer contained an EBR component and a PMMA component, and the composition ratio was EBR / PMMA = 39/61 (wt%). The results are shown in Table 3.
[比較例3]
充分に窒素置換した内容積500mLのガラス製反応器に、実施例21で用いたものと同様のEBR15gとクロロベンゼン200mLを入れ、攪拌下100℃で2時間窒素バブリングを行った。この溶液にMMA100mLを加えて1時間窒素バブリングを行った。この溶液に、塩化銅(I)267mg、PMDETA0.56mLを加えた後、100℃で3時間重合を行った。冷却後、溶液をメタノール1.5L中に注いで撹拌し、上澄みを取り除いた。再びメタノール1.5Lを加えて撹拌後、沈降したゴム状ポリマーを120℃で減圧乾燥して14.7gの褐色ゴム状ポリマーを得た。1H−NMR分析より、得られたポリマー中にはPMMA成分が含まれていないことが分かった。結果を表3に示す。
[Comparative Example 3]
15 g of EBR and 200 mL of chlorobenzene similar to those used in Example 21 were placed in a glass reactor having an internal volume of 500 mL sufficiently purged with nitrogen, and nitrogen bubbling was performed at 100 ° C. for 2 hours with stirring. MMA100mL was added to this solution, and nitrogen bubbling was performed for 1 hour. To this solution, 267 mg of copper (I) chloride and 0.56 mL of PMDETA were added, followed by polymerization at 100 ° C. for 3 hours. After cooling, the solution was poured into 1.5 L of methanol and stirred, and the supernatant was removed. After adding 1.5 L of methanol again and stirring, the precipitated rubber-like polymer was dried under reduced pressure at 120 ° C. to obtain 14.7 g of a brown rubber-like polymer. From 1 H-NMR analysis, it was found that no PMMA component was contained in the obtained polymer. The results are shown in Table 3.
[実施例24]
充分に窒素置換した内容積1Lのガラス製反応器に、エチレン−ブテン共重合体(EBR;Mn=51,000)50gとクロロベンゼン700mLを入れ、攪拌下110℃で2時間窒素バブリングを行った。この溶液にNBS0.625gを加えて110℃で2時間撹拌した後、GMA30mLを加えて1時間窒素バブリングを行った。この溶液に、銅粉末99mg、PMDETA0.65mLを加えた後、110℃で1時間重合を行った。冷却後、溶液をメタノール1.5L中に注いで撹拌し、上澄みを取り除いた。再びメタノール1.5Lを加えて撹拌後、沈降したゴム状ポリマーを120℃で減圧乾燥して55.1gの褐色ゴム状ポリマーを得た。1H−NMR分析より、得られたポリマー中にはEBR成分とPGMA成分が含まれており、その組成比はEBR/PGMA=91/9(wt%)であった。結果を表3に示す。
[Example 24]
Into a glass reactor having an internal volume of 1 L sufficiently purged with nitrogen, 50 g of ethylene-butene copolymer (EBR; Mn = 51,000) and 700 mL of chlorobenzene were placed, and nitrogen bubbling was performed at 110 ° C. for 2 hours with stirring. After adding NBS0.625g to this solution and stirring at 110 degreeC for 2 hours, GMA30mL was added and nitrogen bubbling was performed for 1 hour. After adding 99 mg of copper powder and 0.65 mL of PMDETA to this solution, polymerization was performed at 110 ° C. for 1 hour. After cooling, the solution was poured into 1.5 L of methanol and stirred, and the supernatant was removed. After adding 1.5 L of methanol again and stirring, the precipitated rubber-like polymer was dried under reduced pressure at 120 ° C. to obtain 55.1 g of a brown rubber-like polymer. From the 1 H-NMR analysis, the obtained polymer contained an EBR component and a PGMA component, and the composition ratio was EBR / PGMA = 91/9 (wt%). The results are shown in Table 3.
[実施例25]
NBS,銅粉末、PMDETAの仕込み量を変更した以外は実施例24と同様の操作で、GMAのラジカル重合を行った。1H−NMR分析より、得られたポリマー中にはEBR成分とPGMA成分が含まれており、その組成比はEBR/PGMA=87/13(wt%)であった。結果を表3に示す。
[Example 25]
GMA radical polymerization was performed in the same manner as in Example 24 except that the amounts of NBS, copper powder, and PMDETA were changed. From the 1H-NMR analysis, the obtained polymer contained an EBR component and a PGMA component, and the composition ratio was EBR / PGMA = 87/13 (wt%). The results are shown in Table 3.
本発明により、オレフィン系重合体セグメントとラジカル重合体セグメントとが化学結合した重合体を、工業的に広く製造されているポリエチレンやポリプロピレンなどのオレフィン系重合体を原料にして一段階で製造することができる。そのため、従来技術と比較して製造工程を大幅に簡素化することができ、製造コストやエネルギー消費の面で非常に有利である。 According to the present invention, a polymer in which an olefin polymer segment and a radical polymer segment are chemically bonded is produced in one step using olefin polymers such as polyethylene and polypropylene which are widely produced industrially as raw materials. Can do. Therefore, the manufacturing process can be greatly simplified as compared with the prior art, which is very advantageous in terms of manufacturing cost and energy consumption.
Claims (6)
ハロゲン元素を含まないオレフィン系重合体(A)、周期律表第3族〜第11族から選ばれる遷移金属元素を含む金属化合物(B)、および分子内にハロゲン−ハロゲン結合または窒素−ハロゲン結合を有する活性化剤(C)の存在下、ラジカル重合性単量体を重合させる、重合体の製造方法。 A method for producing a polymer in which an olefin polymer segment and a radical polymer segment are chemically bonded,
Olefin polymer containing no halogen element (A), metal compound (B) containing a transition metal element selected from Group 3 to Group 11 of the periodic table, and halogen-halogen bond or nitrogen-halogen bond in the molecule A method for producing a polymer, wherein a radically polymerizable monomer is polymerized in the presence of an activator (C) having a hydrogen atom.
(A1):CH2=CH−CXH2X+1(xは0または正の整数)で示されるα−オレフィン化合物の単独重合体または共重合体。
(A2):CH2=CH−CXH2X+1(xは0または正の整数)で示されるα−オレフィン化合物と芳香環を有するモノオレフィン化合物との共重合体。
(A3):CH2=CH−CXH2X+1(xは0または正の整数)で示されるα−オレフィン化合物と下記一般式(1)で表される環状モノオレフィン化合物との共重合体。
(A4):CH2=CH−CXH2X+1(xは0または正の整数)で示されるα−オレフィン化合物と不飽和カルボン酸またはその誘導体とのランダム共重合体。
(A5):前記重合体(A1)〜(A4)のいずれかを、不飽和カルボン酸またはその誘導体により変性したもの。
(A1): A homopolymer or copolymer of an α-olefin compound represented by CH 2 ═CH—C X H 2X + 1 (x is 0 or a positive integer).
(A2): A copolymer of an α-olefin compound represented by CH 2 ═CH—C X H 2X + 1 (x is 0 or a positive integer) and a monoolefin compound having an aromatic ring.
(A3): Co-weight of an α-olefin compound represented by CH 2 ═CH—C X H 2X + 1 (x is 0 or a positive integer) and a cyclic monoolefin compound represented by the following general formula (1) Coalescence.
(A4): A random copolymer of an α-olefin compound represented by CH 2 ═CH—C X H 2X + 1 (x is 0 or a positive integer) and an unsaturated carboxylic acid or a derivative thereof.
(A5): A polymer obtained by modifying any of the polymers (A1) to (A4) with an unsaturated carboxylic acid or a derivative thereof.
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JP2005048172A (en) * | 2003-07-14 | 2005-02-24 | Mitsubishi Chemicals Corp | Propylene-based block copolymer |
JP2005194487A (en) * | 2004-01-05 | 2005-07-21 | Dainippon Toryo Co Ltd | Pigment dispersing resin and coating composition containing the same |
WO2006085695A1 (en) * | 2005-02-14 | 2006-08-17 | Toyota Jidosha Kabushiki Kaisha | Graft copolymer and process for producing the same |
WO2006088197A1 (en) * | 2005-02-21 | 2006-08-24 | Mitsui Chemicals, Inc. | Hybrid polymer and method for production thereof |
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JP2005194487A (en) * | 2004-01-05 | 2005-07-21 | Dainippon Toryo Co Ltd | Pigment dispersing resin and coating composition containing the same |
WO2006085695A1 (en) * | 2005-02-14 | 2006-08-17 | Toyota Jidosha Kabushiki Kaisha | Graft copolymer and process for producing the same |
WO2006088197A1 (en) * | 2005-02-21 | 2006-08-24 | Mitsui Chemicals, Inc. | Hybrid polymer and method for production thereof |
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