CN117794998A - Multiblock copolymer, resin composition, and method for preparing the same - Google Patents
Multiblock copolymer, resin composition, and method for preparing the same Download PDFInfo
- Publication number
- CN117794998A CN117794998A CN202280055468.3A CN202280055468A CN117794998A CN 117794998 A CN117794998 A CN 117794998A CN 202280055468 A CN202280055468 A CN 202280055468A CN 117794998 A CN117794998 A CN 117794998A
- Authority
- CN
- China
- Prior art keywords
- carbon atoms
- group
- multiblock copolymer
- resin composition
- formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920006030 multiblock copolymer Polymers 0.000 title claims abstract description 123
- 239000011342 resin composition Substances 0.000 title claims abstract description 103
- 238000000034 method Methods 0.000 title claims abstract description 44
- -1 polypropylene Polymers 0.000 claims abstract description 73
- 239000004743 Polypropylene Substances 0.000 claims abstract description 52
- 229920001155 polypropylene Polymers 0.000 claims abstract description 51
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 45
- 229920001400 block copolymer Polymers 0.000 claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 claims abstract description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 171
- 150000001875 compounds Chemical class 0.000 claims description 116
- 125000000217 alkyl group Chemical group 0.000 claims description 54
- 239000000178 monomer Substances 0.000 claims description 45
- 239000004711 α-olefin Substances 0.000 claims description 31
- 125000003118 aryl group Chemical group 0.000 claims description 26
- 239000001257 hydrogen Substances 0.000 claims description 26
- 229910052739 hydrogen Inorganic materials 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 23
- 239000004793 Polystyrene Substances 0.000 claims description 21
- 229920000098 polyolefin Polymers 0.000 claims description 21
- 125000002947 alkylene group Chemical group 0.000 claims description 20
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 20
- 229920002223 polystyrene Polymers 0.000 claims description 20
- 239000003054 catalyst Substances 0.000 claims description 19
- 150000003623 transition metal compounds Chemical class 0.000 claims description 19
- 230000008569 process Effects 0.000 claims description 18
- 238000010539 anionic addition polymerization reaction Methods 0.000 claims description 17
- 238000000235 small-angle X-ray scattering Methods 0.000 claims description 17
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 16
- 239000003505 polymerization initiator Substances 0.000 claims description 16
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 15
- 239000005977 Ethylene Substances 0.000 claims description 15
- 229920002554 vinyl polymer Polymers 0.000 claims description 14
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 13
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 12
- 239000012986 chain transfer agent Substances 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 claims description 10
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 claims description 10
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 claims description 10
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 claims description 10
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 claims description 10
- DCTOHCCUXLBQMS-UHFFFAOYSA-N 1-undecene Chemical compound CCCCCCCCCC=C DCTOHCCUXLBQMS-UHFFFAOYSA-N 0.000 claims description 10
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 claims description 10
- 238000004458 analytical method Methods 0.000 claims description 10
- VAMFXQBUQXONLZ-UHFFFAOYSA-N n-alpha-eicosene Natural products CCCCCCCCCCCCCCCCCCC=C VAMFXQBUQXONLZ-UHFFFAOYSA-N 0.000 claims description 10
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 claims description 10
- 125000003545 alkoxy group Chemical group 0.000 claims description 9
- 125000003342 alkenyl group Chemical group 0.000 claims description 8
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 8
- 230000009477 glass transition Effects 0.000 claims description 8
- 125000005843 halogen group Chemical group 0.000 claims description 8
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 6
- 229940106006 1-eicosene Drugs 0.000 claims description 5
- FIKTURVKRGQNQD-UHFFFAOYSA-N 1-eicosene Natural products CCCCCCCCCCCCCCCCCC=CC(O)=O FIKTURVKRGQNQD-UHFFFAOYSA-N 0.000 claims description 5
- OWWRMMIWAOBBFK-UHFFFAOYSA-N 3,4-dimethylhex-1-ene Chemical compound CCC(C)C(C)C=C OWWRMMIWAOBBFK-UHFFFAOYSA-N 0.000 claims description 5
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 claims description 5
- LDTAOIUHUHHCMU-UHFFFAOYSA-N 3-methylpent-1-ene Chemical compound CCC(C)C=C LDTAOIUHUHHCMU-UHFFFAOYSA-N 0.000 claims description 5
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 5
- 229940069096 dodecene Drugs 0.000 claims description 5
- 238000006467 substitution reaction Methods 0.000 claims description 5
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 4
- 125000003282 alkyl amino group Chemical group 0.000 claims description 4
- 125000005103 alkyl silyl group Chemical group 0.000 claims description 4
- 125000000304 alkynyl group Chemical group 0.000 claims description 4
- 125000004104 aryloxy group Chemical group 0.000 claims description 4
- 150000002430 hydrocarbons Chemical group 0.000 claims description 4
- 125000004414 alkyl thio group Chemical group 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims description 3
- 125000001769 aryl amino group Chemical group 0.000 claims description 3
- 125000005104 aryl silyl group Chemical group 0.000 claims description 3
- 125000005110 aryl thio group Chemical group 0.000 claims description 3
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 3
- 229910052735 hafnium Inorganic materials 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 3
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- 125000001072 heteroaryl group Chemical group 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 2
- 150000002431 hydrogen Chemical group 0.000 claims 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 30
- 238000006243 chemical reaction Methods 0.000 description 29
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 24
- 229920000642 polymer Polymers 0.000 description 23
- 238000002360 preparation method Methods 0.000 description 22
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 20
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 18
- 238000005481 NMR spectroscopy Methods 0.000 description 18
- 239000011256 inorganic filler Substances 0.000 description 17
- 229910003475 inorganic filler Inorganic materials 0.000 description 17
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 16
- 150000004795 grignard reagents Chemical class 0.000 description 15
- 239000011701 zinc Substances 0.000 description 15
- 150000003752 zinc compounds Chemical class 0.000 description 15
- 239000007818 Grignard reagent Substances 0.000 description 14
- 229920001577 copolymer Polymers 0.000 description 14
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 14
- 239000002904 solvent Substances 0.000 description 14
- 238000005259 measurement Methods 0.000 description 13
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 13
- 239000000463 material Substances 0.000 description 12
- 239000000155 melt Substances 0.000 description 12
- 239000002245 particle Substances 0.000 description 12
- 230000000704 physical effect Effects 0.000 description 12
- 229910052799 carbon Inorganic materials 0.000 description 11
- 238000002156 mixing Methods 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 229910052725 zinc Inorganic materials 0.000 description 11
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 150000001721 carbon Chemical group 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 239000000460 chlorine Substances 0.000 description 7
- 239000000945 filler Substances 0.000 description 7
- 239000012535 impurity Substances 0.000 description 7
- 239000011777 magnesium Substances 0.000 description 7
- 229910052749 magnesium Inorganic materials 0.000 description 7
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 239000006227 byproduct Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 5
- 150000001336 alkenes Chemical class 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 5
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 5
- 239000002574 poison Substances 0.000 description 5
- 231100000614 poison Toxicity 0.000 description 5
- 239000002516 radical scavenger Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000011592 zinc chloride Substances 0.000 description 5
- 235000005074 zinc chloride Nutrition 0.000 description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- 238000004364 calculation method Methods 0.000 description 4
- 239000000539 dimer Substances 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 239000003446 ligand Substances 0.000 description 4
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical class C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 230000001747 exhibiting effect Effects 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920005673 polypropylene based resin Polymers 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 229920000428 triblock copolymer Polymers 0.000 description 3
- OCKGFTQIICXDQW-ZEQRLZLVSA-N 5-[(1r)-1-hydroxy-2-[4-[(2r)-2-hydroxy-2-(4-methyl-1-oxo-3h-2-benzofuran-5-yl)ethyl]piperazin-1-yl]ethyl]-4-methyl-3h-2-benzofuran-1-one Chemical compound C1=C2C(=O)OCC2=C(C)C([C@@H](O)CN2CCN(CC2)C[C@H](O)C2=CC=C3C(=O)OCC3=C2C)=C1 OCKGFTQIICXDQW-ZEQRLZLVSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920002633 Kraton (polymer) Polymers 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 2
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 238000012711 chain transfer polymerization Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical compound CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- LZKNIGOCHYEBST-UHFFFAOYSA-N ethane;methanol;zinc Chemical compound [Zn].[CH2-]C.OC LZKNIGOCHYEBST-UHFFFAOYSA-N 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000007429 general method Methods 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical group 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 238000007561 laser diffraction method Methods 0.000 description 2
- VCPPTNDHEILJHD-UHFFFAOYSA-N lithium;prop-1-ene Chemical compound [Li+].[CH2-]C=C VCPPTNDHEILJHD-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920005606 polypropylene copolymer Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 229920005604 random copolymer Polymers 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 150000003440 styrenes Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 2
- 229920002725 thermoplastic elastomer Polymers 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 238000004627 transmission electron microscopy Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WCFQIFDACWBNJT-UHFFFAOYSA-N $l^{1}-alumanyloxy(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]O[Al] WCFQIFDACWBNJT-UHFFFAOYSA-N 0.000 description 1
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- NTBQZBPZGVORFH-UHFFFAOYSA-N 1-(3-chloropropyl)-4-ethenylbenzene Chemical compound ClCCCC1=CC=C(C=C)C=C1 NTBQZBPZGVORFH-UHFFFAOYSA-N 0.000 description 1
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-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
- WHFHDVDXYKOSKI-UHFFFAOYSA-N 1-ethenyl-4-ethylbenzene Chemical compound CCC1=CC=C(C=C)C=C1 WHFHDVDXYKOSKI-UHFFFAOYSA-N 0.000 description 1
- YTDHOCZRXNHNKS-UHFFFAOYSA-N 2,6-dicyclohexylaniline Chemical compound NC1=C(C2CCCCC2)C=CC=C1C1CCCCC1 YTDHOCZRXNHNKS-UHFFFAOYSA-N 0.000 description 1
- YVSMQHYREUQGRX-UHFFFAOYSA-N 2-ethyloxaluminane Chemical compound CC[Al]1CCCCO1 YVSMQHYREUQGRX-UHFFFAOYSA-N 0.000 description 1
- VJJZJBUCDWKPLC-UHFFFAOYSA-N 3-methoxyapigenin Chemical compound O1C2=CC(O)=CC(O)=C2C(=O)C(OC)=C1C1=CC=C(O)C=C1 VJJZJBUCDWKPLC-UHFFFAOYSA-N 0.000 description 1
- JIGUICYYOYEXFS-UHFFFAOYSA-N 3-tert-butylbenzene-1,2-diol Chemical compound CC(C)(C)C1=CC=CC(O)=C1O JIGUICYYOYEXFS-UHFFFAOYSA-N 0.000 description 1
- QWFHFNGMCPMOCD-UHFFFAOYSA-N 6-bromopyridine-2-carbaldehyde Chemical compound BrC1=CC=CC(C=O)=N1 QWFHFNGMCPMOCD-UHFFFAOYSA-N 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 244000248349 Citrus limon Species 0.000 description 1
- 235000005979 Citrus limon Nutrition 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920011250 Polypropylene Block Copolymer Polymers 0.000 description 1
- 238000004639 Schlenk technique Methods 0.000 description 1
- 239000004113 Sepiolite Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- XNTMUPVTONHBCM-UHFFFAOYSA-N [Li]c1ccccc1C(C)C Chemical compound [Li]c1ccccc1C(C)C XNTMUPVTONHBCM-UHFFFAOYSA-N 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical group CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- 229920005603 alternating copolymer Polymers 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- OJMOMXZKOWKUTA-UHFFFAOYSA-N aluminum;borate Chemical compound [Al+3].[O-]B([O-])[O-] OJMOMXZKOWKUTA-UHFFFAOYSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 229910000085 borane Inorganic materials 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 229910052795 boron group element Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- AOWKSNWVBZGMTJ-UHFFFAOYSA-N calcium titanate Chemical compound [Ca+2].[O-][Ti]([O-])=O AOWKSNWVBZGMTJ-UHFFFAOYSA-N 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000012765 fibrous filler Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000004636 glovebox technique Methods 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- ZLVXBBHTMQJRSX-VMGNSXQWSA-N jdtic Chemical compound C1([C@]2(C)CCN(C[C@@H]2C)C[C@H](C(C)C)NC(=O)[C@@H]2NCC3=CC(O)=CC=C3C2)=CC=CC(O)=C1 ZLVXBBHTMQJRSX-VMGNSXQWSA-N 0.000 description 1
- CYPPCCJJKNISFK-UHFFFAOYSA-J kaolinite Chemical compound [OH-].[OH-].[OH-].[OH-].[Al+3].[Al+3].[O-][Si](=O)O[Si]([O-])=O CYPPCCJJKNISFK-UHFFFAOYSA-J 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 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
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- ZHLDMBMNKCIBQN-UHFFFAOYSA-M magnesium;methanolate;chloride Chemical compound [Cl-].CO[Mg+] ZHLDMBMNKCIBQN-UHFFFAOYSA-M 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000002557 mineral fiber Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229940088417 precipitated calcium carbonate Drugs 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical group C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 229920005653 propylene-ethylene copolymer Polymers 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 229910052624 sepiolite Inorganic materials 0.000 description 1
- 235000019355 sepiolite Nutrition 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 125000005624 silicic acid group Chemical class 0.000 description 1
- NGHMEZWZOZEZOH-UHFFFAOYSA-N silicic acid;hydrate Chemical compound O.O[Si](O)(O)O NGHMEZWZOZEZOH-UHFFFAOYSA-N 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000001464 small-angle X-ray scattering data Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 235000015096 spirit Nutrition 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000013638 trimer Substances 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
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 description 1
- 239000000326 ultraviolet stabilizing agent Substances 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Graft Or Block Polymers (AREA)
Abstract
The present invention relates to a multiblock copolymer, a method of preparing the multiblock copolymer, and a thermoplastic resin composition comprising polypropylene and the multiblock copolymer. The block copolymer has excellent processability and excellent compatibility with polypropylene, and the thermoplastic resin composition of the present invention using the block copolymer exhibits excellent low-temperature impact strength and can be effectively used as a thermoplastic resin composition for manufacturing products requiring high impact resistance such as automobile parts.
Description
Technical Field
The present application claims priority based on korean patent application nos. 10-2021-0130537 and 10-2021-0130578 filed on 1-10-2022-012448 and 10-2022-0124049 filed on 29-9-2022, the entire contents of which are incorporated herein by reference.
The present invention relates to a multiblock copolymer and a method of preparing the same, and more particularly, to a polyolefin-polystyrene-based multiblock copolymer comprising a polystyrene-based block and a polyolefin-based block, and a method of preparing the same.
Background
Block copolymers are materials as widely used for even high-tech devices as typical plastics, and research and development thereof are actively being conducted. In particular, a styrene-olefin copolymer resin containing both a block based on Polyolefin (PO) and a block based on Polystyrene (PS) has excellent heat resistance, light resistance, elasticity, and the like, and can be effectively used in various technical fields.
For polyolefin-polystyrene block copolymers, such as styrene-ethylene-butylene-styrene (SEBS) or styrene-ethylene-propylene-styrene (SEPS), markets on the scale of hundreds of thousands of tons have been developed worldwide. Typically, a polystyrene-block-poly (ethylene-co-1-butene) -block polystyrene (SEBS) triblock copolymer may be used as an example of one of the styrene-olefin copolymer resins. In the structure of the SEBS triblock copolymer, the hard polystyrene domains are separated from the soft poly (ethylene-co-1-butene) matrix and act as physical crosslinking sites and exhibit the properties of thermoplastic elastomers. Based on these properties, SEBS is more widely used in the product group requiring rubber and plastic, and demand is significantly increased according to expansion of the range of use.
Meanwhile, in order to express a luxurious feel of an automotive interior material, a method of injecting a resin composition composed of polycarbonate and acrylonitrile-butadiene-styrene (ABS) and attaching a skin material thereto has been used, but there are problems in that a process is complicated and a unit cost of a product is increased.
Accordingly, polypropylene-based resin compositions comprising polypropylene (PP), an impact reinforcement and an inorganic filler as main components have been used. Polypropylene has excellent rigidity and molding processability, and is widely used as a material for automobile interior and exterior parts, but has a defect of weak impact strength.
The polypropylene-based resin composition using the ethylene-alpha-olefin copolymer has physical properties of balanced impact strength, elasticity and bending strength, and has advantages of good moldability and affordable price, but has a limit in ensuring impact resistance according to different use environments.
In addition, styrene-ethylene-butylene-styrene (SEBS) based thermoplastic elastomers have been used in polypropylene-based resin compositions, but SEBS is expensive and significantly reduces the flowability of polypropylene, and has a problem in that flow marks or shortshots occur.
Accordingly, there is still a need to develop a thermoplastic resin composition that maintains the high flow properties of polypropylene without deteriorating mechanical properties.
[ Prior Art literature ]
[ patent literature ]
(patent document 1) korean registered patent No. 10-1657925
Disclosure of Invention
Technical problem
The object of the present invention is to provide a multiblock copolymer which has excellent processability and comprises a polystyrene-based block and a polyolefin-based block.
Another object of the present invention is to provide a thermoplastic resin composition having high flowability and excellent low-temperature impact strength.
Technical proposal
In order to solve the above-mentioned task, the present invention provides a multiblock copolymer, a method of preparing the multiblock copolymer, and a resin composition comprising polypropylene and the multiblock copolymer.
(1) The present invention provides a multiblock copolymer comprising a polystyrene-based block comprising repeat units derived from an aromatic vinyl-based monomer and a polyolefin-based block comprising repeat units derived from an alpha-olefin-based monomer, wherein the multiblock copolymer has a liquid ordered phase and a lamellar phase, the liquid ordered phase having a domain size (R) of 15.0nm to 22.0nm, an inter-domain distance (D1) of 40.0nm to 60.0nm, and the lamellar phase having a domain size (T) of 2.0nm to 9.0nm, an inter-domain distance (D2) of 10.0nm to 50.0nm, wherein the domain size and the inter-domain distance are measured by small angle X-ray scattering.
(2) The present invention provides the multiblock copolymer according to (1), wherein the multiblock copolymer has a liquid ordered phase as a main phase and a lamellar phase as a secondary phase.
(3) The present invention provides the multiblock copolymer according to (1) or (2), wherein the α -olefin-based monomer is an α -olefin-based monomer having 5 to 20 carbon atoms.
(4) The present invention provides the multiblock copolymer according to any one of (1) to (3), wherein the α -olefin-based monomer is one or more selected from the group consisting of 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-eicosene, 4-dimethyl-1-pentene, 4-diethyl-1-hexene and 3, 4-dimethyl-1-hexene.
(5) The present invention provides the multiblock copolymer according to any one of (1) to (4), wherein the domain size (R) of the liquid ordered phase of the multiblock copolymer is 15.0nm to 20.0nm.
(6) The present invention provides the multiblock copolymer according to any one of (1) to (5), wherein the inter-domain distance (D1) of the liquid-like ordered phase of the multiblock copolymer is 43.0nm to 56.0nm.
(7) The present invention provides the multiblock copolymer according to any one of (1) to (6), wherein the domain size (T) of the lamellar phase of the multiblock copolymer is 2.0nm to 5.0nm.
(8) The present invention provides the multiblock copolymer according to any one of (1) to (7), wherein the inter-domain distance (D2) of the lamellar phase of the multiblock copolymer is 12.0nm to 43.0nm.
(9) The present invention provides a process for preparing the multiblock copolymer according to (1), which comprises: (S1) a step of reacting ethylene with an α -olefin-based monomer in the presence of a catalyst composition comprising a transition metal compound using an organozinc compound as a chain transfer agent to prepare a polyolefin-based block; and (S2) a step of reacting an aromatic vinyl-based monomer and the polyolefin-based block in the presence of an anionic polymerization initiator to prepare a multiblock copolymer.
(10) The present invention provides the method for producing a multiblock copolymer according to (9), wherein the transition metal compound is a compound represented by the following formula 1:
[ 1]
In the formula 1, the components are mixed,
m is Ti, zr or Hf,
R 1 to R 4 Each independently is hydrogen, a substituted or unsubstituted alkyl group of 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group of 3 to 20 carbon atoms, or a substituted or unsubstituted aryl group of 6 to 20 carbon atoms, wherein two or more adjacent ones of them may be linked to form a ring;
R 5 And R is 6 Each independently is hydrogen, a substituted or unsubstituted alkyl group of 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group of 3 to 20 carbon atoms, or a substituted or unsubstituted aryl group of 6 to 20 carbon atoms, wherein the substitution is performed with an alkyl group of 1 to 12 carbon atoms;
each R 7 Independently is a substituted or unsubstituted alkyl group of 4 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group of 4 to 20 carbon atoms, or a substituted or unsubstituted aryl group of 6 to 20 carbon atoms;
n is 1 to 5; and
Y 1 and Y 2 Each independently is a halogen group, an alkyl group of 1 to 20 carbon atoms, an alkenyl group of 2 to 20 carbon atoms, an alkynyl group of 2 to 20 carbon atoms, a cycloalkyl group of 3 to 20 carbon atoms, an aryl group of 6 to 20 carbon atoms, an alkylaryl group of 7 to 20 carbon atoms, an arylalkyl group of 5 to 20 carbon atomsHeteroaryl of 20 carbon atoms, alkoxy of 1 to 20 carbon atoms, substituted or unsubstituted aryloxy of 5 to 20 carbon atoms, alkylamino of 1 to 20 carbon atoms, arylamino of 5 to 20 carbon atoms, alkylthio of 1 to 20 carbon atoms, arylthio of 5 to 20 carbon atoms, alkylsilyl of 1 to 20 carbon atoms, arylsilyl of 5 to 20 carbon atoms, hydroxy, amino, mercapto, silyl, cyano or nitro.
(11) The present invention provides a method for producing a multiblock copolymer according to (9) or (10), wherein the organozinc compound is represented by the following formula 5:
[ 5]
In the formula 5, the components are,
R 8 and R is 10 Each independently is a single bond or an alkylene group of 1 to 10 carbon atoms, R 9 Alkylene of 1 to 10 carbon atoms or-SiR 11 R 12 -, and R 11 And R is 12 Each independently is an alkyl group of 1 to 10 carbon atoms.
(12) The present invention provides the process for producing a multiblock copolymer according to any one of (9) to (11), wherein the anionic polymerization initiator comprises an alkyl lithium compound containing an allyl group, and the allyl group is combined with lithium.
(13) The present invention provides the process for producing a multiblock copolymer according to any one of (9) to (12), wherein the alkyl lithium compound is represented by the following formula 11:
[ 11]
In formula 11, R 13 Is hydrogen or a hydrocarbon group of 1 to 20 carbon atoms
Am is an amine-based compound represented by the following formula 12:
[ 12]
In the formula 12, the components are,
R 14 to R 18 Each independently hydrogen or a hydrocarbyl group of 1 to 20 carbon atoms, and
a and b are each independently integers from 0 to 3, wherein a and b are not both 0.
(14) The present invention provides a thermoplastic resin composition comprising polypropylene and the multiblock copolymer according to any one of (1) to (8).
(15) The present invention provides the thermoplastic resin composition according to (14), wherein the polypropylene and the multiblock copolymer are contained in a weight ratio of 1:0.1 to 1:9.
(16) The present invention provides the thermoplastic resin composition according to (14) or (15), wherein the thermoplastic resin composition satisfies the following conditions a) to c):
a) The height of the stress variation (tan delta) peak according to temperature, derived by dynamic viscoelasticity analysis, is 0.02 to 0.13; b) The radius (Rv) of the dispersed phase is 0.10 μm to 0.50 μm; and c) a glass transition temperature (Tg) of from-60 ℃ to-30 ℃.
(17) The present invention provides the thermoplastic resin composition according to any one of (14) to (16), wherein the thermoplastic resin composition satisfies b) that the radius (Rv) of the dispersed phase is 0.10 μm to 0.27 μm.
Advantageous effects
The multiblock copolymer provided in the present invention exhibits excellent processability and can be effectively used for manufacturing various molded products and resin compositions using the multiblock copolymer.
In addition, the thermoplastic resin composition provided in the present invention uses polypropylene and a multiblock copolymer having excellent compatibility with polypropylene and exhibits excellent low temperature impact strength, and thus can be effectively used as a thermoplastic resin composition for manufacturing products requiring high impact resistance (e.g., automobile parts).
Detailed Description
Hereinafter, the present invention will be described in more detail to aid understanding of the present invention.
It should be understood that words or terms used in the specification and claims of the present invention should not be construed as meaning defined in commonly used dictionaries. It is to be understood that words or terms should be interpreted to have meanings consistent with their meanings in the technical ideas of the present invention based on the principle that the inventor can properly define words to best explain the present invention.
In the present specification, "alkyl" refers to a straight or branched hydrocarbon residue.
In the present invention, "alkyl" refers to a straight or branched hydrocarbon residue.
In the present invention, "alkenyl" refers to a straight-chain or branched alkenyl group.
In the present invention, "aryl" preferably has 6 to 20 carbon atoms, and particularly includes, but is not limited to, phenyl, naphthyl, anthracenyl, pyridyl, dimethylanilino, anisole (aniolyl), and the like.
In the present invention, "alkylaryl" refers to an aryl group substituted with an alkyl group.
In the present invention, "arylalkyl" refers to an alkyl group substituted with an aryl group.
In the present invention, the "alkylsilyl group" may be a silyl group substituted with an alkyl group of 1 to 20 carbon atoms, for example, a trimethylsilyl group or a triethylsilyl group.
In the present invention, "alkylamino" refers to an amino group substituted with an alkyl group, and may include a dimethylamino group, a diethylamino group, and the like, but is not limited thereto.
In the present invention, "hydrocarbon group" means a monovalent hydrocarbon group of 1 to 20 carbon atoms, which, regardless of its structure, consists of only carbon and hydrogen, and includes alkyl, aryl, alkenyl, alkynyl, cycloalkyl, alkylaryl or arylalkyl groups, unless otherwise mentioned.
In this specification, the term "composition" includes mixtures of materials comprising the respective compositions as well as reaction products and decomposition products formed from the materials of the respective compositions.
In the present specification, the term "polymer" refers to a polymer compound prepared by polymerizing monomers of either the same type or different types. Similarly, the generic term polymer encompasses the term homopolymer, which is generally used to refer to polymers prepared from only one type of monomer, and the term interpolymer, which is specified below.
In the present specification, the term "copolymer" refers to a polymer prepared by polymerization of at least two different monomers.
In this specification, the number "0" after the decimal point may be omitted.
The present invention will be described in detail below.
Multiblock copolymers
The multiblock copolymer of the present invention is a multiblock copolymer comprising a polystyrene-based block comprising repeating units derived from an aromatic vinyl-based monomer and a polyolefin-based block comprising repeating units derived from an alpha-olefin-based monomer, wherein the multiblock copolymer has a liquid ordered phase having a domain size (R) of 15.0nm to 22.0nm, an inter-domain distance (D1) of 40.0nm to 60.0nm, and an inter-domain distance (T) of 2.0nm to 9.0nm, and an inter-domain distance (D2) of 10.0nm to 50.0nm, and a lamellar phase, the domain size and the inter-domain distance being measured by small angle X-ray scattering.
The microstructure and morphology of the polymer and/or copolymer can be ascertained if analyzed using small angle X-ray scattering (SAXS) and Transmission Electron Microscopy (TEM). In particular, by indexing of small angle X-ray scattering (SAXS) analysis, the phase of the polymer can be predicted, and if fitting is performed assuming a model of the diffraction peaks of the SAXS pattern, information of the polymer structure, such as specific phase domain size and inter-domain distance, can be obtained. Further, by analyzing Transmission Electron Microscope (TEM) images together, the morphology of the polymer can be understood.
As described below, the multiblock copolymer of the present invention is prepared by using a specific transition metal compound having a novel structure as a catalyst, and has a liquid-like ordered phase as a main phase and a lamellar phase as a secondary phase in analysis by small angle X-ray scattering (SAXS). The major and minor phases can be distinguished by index of small angle X-ray scattering (SAXS) analysis. The intensity of the secondary phases is relatively very small compared to the primary phase and they can be distinguished.
In the specification of the present invention, the domain size of the liquid-like ordered phase is represented by R, the inter-domain distance is represented by D1, and the domain size (R) of the liquid-like ordered phase of the multiblock copolymer of the present invention is 15.0nm to 22.0nm, and the inter-domain distance (D1) is 40.0nm to 60.0nm.
Furthermore, in the multiblock copolymer according to an embodiment of the present invention, the domain size (R) of the liquid ordered phase may be particularly 15.0nm or more, 15.2nm or more, 15.5nm or more, and 22.0nm or less, 21nm or less, 20.5nm or less, 20.0nm or less, 19.5nm or less, 19.0nm or less, more particularly, 15.0nm to 20.0nm, 15.0nm to 19.0nm, 15.5nm to 20.0nm, or 15.5nm to 19.0nm.
In addition, in the multiblock copolymer according to the embodiment of the present invention, the inter-domain distance (D1) of the liquid ordered phase may be particularly 40.0nm or more, 40.5nm or more, 41.0nm or more, 41.5nm or more, 42.0nm or more, 42.5nm or more, 43.0nm or more, and 59.0nm or less, 58.0nm or less, 57.0nm or less, 56.0nm or less, 55.5nm or less, 55.0nm or less, more particularly, 42.5nm to 56.0nm, 42.5nm to 55.5nm, 42.5nm to 55.0nm, 43.0nm to 56.0nm, or 43.0nm to 55.0nm.
In the present specification, the domain size of the lamellar phase is represented by T, the inter-domain distance is represented by D2, and the lamellar phase of the multiblock copolymer of the present invention has a domain size (T) of 2.0nm to 9.0nm and an inter-domain distance (D2) of 10.0nm to 50.0nm.
In addition, in the multiblock copolymer according to an embodiment of the present invention, the domain size (T) of the lamellar phase may be particularly 2.0nm to 8.0nm, 2.0nm to 7.0nm, 2.0nm to 6.0nm, 2.0nm to 5.0nm, 2.0nm to 4.5nm, 2.2nm to 8.0nm, 2.2nm to 7.0nm, 2.2nm to 6.0nm, 2.2nm to 5.0nm, 2.2nm to 4.5nm, more particularly 2.2nm to 4.0nm.
Further, in the multiblock copolymer according to the embodiment of the present invention, the inter-domain distance (D2) of the lamellar phase may be particularly 10.0nm or more, 10.5nm or more, 11.0nm or more, 11.5nm or more, 12.0nm or more, and 48.0nm or less, 46.0nm or less, 45.0nm or less, 44.0nm or less, 43.0nm or less, more particularly, 11.0nm to 44.0nm, 11.5nm to 44.0nm, 12.0nm to 44.0nm, or 12.0nm to 43.0nm.
As described above, the domain size and the inter-domain distance are measured by small angle X-ray scattering, and the ranges of the domain size and the inter-domain distance are information on the microstructure of the multiblock copolymer of the present invention to illustrate the properties of the multiblock copolymer of the present invention.
The excellent processability of the multiblock copolymer of the present invention can be confirmed by the melt flow index of the resin composition prepared during the preparation of the thermoplastic resin composition by mixing with polypropylene. The multiblock copolymer of the present invention satisfying the above range may exhibit excellent miscibility during the preparation of a resin composition by mixing with polypropylene, and the resin composition thus prepared may maintain excellent flow properties. In particular, when a resin composition is prepared by mixing the multiblock copolymer of the present invention with polypropylene in a weight ratio of 1:0.11 to 1:9, the resin composition thus prepared may exhibit a melt flow rate (MFR, 230 ℃ C., 2.16 kg) of 20g/10min to 100g/10 min. The melt flow rate may be a melt flow rate exhibited by a thermoplastic resin composition comprising polypropylene and a multiblock copolymer in a weight ratio of 1:0.11 to 1:4, 1:0.11 to 1:3, 1:0.11 to 1:2.4, 1:0.11 to 1:1.5, 1:0.11 to 1:1, 1:0.17 to 1:1.5, 1:0.17 to 1:1, more particularly, 1:0.17 to 1:0.25.
If the resin composition comprises polypropylene and a multiblock copolymer in a weight ratio of 1:0.25, the melt flow rate may be specifically 20g/10min or more, 20.5g/10min or more, 21.0g/10min or more, and 100g/10min or less, 90g/10min or less, 80g/10min or less, 70g/10min or less, 60g/10min or less, 50g/10min or less, 40g/10min or less, 30g/10min or less. Melt flow rate was measured according to ASTM-D1238 at 230℃under a load of 2.16 kg.
The multiblock copolymers may have a weight average molecular weight (Mw) of 100,000 to 300,000g/mol, specifically 105,000g/mol or more, and 300,000g/mol or less, 250,000g/mol or less, more specifically 120,000 to 240,000g/mol.
The molecular weight distribution (PDI) of the multiblock copolymer may be 1.5 to 3.0, particularly 1.55 or more, 1.6 or more, 1.65 or more, and 2.8 or less, 2.6 or less, 2.5 or less, 2.3 or less, 2.0 or less, more particularly 1.65 to 2.0.
The molecular weight distribution is calculated from the ratio of (weight average molecular weight)/(number average molecular weight), and the weight average molecular weight and the number average molecular weight are molecular weights in terms of polystyrene analyzed by Gel Permeation Chromatography (GPC).
The multiblock copolymer of the present invention is a polyolefin-polystyrene-based multiblock copolymer comprising a polystyrene-based block comprising repeating units derived from an aromatic vinyl-based monomer and a polyolefin-based block comprising repeating units derived from an ethylene-based monomer and repeating units derived from an alpha-olefin-based monomer, and the alpha-olefin-based monomer may be an alpha-olefin of 5 to 20 carbon atoms, particularly an alpha-olefin of 5 to 14 carbon atoms.
The alpha-olefin-based monomer may be, for example, one or more selected from the group consisting of 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-eicosene, 4-dimethyl-1-pentene, 4-diethyl-1-hexene and 3, 4-dimethyl-1-hexene, in particular 1-hexene.
Method for producing multiblock copolymers
The process for preparing the multiblock copolymers of the present invention comprises: (S1) a step of reacting ethylene with an α -olefin-based monomer in the presence of a catalyst composition comprising a transition metal compound using an organozinc compound as a chain transfer agent to prepare a polyolefin-based block; and (S2) a step of reacting an aromatic vinyl-based monomer and the polyolefin-based block in the presence of an anionic polymerization initiator to prepare a multiblock copolymer.
Step (S1)
Step (S1) is a step of reacting ethylene with an α -olefin-based monomer in the presence of a catalyst composition comprising a transition metal compound, using an organozinc compound as a chain transfer agent, to prepare a polyolefin-based block.
According to an embodiment of the present invention, the transition metal catalyst is a catalyst for growing an olefin-based polymer by coordination chain transfer polymerization, and may be a catalyst composition including a transition metal catalyst as a main catalyst and a cocatalyst.
In the present invention, the transition metal compound may be a compound represented by the following formula 1.
[ 1]
In the formula 1, the components are mixed,
m is Ti, zr or Hf,
R 1 to R 4 Each independently is hydrogen, a substituted or unsubstituted alkyl group of 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group of 3 to 20 carbon atoms, or a substituted or unsubstituted aryl group of 6 to 20 carbon atoms, wherein two or more adjacent ones of them may be linked to form a ring;
R 5 and R is 6 Each independently is hydrogen, a substituted or unsubstituted alkyl group of 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group of 3 to 20 carbon atoms, or a substituted or unsubstituted aryl group of 6 to 20 carbon atoms, wherein the substitution is performed with an alkyl group of 1 to 12 carbon atoms;
each R 7 Independently is a substituted or unsubstituted alkyl group of 4 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group of 4 to 20 carbon atoms, or a substituted or unsubstituted aryl group of 6 to 20 carbon atoms;
n is 1 to 5; and
Y 1 and Y 2 Each independently of the otherIs a halogen group, an alkyl group of 1 to 20 carbon atoms, an alkenyl group of 2 to 20 carbon atoms, an alkynyl group of 2 to 20 carbon atoms, a cycloalkyl group of 3 to 20 carbon atoms, an aryl group of 6 to 20 carbon atoms, an alkylaryl group of 7 to 20 carbon atoms, an arylalkyl group of 7 to 20 carbon atoms, a heteroaryl group of 5 to 20 carbon atoms, an alkoxy group of 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group of 5 to 20 carbon atoms, an alkylamino group of 1 to 20 carbon atoms, an arylamino group of 5 to 20 carbon atoms, an alkylthio group of 1 to 20 carbon atoms, an arylthio group of 5 to 20 carbon atoms, an alkylsilyl group of 1 to 20 carbon atoms, an arylsilyl group of 5 to 20 carbon atoms, a hydroxyl group, an amino group, a mercapto group, a silyl group, a cyano group or a nitro group.
In particular, in formula 1, M may be Hf.
In addition, in particular, in formula 1, R 1 To R 4 May each independently be hydrogen; or a substituted or unsubstituted alkyl group of 1 to 20 carbon atoms, wherein two or more of them adjacent may be linked to form a ring. Alternatively, R 1 And R is 2 Can each independently be an alkyl group of 1 to 20 carbon atoms and can be linked to each other to form an aromatic ring of 5 to 20 carbon atoms, and R 3 And R is 4 May be hydrogen.
In addition, in particular, in formula 1, R 5 And R is 6 Each independently is hydrogen; or a substituted or unsubstituted aryl group of 6 to 20 carbon atoms, wherein the substitution is made with an alkyl group of 1 to 6 carbon atoms.
Further, in particular, in formula 1, each R 7 An alkyl group of 4 to 20 carbon atoms which may be independently substituted or unsubstituted; substituted or unsubstituted cycloalkyl of 4 to 20 carbon atoms; or a substituted or unsubstituted aryl group of 6 to 20 carbon atoms.
In particular, in formula 1, n may be 1 to 3, preferably 2.
In particular, in formula 1, X 1 And X 2 May each independently be an alkyl group of 1 to 20 carbon atoms.
More specifically, the transition metal compound represented by formula 1 may be a compound represented by the following formula 1 a.
[ 1a ]
In the case of the composition of formula 1a,
M、R 5 to R 7 、Y 1 And Y 2 As defined above.
The transition metal compound represented by formula 1 may be specifically selected from the following compounds, but is not limited thereto, and all transition metal compounds corresponding to formula 1 are included in the present invention.
[ 1-1]
[ 1-2]
[ 1-3]
[ 1-4]
[ 1-5]
[ 1-6]
[ 1-7]
[ 1-8 ]]
Further, the present invention provides a ligand compound represented by the following formula 2.
[ 2]
In the formula 2, the components are mixed,
R 1 to R 4 Each independently is a substituted or unsubstituted alkyl group of 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group of 3 to 20 carbon atoms, or a substituted or unsubstituted aryl group of 6 to 20 carbon atoms, wherein two or more adjacent ones of them may be linked to form a ring;
R 5 and R is 6 Each independently is hydrogen, a substituted or unsubstituted alkyl group of 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group of 3 to 20 carbon atoms, or a substituted or unsubstituted aryl group of 6 to 20 carbon atoms, wherein the substitution is performed with an alkyl group of 1 to 12 carbon atoms;
each R 7 Independently is a substituted or unsubstituted alkyl group of 4 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group of 4 to 20 carbon atoms, or a substituted or unsubstituted aryl group of 6 to 20 carbon atoms; and
n is 1 to 5.
That is, the transition metal compound of the present invention may be prepared by a step comprising reacting a ligand compound represented by the following formula 2 and a compound represented by the formula 3.
[ 2]
[ 3]
M(Y 1 Y 2 ) 2
In the above-mentioned method, the step of,
R 1 to R 7 、M、Y 1 And Y 2 The same definition as above.
Meanwhile, in the process of preparing the transition metal compound represented by formula 1 of the present invention, the reaction may be performed by the following method.
[ reaction 1]
[ reaction 2]
In the present invention, the organozinc compound is used as a chain transfer agent, which is a material for preparing a copolymer by performing chain transfer induction during the preparation process in polymerization, and may be a chain transfer agent for preparing a block copolymer by coordination chain transfer polymerization.
In the embodiment of the present invention, the chain transfer agent may contain the organozinc compound represented by the following formula 5, and in particular, the chain transfer agent may contain 96mol% or more of the organozinc compound represented by the following formula 5, and preferably, may not include by-products other than the organozinc compound represented by the formula 5.
[ 5]
In the formula 5, the components are,
R 8 and R is 10 Each independently is a single bond or an alkylene group of 1 to 10 carbon atoms, R 9 Alkylene of 1 to 10 carbon atoms or-SiR 11 R 12 -, and R 11 And R is 12 Each independently of the otherAlkyl of 1 to 10 carbon atoms.
Furthermore, according to an embodiment of the present invention, in formula 5, R 8 And R is 10 Can each independently be a single bond or an alkylene group of 1 carbon atom, R 9 Alkylene or-SiR which may be 1 carbon atom 11 R 12 -, and R 11 And R is 12 Each independently is an alkyl group of 1 carbon atom.
According to an embodiment of the present invention, the organozinc compound represented by formula 5 may be one selected from the organozinc compounds represented by formulas 5-1 to 5-4, preferably, any one of formulas 5-3 and 5-4 below.
[ 5-1]
[ 5-2]
/>
[ 5-3]
[ 5-4]
According to an embodiment of the present invention, the chain transfer agent may preferably contain 97mol% or more, preferably 98mol% or more, or 99mol% or more of the organozinc compound of formula 5. Most preferably, by-products other than organozinc compounds may not be included. This means that impurities containing chlorine or magnesium, such as by-products of dimers, are not included other than the organozinc compound represented by formula 5. That is, the chain transfer agent may include only the organozinc compound represented by formula 5.
If in a bagPolymerization can be performed by reacting ethylene with an alpha-olefin-based monomer using an organozinc compound of formula 5 as a chain transfer agent in the presence of a catalyst composition containing a transition metal compound, zinc (Zn) and R in the organozinc compound 10 With the insertion of ethylene and an alpha-olefin based monomer. In an embodiment of the method of preparing a multiblock copolymer of the present invention, if the compound of formula 4 is used as the organozinc compound for preparing the polyolefin-based block by reacting ethylene with the α -olefin-based monomer, an olefin-based polymer block intermediate may be prepared, and an example of the olefin-based polymer block intermediate may be represented by formula 6
[ 6]
In formula 6, R 8 And R is 10 May each independently be a single bond or an alkylene group of 1 to 10 carbon atoms, R 9 Alkylene or-SiR, which may be 1 to 10 carbon atoms 11 R 12 -,R 11 And R is 12 Each independently is an alkyl group of 1 to 10 carbon atoms, and PO may be an olefin-based polymer block.
According to an embodiment of the present invention, the organozinc compound may be prepared by a method comprising the steps of: a step of preparing a Grignard reagent containing a styrene residue; and a step of reacting the prepared grignard reagent with a zinc compound to prepare an organozinc compound represented by formula 5, and the zinc compound may be an alkyl zinc alkoxide.
According to an embodiment of the present invention, the organozinc compound prepared by the preparation method of the organozinc compound and synthesized from the organozinc compound represented by formula 5 into a single compound does not contain byproducts such as dimers, and further, does not include chlorine-containing impurities such as organozinc chloride (R-Zn-Cl) which may act as a catalyst poison. In addition, if the organozinc compound represented by formula 5 is prepared according to the preparation method of the organozinc compound, a single compound is synthesized, and an excellent effect of synthesis reproduction can be achieved. Meanwhile, in preparing the organozinc compound, as in the present invention, it may be important to select a grignard reagent containing a styrene residue and a zinc compound in order to remove byproducts and impurities.
According to an embodiment of the present invention, the grignard reagent containing a styrene residue may be represented by the following formula 7.
[ 7]
In formula 7, R 8 And R is 10 May each independently be a single bond or an alkylene group of 1 to 10 carbon atoms, R 9 Alkylene or-SiR, which may be 1 to 10 carbon atoms 11 R 12 -,R 11 And R is 12 May each independently be an alkyl group having 1 to 10 carbon atoms, and X may be a halogen group.
In addition, according to an embodiment of the present invention, in formula 7, R 8 And R is 10 Can each independently be a single bond or an alkylene group of 1 carbon atom, R 9 Alkylene or-SiR which may be 1 carbon atom 11 R 12 -, and R 11 And R is 12 May each independently be an alkyl group of 1 carbon atom.
According to an embodiment of the present invention, the grignard reagent containing a styrene residue represented by formula 7 may be one selected from the group consisting of the grignard reagents containing a styrene residue represented by the following formulas 7-1 to 7-4.
[ 7-1]
[ 7-2]
[ 7-3]
[ 7-4]
According to an embodiment of the present invention, the Grignard reagent containing a styrene residue represented by formula 7 may be represented by R 8 The substituted halides (-X) are prepared by reaction with magnesium, especially magnesium powder or magnesium metal.
According to an embodiment of the present invention, the grignard reagent containing a styrene residue represented by formula 7 may be prepared by reacting a compound represented by formula 8 below with magnesium, particularly magnesium powder or magnesium metal.
[ 8]
In formula 8, R 8 And R is 10 May each independently be a single bond or an alkylene group of 1 to 10 carbon atoms, R 9 Alkylene or-SiR, which may be 1 to 10 carbon atoms 11 R 12 -,R 11 And R is 12 May each independently be an alkyl group of 1 to 10 carbon atoms, and X may be a halogen group.
According to an embodiment of the present invention, in formula 8, R 8 And R is 10 May each independently be a single bond or an alkylene group of 1 to 3 carbon atoms, R 9 Alkylene or-SiR, which may be 1 to 3 carbon atoms 11 R 12 -,R 11 And R is 12 May each independently be an alkyl group of 1 to 3 carbon atoms, and X may be a halogen group.
Furthermore, according to an embodiment of the present invention, in formula 8, R 8 And R is 10 Can each independently be a single bond or an alkylene group of 1 carbon atom, R 9 Alkylene or-SiR which may be 1 carbon atom 11 R 12 -,R 11 And R is 12 Can each independently be 1 carbon atomAlkyl of the sub-group, and X may be a halogen group selected from Cl, br and I.
According to an embodiment of the present invention, the compound represented by formula 8 may be one selected from the compounds represented by the following formulas 8-1 to 8-4.
[ 8-1]
[ 8-2]
[ 8-3]
[ 8-4]
According to an embodiment of the present invention, in preparing the grignard reagent containing a styrene residue represented by formula 7, the reaction of the compound represented by formula 8 with magnesium powder or magnesium metal may be performed with an excessive molar ratio, that is, a molar ratio of magnesium powder or magnesium metal greater than 1 mole with respect to 1 mole of the compound represented by formula 8 may be used, and in this case, 50mol% or more, 60mol% or more, 70mol% or more, 80mol% or more, 90mol% or more, 95mol% or more, or 99mol% or more of the compound represented by formula 8 may be converted into the grignard reagent containing a styrene residue represented by formula 7.
According to an embodiment of the present invention, the reaction of the compound represented by formula 8 with magnesium powder or magnesium metal may be performed in a molar ratio of greater than 1:1 to 1:10, greater than 1:1 to 1:5, greater than 1:1 to 1:2, or 1:1.01 to 1:1.60, and within this range, the conversion rate with the grignard reagent containing styrene residues represented by formula 7 may be high, the residual magnesium content after the reaction may be minimized, and the residual magnesium powder or magnesium metal may be easily removed.
In preparing organozinc compounds according to embodiments of the present invention, it is desirable that the zinc compound be a zinc compound that is capable of being substituted on zinc with the same two organic groups. Thus, zinc chloride (ZnCl) can be easily considered 2 ) However, if zinc chloride is used as the zinc compound, there is a problem of residual impurities including chlorine (for example, alkyl zinc chloride), which may act as a catalyst poison. Thus, in the present invention, an alkyl zinc alkoxide is used as the zinc compound.
According to an embodiment of the present invention, the alkyl group of the alkyl zinc alkoxide may be an alkyl group of 1 to 10 carbon atoms, an alkyl group of 1 to 5 carbon atoms, an alkyl group of 1 to 3 carbon atoms, or an ethyl group, and the alkoxy group may be an alkoxy group of 1 to 10 carbon atoms, an alkoxy group of 1 to 5 carbon atoms, an alkoxy group of 1 to 3 carbon atoms, or a methoxy group. In one embodiment, the zinc compound may be ethylzinc methoxide.
According to embodiments of the present invention, the alkyl zinc alkoxide may be prepared from a dialkyl zinc. In a specific embodiment, the alkyl zinc alkoxide may be prepared by reacting a dialkyl zinc and an alcohol in situ. In this case, the alkyl group of the dialkylzinc may be the same as that of the above-mentioned alkylzinc alkoxide, and the alcohol may be an alcohol in which hydrogen and an alkoxy group of the alkylzinc alkoxide are bonded.
According to an embodiment of the present invention, if an alkyl zinc alkoxide is used as a zinc compound, an alkoxymagnesium halide is generated during the reaction of a grignard reagent with the zinc compound, and since this is an insoluble salt, it is easy to filter, thereby preventing impurities from remaining.
According to an embodiment of the present invention, the reaction of the grignard reagent and the zinc compound may be performed at a molar ratio of 10:1 to 1:10, 5:1 to 1:5, 3:1 to 1:3, 2:1 to 1:2, 1.5:1 to 1:1.5, or 1:1 on a molar ratio basis, and within this range, a single compound may be synthesized, byproducts such as dimers may be removed, impurities containing chlorine that may act as a catalyst poison may be removed, and impurities including magnesium that may act as a catalyst poison may be easily removed.
According to the embodiment of the present invention, all steps and all reactions of the preparation method of the zinc compound can be performed in an organic solvent, and the reaction temperature and reaction pressure can be controlled according to the purpose of improving the yield and purity.
In the preparation method of the zinc compound according to the embodiment of the present invention, the catalyst poison can be completely removed by replacing the conventional borane-based compound containing a styrene residue with a grignard reagent containing a styrene residue and replacing the alkyl zinc or zinc chloride with an alkyl zinc alkoxide.
In addition, by modification of this method, unlike the conventional method in which a mixture of a dimer, a trimer and a zinc compound having a terminal saturated is obtained as a product, a compound of a monomer type having a terminal vinyl group completely conserved is obtained as a single compound. Thus, the storage stability of the zinc compound can be improved, the physical properties of the final copolymer can be improved, and the yield of diblock rather than triblock copolymers can be significantly reduced.
In addition, the catalyst composition may further include a compound represented by the following formula 9, and the compound represented by the formula 8 may function as a cocatalyst and a scavenger.
[ 9]
-[Al(R a )-O] m -
In the formula 9, the components are mixed,
each R a Independently a halogen group; a hydrocarbyl group of 1 to 20 carbon atoms; or halogen substituted hydrocarbyl of 1 to 20 carbon atoms, and
m is an integer of 2 or more.
The compound represented by formula 9 is not particularly limited as long as it is an alkylaluminoxane. Preferred examples may be Modified Methylaluminoxane (MMAO), methylaluminoxane (MAO), ethylaluminoxane, isobutylaluminoxane, butylaluminoxane, etc. and particularly preferred compounds may be Modified Methylaluminoxane (MMAO).
The compound represented by formula 9 is an oligomer type compound produced by the reaction of aluminum alkyl with water, and if used as a cocatalyst, chain transfer can be reduced. Accordingly, a copolymer having a high molecular weight can be prepared, and the generation of homopolyolefin by side reaction can be prevented. Thus, finally, a polyolefin-polystyrene based multiblock copolymer exhibiting excellent physical properties such as high tensile strength can be prepared.
Meanwhile, as described above, the compound represented by formula 9 may inhibit chain transfer, but conversely, for example, if a compound such as an aluminum alkyl is used as a cocatalyst, chain transfer occurs in large amounts, the molecular weight of the copolymer may decrease, the yield of the homopolyolefin may increase, and a problem of deterioration of the physical properties of the block copolymer may occur.
Thus, by using the transition metal compound represented by formula 1 and the compound represented by formula 5 in combination in the present invention, a multiblock copolymer satisfying the above conditions can be produced.
In addition, the transition metal compound represented by formula 1 and the compound represented by formula 9 may be used in a type supported by a carrier. As the carrier, silica or alumina may be used, but is not limited thereto.
In addition, the catalyst composition may further comprise a compound represented by the following formula 10.
[ 10]
[L-H] + [Z(A) 4 ] - Or [ L ]] + [Z(A) 4 ] -
In the process of 10, the process is carried out,
z is an element in group 13,
each a is independently an aryl group of 6 to 20 carbon atoms, wherein one or more hydrogen atoms may be substituted with substituents; or alkyl of 1 to 20 carbon atoms
The substituent of A is halogen; or a hydrocarbyl group of 1 to 20 carbon atoms; alkoxy of 1 to 20 carbon atoms; or an aryloxy group of 6 to 20 carbon atoms.
For example, step (S1) may be performed in a homogeneous solution state. In this case, a hydrocarbon solvent may be used as the solvent, or an olefin monomer itself may be used as the medium. The hydrocarbon solvent may include aliphatic hydrocarbon solvents of 4 to 20 carbon atoms, particularly isobutane, hexane, cyclohexane, methylcyclohexane and the like. The solvent may be used alone or as a mixture of two or more thereof.
The polymerization temperature of step (S1) may vary depending on the reaction material, reaction conditions, etc., and may be particularly 70 to 170 ℃, particularly 80 to 150 ℃, or 90 to 120 ℃. Within the above range, the solubility of the polymer may be increased, and the catalyst may be thermally stable.
The polymerization in step (S1) may be carried out batchwise, semicontinuously or continuously, or may be carried out by two or more steps having different reaction conditions.
The compound prepared by the above step (S1) may function as a precursor for preparing the polyolefin-polystyrene-based multiblock copolymer of the present invention by the anionic polymerization of step (S2), which will be explained later.
In embodiments of the present invention, the alpha-olefin-based monomer may be an alpha-olefin of 5 to 20 carbon atoms, particularly an alpha-olefin of 5 to 14 carbon atoms.
In the embodiment of the present invention, as examples of the α -olefin, one or more selected from 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-eicosene, 4-dimethyl-1-pentene, 4-diethyl-1-hexene and 3, 4-dimethyl-1-hexene may be included, more particularly 1-hexene.
Step (S2)
Step (S2) is a step of reacting an aromatic vinyl-based monomer with a polyolefin-based block to prepare a multiblock copolymer.
In the step (S2), an aromatic vinyl-based monomer may be continuously inserted into (polyalkenyl) contained in the compound formed in the step (S1) 2 Zinc-carbon bonds of Zn to form polystyrene-based chains and, at the same time, originate from the presence ofThe styrene group of the chain extender at the end of the compound formed by step (S1) may participate as a copolymer moiety with the aromatic vinyl-based monomer to be linked to the polystyrene chain. In addition, the multiblock copolymer produced by the method can be easily quenched by the reaction of the terminal group with water, oxygen or an organic acid, and in this way, conversion to an industrially useful polyolefin-polystyrene-based multiblock copolymer can be achieved.
The aromatic vinyl-based monomer may be an aromatic vinyl-based monomer of 6 to 20 carbon atoms. Aromatic vinyl-based monomers including, for example, ethylene substituted with aryl groups of 6 to 20 carbon atoms, ethylene substituted with phenyl groups, e.g., styrene, alpha-methylstyrene, vinyltoluene, ethylene substituted with C 1-3 Alkyl-substituted alkylstyrenes (e.g., o-methylstyrene, m-methylstyrene, p-ethylstyrene, etc.), or halogen-substituted styrenes, more particularly, styrenes may be used.
In the embodiment of the present invention, the anionic polymerization initiator may be an alkyllithium compound represented by the following formula 11.
[ 11]
In the formula 11, the components are,
R 13 is hydrogen or a hydrocarbon group of 1 to 20 carbon atoms,
am is an amine-based compound represented by the following formula 12,
[ 12]
In the formula 12, the components are,
R 14 to R 18 Each independently hydrogen or a hydrocarbyl group of 1 to 20 carbon atoms, and
a and b are each independently integers from 0 to 3, wherein a and b are not both 0.
In an embodiment of the invention, R 13 May be hydrogen, alkyl of 1 to 20 carbon atoms, cycloalkyl of 3 to 20 carbon atoms, or substituted or unsubstituted arylalkyl of 7 to 20 carbon atoms;
R 14 to R 18 May each independently be hydrogen, an alkyl group of 1 to 20 carbon atoms, an alkenyl group of 1 to 20 carbon atoms, a cycloalkyl group of 3 to 20 carbon atoms, a substituted or unsubstituted aryl group of 6 to 20 carbon atoms, or a substituted or unsubstituted arylalkyl group of 7 to 20 carbon atoms; and
a and b may each independently be an integer of 0 to 2.
In addition, in an embodiment of the present invention, R 13 To R 18 May each independently be hydrogen or alkyl of 1 to 20 carbon atoms; and a is 1 or 2, and b may be 0 or 1.
In particular, a is an integer from 1 to 3, b may be an integer from 0 to 3, more particularly a is 1 or 2, b may be an integer from 0 to 2, more particularly a is 1 or 2, and b may be 0 or 1.
In the embodiment of the present invention, am in formula 11 may be represented by the following formula 13 or 14.
[ 13]
[ 14]
In the method, in the process of the invention,
R 14 、R 15 and R is 18 Each independently is hydrogen or an alkyl group of 1 to 20 carbon atoms.
In addition, in the embodiment of the present invention, am in formula 11 may be specifically represented by the following formula 13a or formula 14 a.
[ 13a ]
[ 14a ]
In the preparation method of the multiblock copolymer of the present invention, the compound represented by formula 11 is used as an anionic polymerization initiator, and the polystyrene-based chain may be grown from the organozinc compound prepared in step S1, specifically, wherein the polyolefin-based chain grows centering on zinc (Zn) (polyalkenyl) 2 Polyolefin of Zn.
The anionic polymerization initiator can be prepared by the following preparation method.
The preparation method of the anionic polymerization initiator includes a process of injecting and reacting a compound represented by formula 16 and a compound represented by formula 12 in the presence of a compound represented by formula 15.
[ 12]
[ 15]
B-Li
[ 16]
In the method, in the process of the invention,
R 13 to R 18 Each independently is hydrogen or a hydrocarbyl group of 1 to 20 carbon atoms;
a and b are each independently integers from 0 to 3, wherein a and b are not both 0 at the same time;
b is an alkyl group of 1 to 20 carbon atoms.
In an embodiment of the invention, R 13 May be hydrogen or a hydrocarbon group of 1 to 20 carbon atoms;
R 14 to R 18 May each independently be hydrogen, an alkyl group of 1 to 20 carbon atoms, an alkenyl group of 1 to 20 carbon atoms, a cycloalkyl group of 3 to 20 carbon atoms, a substituted or unsubstituted aryl group of 6 to 20 carbon atoms, or a substituted or unsubstituted arylalkyl group of 7 to 20 carbon atoms; a and b may each independently be an integer of 0 to 2; and B may be an alkyl group of 1 to 12 carbon atoms.
In addition, in an embodiment of the present invention, R 14 To R 18 Each independently is hydrogen or alkyl of 1 to 20 carbon atoms; a is an integer of 1 or 2, b may be an integer of 0 or 1; and B may be an alkyl group of 1 to 8 carbon atoms.
In particular, a is an integer from 1 to 3, b may be an integer from 0 to 3, more particularly a is 1 or 2, and b may be an integer from 0 to 2, more particularly a is 1 or 2, and b may be 0 or 1.
The alkyllithium compound represented by formula 16 may be, for example, n-BuLi, and n-BuLi is a material widely used as an anionic polymerization initiator, is easily available, and has excellent monovalent efficiency.
In the preparation method of the anionic polymerization initiator, a process of reacting the compound represented by formula 15 with the compound represented by formula 16 may be first performed, and then, by reacting with the compound of formula 12, the compound represented by formula 11 may be prepared. Specifically, by reacting the compound represented by formula 15 with the compound represented by formula 16, allyllithium as an intermediate may be formed, and allyllithium may react with the compound of formula 12, eventually forming the anionic polymerization initiator of formula 11.
In addition, the process of injecting and reacting the compound represented by formula 16 and the compound represented by formula 12 in the presence of the compound represented by formula 15 may be performed without an additional solvent. The condition of no additional solvent means that no separate compound that can act as a solvent, or a small amount of a compound that does not significantly react with the compound represented by formula 15 in the presence of the compound represented by formula 16, is present in addition to the compound represented by formula 15 and the compound represented by formula 12.
If the reaction is performed without an additional solvent, the reaction of the compound represented by formula 15 and the compound represented by formula 16 may proceed mainly, and the anionic polymerization initiator of formula 11 may be efficiently prepared. If a separate solvent is present, the anionic polymerization initiator of formula 11, the compound produced by the reaction of the compound represented by formula 15 and the compound represented by formula 12, and the decomposed compound of the compound produced by the compound represented by formula 15 and the compound represented by formula 12 may be present ineffectively as a mixture.
Thermoplastic resin composition
The thermoplastic resin composition according to the present invention comprises polypropylene and the multiblock copolymer according to the embodiment of the present invention, and the thermoplastic resin composition according to the present invention is a resin composition comprising polypropylene and the multiblock copolymer. The multiblock copolymer comprises a polystyrene-based block comprising repeating units derived from an aromatic vinyl-based monomer and a polyolefin-based block comprising repeating units derived from an ethylene-based monomer and is characterized by having a liquid ordered phase having a domain size (R) of 15.0nm to 22.0nm, an inter-domain distance (D1) of 40.0nm to 60.0nm, and a lamellar phase having a domain size (T) of 2.0nm to 9.0nm, and an inter-domain distance (D2) of 10.0nm to 50.0nm. The domain size and the inter-domain distance are measured by small angle X-ray scattering.
The thermoplastic resin composition according to the present invention may satisfy the following conditions a) to c).
a) The height of the stress variation (Tan delta ) peak according to temperature derived by dynamic viscoelasticity analysis is 0.02 to 0.13;
b) The radius (Rv) of the dispersed phase is 0.10 μm to 0.50 μm; and
c) The glass transition temperature (Tg) is from-60℃to-30 ℃.
The height of the stress variation peak of the thermoplastic resin composition according to the temperature and the glass transition temperature can be determined by measurement of a Dynamic Mechanical Analyzer (DMA), and the dispersibility of the block copolymer in the polypropylene matrix in the resin composition can be obtained by analysis by a Scanning Electron Microscope (SEM). The dispersion property and dynamic property (rheological property) of the thermoplastic resin composition can be used as an index for judging the compatibility between the polypropylene matrix and the block copolymer.
The thermoplastic resin composition according to the present invention satisfies the height range of stress variation (Tan delta ) peak according to temperature, radius of dispersed phase and glass transition temperature derived from dynamic viscoelasticity analysis, and has excellent compatibility between polypropylene and multiblock copolymer contained therein, thereby exhibiting excellent impact resistance.
a) The height of the stress variation (Tan δ ) peak according to temperature derived by dynamic viscoelasticity analysis is 0.02 to 0.13, particularly, 0.03 or more, 0.04 or more, and 0.13 or less, 0.12 or less, 0.11 or less, more particularly, 0.05 to 0.11.
The height of the stress variation (Tan δ ) peak according to temperature is an index showing properties related to the viscoelasticity of the polymer, and is a value obtained by dividing the loss modulus value by the storage modulus value. As the loss modulus value increases, and as the storage modulus value decreases, the height value of the stress variation (Tan δ ) peak may increase. A large tan delta value means that if an impact is applied to the polymer, the degree of dissipation of energy transferred from the impact is high. In addition, the greater the tan δ value, the better the effect as an impact reinforcement.
The thermoplastic resin composition according to the present invention satisfies the range of tan delta, and when compared with a thermoplastic resin composition comprising general polypropylene and a multiblock copolymer, if the multiblock copolymer is contained in the same content, it exhibits a relatively high tan delta value and may exhibit excellent impact dissipation effects.
b) The radius (Rv) of the dispersed phase is 0.10 μm to 0.50 μm, in particular, 0.10 μm or more, 0.12 μm or more, 0.15 μm or more, 0.18 μm or more, 0.19 μm or more, 0.20 μm or more, and 0.45 μm or less, 0.40 μm or less, 0.35 μm or less, 0.30 μm or less, 0.29 μm or less, 0.28 μm or less, 0.27 μm or less, more in particular, 0.10 μm to 0.27 μm,0.21 μm or less, 0.27 μm.
The thermoplastic resin composition according to the present invention may exhibit excellent dispersibility if the radius (Rv) of the dispersed phase is reduced, and the thermoplastic resin composition satisfies the range of the radius (Rv) of the dispersed phase and exhibits excellent dispersibility.
c) The glass transition temperature (Tg) is from-60℃to-30℃and may be specifically from-58℃to-57℃to-56℃to-55℃and from-35℃to-40℃to-45℃to-46℃to-47℃to-48℃to-49℃and more specifically from-55℃to-49 ℃.
The multiblock copolymer contained in the thermoplastic resin composition of the present invention is the same as explained in the above multiblock copolymer.
In the thermoplastic resin composition according to the embodiment of the present invention, the polypropylene may be particularly a homopolymer of polypropylene, or a copolymer of propylene and an α -olefin monomer, and in this case, the copolymer may be an alternating, random or block copolymer.
The alpha-olefin-based monomers may in particular be aliphatic olefins of 2 to 12 carbon atoms, or 2 to 8 carbon atoms. More specifically, ethylene, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-eicosene, 4-dimethyl-1-pentene, 4-diethyl-1-hexene, 3, 4-dimethyl-1-hexene and the like may be used, and any one of them or a mixture of two or more thereof may be used.
More specifically, the polypropylene may be any one selected from polypropylene copolymers, propylene- α -olefin copolymers and propylene-ethylene- α -olefin copolymers, or a mixture of two or more thereof, and in this case, the copolymers may be random or block copolymers.
In addition, the Melt Index (MI) of polypropylene measured at 230℃and a load of 2.16kg may be 0.5g/10min to 100g/10min, and in particular, the Melt Index (MI) may be 1g/10min to 90g/10min. If the melt index of polypropylene deviates from this range, defects may occur during injection molding of the thermoplastic resin composition.
In particular, in the thermoplastic resin composition according to an embodiment of the present invention, the polypropylene may be a copolymer, more particularly, a propylene-ethylene copolymer or a high crystalline polypropylene (HCPP) having a Melt Index (MI) measured at 230 ℃ and under a load of 2.16kg of 0.5g/10min to 100g/10min, particularly, 1g/10min to 90g/10min, more particularly, 2g/10min to 50g/10 min. If a copolymer having such physical properties is contained as polypropylene in the above-mentioned amount range, strength properties, particularly strength properties at room temperature, can be improved.
Copolymers may be prepared by using general preparation reactions of polymers to satisfy the above physical property conditions, or may be commercially obtained and used. Specific examples may include SEETE from LG Chemie, inc TM M1600, CB5230 of Korean Petrochemical Co., ltd.
In addition, in the thermoplastic resin composition according to the embodiment of the present invention, the polypropylene may be particularly one or more random propylene copolymers having a DSC melting temperature in the range of 120℃to 160℃and a Melt Flow Rate (MFR) measured at 230℃and under a load of 2.16kg according to ASTM-D1238 in the range of 5g/10min to 120g/10min, and may be contained in an amount of 20wt% to 90wt%, particularly 30wt% to 70wt%, more particularly 40wt% to 60wt% relative to the total weight of the polypropylene-based composite. If the content of polypropylene having such physical properties is within the above-mentioned content range, the mechanical strength (including hardness) of the thermoplastic resin composition can be improved. Random propylene copolymers may be prepared by using the general preparation reactions of the polymers to meet the physical property conditions described above, or may be commercially available and used. Specific examples may include Braskem of Braskem America Inc TM PP R7021-50RNA, formolene from Taiwan plastics Co., USA TM 7320A, etc.
Meanwhile, the thermoplastic resin composition according to the embodiment of the present invention may optionally further include an inorganic filler as well as polypropylene and a multiblock copolymer to improve mechanical properties of the thermoplastic resin composition.
The inorganic filler may specifically be a powder type filler, a flake type filler, a fiber type filler, or a balloon type filler, and any one of them or a mixture of two or more thereof may be used. In particular, the powder filler may include: natural silicic acids or silicates, such as fine talc, kaolinite, plastic clay, and sericite; carbonates such as precipitated calcium carbonate, ground calcium carbonate, and magnesium carbonate; hydroxides, such as aluminum hydroxide and magnesium hydroxide; oxides such as zinc oxide, magnesium oxide, and titanium oxide; synthetic silicic acid or silicate such as calcium silicate hydrate, aluminum silicate hydrate, silicic acid hydrate, and silicic acid anhydride; silicon carbide, and the like. Further, as the flake filler, mica or the like may be included. The fibrous filler may include basic magnesium sulfate whiskers, calcium titanate whiskers, aluminum borate whiskers, sepiolite, processed Mineral Fibers (PMF), potassium titanate, and the like. As the balloon-type filler, a glass balloon or the like may be included. Among them, talc may be used.
In addition, the inorganic filler may be surface-treated to improve the strength properties and molding processability of the thermoplastic resin composition.
In particular, the inorganic filler may be subjected to physical or chemical surface treatment using a surface treatment agent such as a silane coupling agent, a higher fatty acid, a fatty acid metal salt, an unsaturated organic acid, an organic titanate, a resin acid, and polyethylene glycol.
Furthermore, the inorganic filler may have an average particle diameter (D) of 1 μm to 20. Mu.m, particularly 3 μm to 15. Mu.m, more particularly 5 μm to 10. Mu.m 50 ). If the average particle diameter of the inorganic filler is too small, it is difficult to uniformly disperse due to agglomeration of the inorganic filler particles when mixed with polypropylene and the multiblock copolymer, and as a result, the effect of improving the mechanical properties of the resin composition may become insignificant. In addition, if the average particle diameter of the inorganic filler is too large, deterioration of physical properties may be caused due to deterioration of dispersibility of the inorganic filler itself.
In the present invention, the average particle size of the inorganic fillerDiameter (D) 50 ) Can be defined as particle size based on a 50% particle size distribution. In the present invention, the average particle diameter (D 50 ) It can be measured by, for example, an observation electron microscope using a Scanning Electron Microscope (SEM), a field emission scanning electron microscope (FE-SEM), or the like, or by a laser diffraction method. In the case of measurement by the laser diffraction method, more specifically, inorganic filler particles are dispersed in a dispersion medium and introduced into a commercially available laser diffraction particle size measuring apparatus (e.g., microtrac MT 3000), and then the average particle diameter (D) based on the 50% particle diameter distribution in the measuring apparatus can be calculated 50 )。
The inorganic filler may be contained in 0.1 to 40 parts by weight with respect to 100 parts by weight of the resin composition. If the amount of the inorganic filler in the resin composition is less than 0.1 parts by weight relative to 100 parts by weight of the resin composition, the improvement effect due to the inclusion of the inorganic filler is insignificant, whereas if the amount is more than 40 parts by weight, the processability of the resin composition may be deteriorated. More specifically, the inorganic filler may be contained in 0.1 to 20 parts by weight relative to the total weight of the resin composition.
The thermoplastic resin composition according to the embodiment of the present invention satisfying the configuration and amount conditions as described above may be prepared by mixing the multiblock copolymer, polypropylene and optional inorganic filler, and then heating. In this case, the type and amount of polypropylene are the same as described above.
The mixing process may be carried out by a general method. In particular, mixing can be carried out using a super mixer or ribbon mixer.
The thermoplastic resin composition according to the embodiment of the present invention can be used for blow molding, extrusion molding or injection molding in various fields, and can be used for packaging, construction and household goods, for example, materials for automobiles, wiring, toys, fibers and medicine. In particular, since physical properties such as heat resistance and rigidity are excellent and also excellent tensile properties and impact strength are provided at room temperature even at low temperature, the thermoplastic resin composition can be effectively used for interior and exterior parts of automobiles.
According to another embodiment of the present invention, a molded article and an automobile part manufactured using the thermoplastic resin composition satisfying physical properties can be provided.
The shaped articles may in particular comprise blow-molded articles, cast-molded articles, extrusion-laminated molded articles, extrusion-molded articles, foam-molded articles, injection-molded articles, sheets, films, fibers, monofilaments or nonwovens.
Further, the automotive parts may be interior and exterior materials of an automobile.
Process for producing resin composition
The resin composition of the present invention may be prepared by a preparation method including the step of mixing the multiblock copolymer prepared by the preparation method of the multiblock copolymer with polypropylene.
In an embodiment of the method for producing a resin composition of the present invention, the method for producing a multiblock copolymer is the same as described above, and the configuration of the resin composition is also the same as described above.
The resin composition according to the embodiment of the present invention satisfying the configuration and amount conditions as described above may be prepared by mixing the multiblock copolymer, polypropylene, and optional inorganic filler, and then heating. In this case, the type and amount of polypropylene are the same as described above.
The mixing process may be carried out by a general method. In particular, mixing can be carried out using a super mixer or ribbon mixer.
In addition, during the mixing process, additives such as an antioxidant, a heat stabilizer, an ultraviolet stabilizer, and an antistatic agent may be further included as needed, and a small amount of a binder resin or an additive having a polar group may be optionally further used in an appropriate amount range to improve coatability.
In addition, the heating process may be performed at a temperature above the melting point of polypropylene and below 210 ℃. The heating process may be carried out using various conventional mixers such as a twin-screw extruder, a single-screw extruder, a roll mill, a kneader, and a Banbury mixer.
Examples
Hereinafter, the present invention will be explained in more detail with reference to embodiments. However, the embodiments are for illustrating the present invention, and the scope of the present invention is not limited thereto.
Reagents and Experimental conditions
All experiments were performed under inert atmosphere using standard glove box and Schlenk techniques. Toluene, hexane and Tetrahydrofuran (THF) were distilled together with benzophenone carbonyl radical and used. Methylcyclohexane (anhydrous grade) used in the polymerization reaction was purchased from Tokyo Chemical Industry (TCI), purified by Na/K synthesis and used. Sublimation-grade HfCl 4 Purchased from Streme and used as received. The ethylene-propylene gas mixture was purified with trioctylaluminum (0.6M in mineral spirits) in a bomb reactor (2.0L).
Recording using ECZ 600 device (JOEL) 1 H NMR (600 MHz) and 13 c NMR (150 MHz) spectrum.
GPC data were analyzed in 1,2, 4-trichlorobenzene at 160deg.C using a PL-GPC 220 system equipped with a refractive index detector and two columns (Plarian Mixed-B7.5x 300mm Varian[Polymer Lab).
(1) Preparation of transition metal compounds
[ 1-1]
(i) Preparation of ligand compounds
/>
2, 6-dicyclohexylaniline (0.772 g,3.00 mmol) and 6-bromo-2-pyridinecarboxaldehyde (0.5538 g,3.00 mmol) were dissolved in toluene (5 mL) and molecular sieves were injected therein. The mixture thus obtained was heated to 70 ℃ while stirring overnight. After filtration, the solvent was removed using a rotary evaporator. Yellow solid (1.07 g, 84%) was obtained.
1 H NMR(C 6 D 6 ):δ8.41(s,1H,NCH),8.09(d,J=7.8Hz,1H),7.53(m,3H),6.85(d,J=7.8Hz,1H),6.63(t,J=7.8Hz,1H),2.74(m,2H),1.87(d,J=12Hz,4H),1.64(d,J=12.6Hz,4H),1.54(d,J=10.8Hz,2H),1.39(quartet,J=10.2Hz,4H),1.11(m,6H)ppm。
13 C NMR(C 6 D 6 ):δ26.55,27.33,34.25,39.30,119.42,124.32,125.21,129.83,136.68,138.82,142.54,148.94,155.95,162.06ppm。
HRMS (EI) M/z calculation ([ M) + ]C 24 H 29 BrN 2 ) 424.1514. Actual measurement 424.1516.
Under nitrogen, 1.07g (2.51 mmol), 1-naphthyridine boric acid (0.457 g,2.64 mmol), na 2 CO 3 (0.700 g,6.60 mmol) and toluene (5 mL) were charged into a schlenk flask. Injection of degassed H 2 O/EtOH (1 mL, v/v, 1:1) and (Ph) 3 P) 4 Pd (7.83 mg,0.00678 mmol) in toluene (1 mL). A lemon yellow oil (0.710 g, 60%) was obtained by column chromatography on silica gel using hexane and ethyl acetate (containing a small amount of triethylamine) (v/v, 90:3:1).
1 H NMR(C 6 D 6 ):δ8.70(s,1H,NCH),8.41(d,J=7.8Hz,1H),8.31(d,J=7.8Hz,1H),7.68(d,J=7.2Hz,1H),7.65(d,J=7.8Hz,1H),7.54(d,J=7.2Hz,1H),7.27(m,4H),7.20(m,4H),2.93(m,2H),1.90(d,J=12Hz,4H),1.61(d,J=13.2Hz,4H),1.50(d,J=12.6Hz,2H),1.38(m,4H),1.11(m,6H),ppm。
13 C NMR(C 6 D 6 ):δ26.63,27.38,34.35,39.36,119.21,124.32,124.98,125.50,126.15,126.21,126.64,126.75,128.15,128.73,129.38,131.81,134.52,136.94,137.14,138.52,149.48,155.13,159.79,164.05ppm。
HRMS (EI) M/z calculation ([ M) + ]C 34 H 36 N 2 ) 472.2878. Actual measurement 472.2878.
2-isopropylphenyl lithium (0.114 g, 0.284 mmol) dissolved in diethyl ether (8 mL) was added dropwise to a schlenk flask containing a solution of compound (0.247 g, 0.323 mmol) in diethyl ether (20 mL). After stirring for 3 hours, an aqueous solution (10 mL) of ammonium chloride (0.30 g) was added, and the product was extracted with diethyl ether (3X 10 mL). The oil thus produced was dried under high vacuum at 60 ℃ overnight. A yellow solid (0.257 g, 83%) was obtained.
1 H NMR(C 6 D 6 ) Delta 8.24 (m, 1H), 7.90 (m, 1H), 7.64 (m, 1H), 7.62 (d, J=7.8 Hz, 1H), 7.56 (d, J=7.2 Hz, 1H), 7.26 (m, 3H), 7.22 (m, 4H), 7.11 (m, 5H), 5.62 (d, J=5.4 Hz,1H, NCH), 4.59 (d, J=5.4 Hz,1H, NH), 3.31 (septet), J=7.2 Hz,1H, CH), 2.74 (m, 2H), 1.79 (d, J=7.8 Hz, 2H), 1.64 (m, 4H), 1.54 (m, 4H), 1.32 (m, 4H), 1.08 (m, 2H), 1.03 (d, J=6.6 Hz,3H, CH) 3 ),1.00(m,1H),0.980(d,J=6.6Hz,3H,CH 3 ),0.921(m,3H)ppm。
13 C NMR(C 6 D 6 ):δ23.78,24.45,26.63,27.42,27.54,28.96,34.77,35.08,39.01,67.64,119.99,122.89,124.13,124.80,125.36,125.77,126.08,126.46,126.56,126.71,127.58,128.55,129.35,131.84,134.64,136.94,138.77,141.88,142.24,144.97,146.32,159.28,163.74ppm。
HRMS (EI) M/z calculation ([ M) + ]C 43 H 48 N 2 ) 592.3817. Actual measurement 592.3819.
(ii) Preparation of transition metal compounds
A solution of the ligand compound (0.150 g, 0.255 mmol) in toluene (1.5 g) was charged into the schlenk flask, and n-butyllithium (0.17 mL, 1.6M solution in hexane, 0.27 mmol) was added dropwise thereto at room temperature. After stirring for 1 hour, hfCl in solid form was added thereto 4 (0.0814 g,0.254 mmol). The reaction mixture was heated and stirred at 100 ℃ for 2 hours. After cooling, meMgBr (0.29 mL,3.1M in diethyl ether, 0.89 mmol) was injected and stirred at room temperature overnight. After removal of volatiles via vacuum line, the product was extracted with toluene (1.5 g). The extract was filtered through celite filtration. The solvent was removed via vacuum line and the residue was triturated in hexane (2 mL) to give a yellow solid (0.128 g, 63%).
1 H NMR(C 6 D 6 ):δ8.58(d,J=7.8Hz,1H),8.29(d,J=8.4Hz,1H),7.79(d,J=7.8Hz,1H),7.71(d,J=7.2Hz,1H),7.54(d,J=7.8Hz,1H),7.46(m,1H),7.30(m,2H),7.15(m,3H),7.09(m,3H),6.88(t,J=7.8Hz,1H),6.62(d,J=8.4Hz,1H),6.48(s,1H,NCH),3.39(m,1H),2.92(m,2H),2.15(d,J=13.8Hz,1H),2.10(d,J=13.8Hz,2H),1.80(m,2H),1.65(m,3H),1.29(m,6H),1.17(d,J=7.2Hz,3H,CH 3 ),1.07(m,3H),0.99(s,3H,HfCH 3 ),0.95(m,2H),0.73(d,J=7.2Hz,3H,CH 3 ),0.70(s,3H,HfCH 3 ),0.23(m,1H)ppm。
13 C NMR(C 6 D 6 ):δ23.31,25.04,26.63,26.74,27.70,27.76,27.81,28.29,28.89,35.00,35.66,36.62,37.02,38.13,40.88,62.53,67.00,77.27,119.30,120.30,124.29,125.52,125.60,125.97,126.95,127.06,127.73,129.91,130.00,130.09,130.85,134.36,135.80,140.73,140.89,144.02,145.12,146.31,146.38,146.49,164.46,170.79,206.40ppm。
Analytical calculations (C) 45 H 52 HfN 2 ) C,67.61; h,6.56; n,3.50%. Actual measurement C,67.98; h,6.88; n,3.19%.
(2) Preparation of organozinc compounds
To 78ml of diethyl ether were added 4-vinylbenzyl chloride (15.0 g,98.3 mmol) and magnesium metal (2.428 g,108.1 mmol) and stirred at 0℃for 1.0 h. Then, diatomaceous earth filtration was performed to remove the excessive added magnesium. p-toluenesulfonyl-OCH was dissolved in 27ml diethyl ether 2 CH 2 Cl (19.2 g,81.9 mmol) was added dropwise to the 4-vinylbenzyl-MgCl reagent prepared above. Stirred overnight and filtered over celite to remove magnesium chloride toluene sulfonate (MgCl (OTs)) as an insoluble salt. The thus-filtered cake was washed 3 times with 70ml of hexane, and the solvent was removed by a rotary evaporator to obtain 14.2g of a crude product. Tert-butylcatechol (43 mg,3,000 ppm) was added as a radical scavenger, and vacuum distillation was performed at 85℃under full vacuum to obtain a compound represented by the following formula 8-4-1. The weight of the obtained compound was measured, and the yield was 81wt% (12.0 g), which was measured 1 H NMR 13 C NMR spectrum.
[ 8-4-1]
1 H NMR(C 6 D 6 ):δ7.20(d,J=8.4Hz,2H),6.88(d,J=8.4Hz,2H),6.61(dd,J=16,9.6Hz,1H,=CH),5.63(d,J=16Hz,1H,=CH 2 ),5.09(d,J=9.6Hz,1H,=CH 2 ),3.04(t,J=6.6Hz,2H,CH 2 ),2.42(t,J=6.6Hz,2H,CH 2 ) 1.64 (quintet, J=6.6 Hz,2H, CH) 2 Cl)ppm。
13 C NMR(C 6 D 6 ):δ32.61,34.12,44.07,113.13,126.74,128.97,135.99,137.11,140.63ppm。
Then, the compound (4- (3-chloropropyl) styrene represented by the formula 8-4-1, 10.0g,55.3 mmol) thus prepared was dissolved in a mixed solvent of 20ml of toluene and 7.98g (111 mmol) of Tetrahydrofuran (THF), and was added dropwise to a suspension of magnesium powder (2.02 g,83.0 mmol) stirred in 40ml of toluene at room temperature. After stirring for 5.0 hours and slowly generating slight heat, the reaction mixture was filtered over celite to remove the excess added magnesium. Will be prepared by reacting diethyl zinc (Et 2 Zn,6.83g,55.3 mmol) and methanol (1.78 g,55.3 mmol) were reacted in situ in 30ml toluene at room temperature for 1.0 hour to give ethylzinc methoxide (EtZn (OMe), 6.94g,55.3mmol, 1 equivalent compared to Grignard reagent) which was added to the filtrate. Then, 60ml of toluene was added, stirred at room temperature for 1.0 hour, and the solvent was removed using a high vacuum line. Then, 96g of hexane was added, and methoxy magnesium chloride (MgCl (OMe)) was removed as an insoluble salt on celite. The filtrate was stored at-30 ℃ to deposit the compound represented by formula 5-4 as a solid content of white crystals. As a result of measurement of the weight, the yield was 56% by weight (7.28 g), measurement 1 H NMR 13 C NMR spectrum.
[ 5-4]
1 H NMR(C 6 D 6 ):δ7.24(d,J=7.8Hz,2H),6.90(d,J=7.8Hz,2H),6.64(dd,J=17,11Hz,1H,=CH),5.66(d,J=17Hz,1H,=CH 2 ),5.11(d,J=11Hz,1H,=CH 2 ),2.43(t,J=7.2Hz,2H,CH 2 ) 1.80 (quintet, J=7.2 Hz,2H, CH) 2 ),-0.19(t,J=7.2Hz,2H,CH 2 Zn)ppm。
13 C NMR(C 6 D 6 ):δ12.66,28.82,40.09,113.15,127.31,129.23,136.05,137.10,142.91ppm。
(3) Preparation of anionic polymerization initiator
n-BuLi (0.14 mg,2.2 mmol) was added dropwise to a solution of pentamethyldiethylenetriamine (PMDTA, 0.37g,2.2 mmol) in 1-octene (13.0 g). After stirring overnight at room temperature, a yellow solution of pentylallyl-Li (PMDTA) (0.16 mmol-Li/g) was obtained. By passing through 1 The H NMR spectrum was analyzed for aliquots. Recording 1 After H NMR spectrum, use H 2 O (or D) 2 O) quenching C 6 D 6 Solution and use anhydrous MgSO 4 The short pad was filtered from the pipette and re-recorded 1 H NMR spectrum.
Preparation of polyolefin-polystyrene based multiblock copolymers
Example 1
The parr reactor (3.785L) was dried under vacuum at 120℃for 2 hours. A solution of MMAO (1.2 mg,2,020. Mu. Mol-Al) in methylcyclohexane (1,200 g) was injected into the reactor as scavenger. The resulting mixture was stirred at 120 ℃ for 1 hour using a heating jacket and the solution was removed using a cannula.
The reactor was charged with methylcyclohexane (1,200 g) containing MMAO (2,020. Mu. Mol-Al) as a scavenger, and 1-hexene (560 g) was added as an alpha-olefin monomer, and then the temperature was set to 90 ℃. A solution of an organozinc compound (2,496. Mu. Mol) of formula 5-4 in methylcyclohexane (5 g) was added as a chain transfer agent, and a mixture containing [ (C) was injected 18 H 37 ) 2 N(H)Me] + [B(C 6 F 5 ) 4 ] - (1.0 eq.) A solution of activated transition metal compound (12. Mu. Mol-Hf) in methylcyclohexane. The valve of the ethylene tank was opened and the polymerization was carried out at a temperature in the range of 90 to 120℃for 40 minutes while maintaining the pressure in the reactor at 25 bar. After polymerization, ethylene gas was vented and the temperature of the reactor was again controlled at 90 ℃.
If the temperature reached 90℃pentylallyl-Li (PMDTA) (2,600. Mu. Mol) in methylcyclohexane (10 g) was added. After maintaining the temperature at 90℃for 30 minutes while stirring, styrene (104 g) was injected. The temperature was controlled in the range of 90 to 100 c using a heating jacket. The viscosity gradually increased and reached a nearly invisible state within 5 hours. Removing an aliquot for passage 1 H NMR spectroscopic analysis. From aliquots 1 H NMR analysis confirmed complete conversion of styrene. After complete conversion of styrene, 2-ethylhexanoic acid and ethanol were injected continuously. The polymer mass thus obtained was dried in a vacuum oven at 80 ℃ overnight.
Examples 2 to 4
The same procedure as in example 1 was conducted except that the reaction conditions were changed as in the following Table 1.
Comparative example 1
G1650 from Kraton was used as a commercially available SEBS.
Comparative example 2
G1651 from Kraton was used as a commercially available SEBS.
Comparative example 3
The same process as in example 1 was conducted, except that diethyl zinc was used instead of the organozinc compounds of formulas 5-4 in example 1 to prepare a polymer.
Comparative example 4
Me is prepared 3 SiCH 2 Li (2,600. Mu. Mol,291.4 mg) and PMDETA (2,600. Mu. Mol,537.3 mg) were mixed with methylcyclohexane (20.7 g) and stirred at room temperature for 30 minutes to prepare an anionic polymerization initiator.
Except for using Me 3 SiCH 2 Li (PMDETA) instead of pentylallyl-Li (PMDTA) as anionic initiator and in example 1The same process as in example 1 was conducted except that the reaction conditions were changed to prepare a multiblock copolymer as in the following table 1.
Comparative example 5
Except for using Oc 3 The same procedure as in example 1 was conducted except that Al (2962.1 mg,2,020. Mu. Mol-Al/25 wt% in hexane solution) was used as a scavenger instead of MMAO and the reaction conditions were changed in the following Table 1 in example 1 to prepare a multiblock copolymer.
TABLE 1
Experimental example 1 Small-Angle X-ray Scattering
Small angle X-ray scattering (SAXS) was performed using u-SAXS beam line 9A of the Pohang light source. A sample of the sample type is attached to the sample holder. The corresponding samples were measured at 6.5m SDD for 5 seconds and the air scattering intensity measured at the same time was used as background. The 2D image obtained in the experimental example was averaged into a circle based on beam stop (beam stop) and converted into a 1D image. By using it, each of the main phase and the sub phase is assumed, and modeling is performed to obtain a domain size and an inter-domain distance.
TABLE 2
As shown in Table 2, the multiblock copolymer of the examples has a liquid ordered phase having a domain size (R) of 15.0nm to 22.0nm, an inter-domain distance (D1) of 40.0nm to 60.0nm, a domain size (T) of 2.0nm to 9.0nm, and an inter-domain distance (D2) of 10.0nm to 50.0nm, and a lamellar phase. Unlike the case where a general multiblock copolymer is mixed with polypropylene, which may greatly reduce the melt flow rate to greatly deteriorate the processability, if the multiblock copolymer of the present invention satisfying such conditions is used to prepare a resin composition compound, miscibility with polypropylene may be excellent, the flow properties of polypropylene may be maintained, and thus the prepared resin composition may exhibit excellent flow properties and high melt flow rate to exhibit the effect of excellent processability.
Preparation of resin composition
Example 1A
To 0.11 part by weight of the multiblock copolymer of example 3 was added 1 part by weight of polypropylene (CB 5230, korean Petrochemical Co., ltd.) having a melt index of 30g/10min (230 ℃,2.16 kg), and compounding was performed using a twin screw extruder to prepare a resin composition compound. The temperature at this time was 180℃to 200℃and the screw speed was 100rpm.
Example 2A
A resin composition compound was prepared by the same method as in example 1A, except that the contents of the multiblock copolymer and the polypropylene of example 3 were changed to 0.25 parts by weight and 1 part by weight, respectively.
Example 3A
A resin composition compound was prepared by the same method as in example 1A, except that the contents of the multiblock copolymer and the polypropylene of example 3 were changed to 0.43 parts by weight and 1 part by weight, respectively.
Example 4A
A resin composition compound was prepared by the same method as in example 2A, except that the multiblock copolymer of example 2 was used instead of the multiblock copolymer of example 3.
Comparative examples 1 to 3
A resin composition compound was prepared by the same method as in example 1A, except that the multiblock copolymer of comparative example 1 was used instead of the multiblock copolymer of example 3.
Comparative examples 4 to 7
A resin composition compound was prepared by the same method as in example 4A, except that the multiblock copolymers of comparative examples 2 to 5 were used instead of the multiblock copolymer of example 3.
Experimental example
(1) Measurement of the height of stress variation peaks as a function of temperature
The y value of the point at which the tan delta value is maximum in the range of-80 ℃ to 40 ℃ is measured on a graph showing the amount of change (y axis) in the loss tangent (tan delta) for the temperature (x axis) obtained by Dynamic Mechanical Analysis (DMA).
Loss modulus, storage modulus and tan delta values were measured by DMA at 1Hz and 0.1% strain in the range of-90 ℃ to 100 ℃.
(2) Measurement of dispersed phase radius (Rv)
The disperse phase radius can be measured on SEM images of the resin composition. Rv values were obtained from a gaussian distribution of measured dispersed phase radii.
(3) Measurement of stress variation peak (tan delta peak) temperature
The glass transition temperature (Tg) is a fundamental index of a material related to the physical properties and processability of a polymer, and the temperature showing tan δ peak tends to be similar to the glass transition temperature (Tg) of a polymer. In the present specification, a tan δ peak temperature value is used.
(4) Measurement of Low temperature impact Strength
The respective resin compositions of examples 1A to 6A and comparative examples 1A to 6A were injected into a mold at 210℃under a pressure of 6 bar in 10 seconds, and notched shapes having dimensions of 63.5mm by 10.16mm by 3.2mm were molded based on ASTM D256. For the sample thus produced, a pendulum with a load of 0.944kg was suspended using an Izod impactor model 104 of Tinius Olsen company, based on ASTM D256, and the impact strength at low temperature (-30 ℃) was measured.
In particular, the impact strength at low temperature (-30 ℃) was measured by the following method: the fabricated sample was placed in a low temperature chamber set at-30 ℃, the sample was exposed at-30 ℃ for 12 hours or more, the sample was taken out of the low temperature chamber, and the impact strength was measured within 3 seconds.
(5) Measurement of melt flow Rate (MFR, 230 ℃,2.16 kg)
The respective resin compositions prepared in examples 2A, 4A and 6A and comparative examples 2A, 4A and 6A were recovered, and MFR (230 ℃ C., 2.16 kg) was measured according to ASTM-D1238.
TABLE 3
Referring to table 3, it can be confirmed that the resin composition of the example exhibits significantly excellent low temperature impact strength when compared with the resin composition of the comparative example if the same content of the multiblock copolymer is contained. In particular, it was confirmed that, although the same content of the multiblock copolymer was contained, when the resin composition of example 1A was compared with the resin composition of comparative example 1A, when the resin compositions of examples 2A and 4A to 6A were compared with the resin compositions of comparative examples 2A and 4A to 6A, and when the resin composition of example 3A was compared with the resin composition of comparative example 3A, the resin composition of example showed significantly high low-temperature impact strength. In addition, it was confirmed that the resin composition of the example exhibited even better impact dissipation and absorption effects when compared to the resin composition of the comparative example containing the same content of the multiblock copolymer.
It can be confirmed that the resin composition of the example has a relatively small dispersed phase radius (Rv) value and exhibits even better dispersion properties when compared to the resin composition of the comparative example. In addition, it can be confirmed that the resin composition of examples has a relatively large tan δ value and exhibits even better impact dissipation and absorption properties.
In particular, as demonstrated in table 4 below, the resin compositions of the examples exhibited significantly high melt flow rate values if the same content of multiblock copolymer was contained, while exhibiting significantly high low temperature impact strength as compared to the resin compositions of the comparative examples.
TABLE 4
As demonstrated in table 4, the resin compositions of examples 2A and 4A to 6A including the multiblock copolymers of examples 1 to 4 exhibited significantly high melt flow rate values when compared to the resin compositions of comparative examples 2A and 4A to 6A including the multiblock copolymers of comparative examples 2, 3 and 5.
As described above, it was confirmed that the resin composition of the present invention including the multiblock copolymer of the present invention and polypropylene includes the specific multiblock copolymer of the present invention, and may exhibit excellent processability and remarkably excellent low temperature impact strength.
Claims (17)
1. A multi-block copolymer comprising a polystyrene-based block comprising repeat units derived from an aromatic vinyl-based monomer and a polyolefin-based block comprising repeat units derived from an ethylene-based monomer and repeat units derived from an alpha-olefin-based monomer, wherein
The multiblock copolymer has a liquid ordered phase and a lamellar phase,
the liquid ordered phase has a domain size (R) of 15.0nm to 22.0nm, an inter-domain distance (D1) of 40.0nm to 60.0nm, and
the lamellar phase has a domain size (T) of 2.0nm to 9.0nm and an inter-domain distance (D2) of 10.0nm to 50.0nm, wherein the domain size and the inter-domain distance are measured by small angle X-ray scattering.
2. The multi-block copolymer of claim 1, wherein the multi-block copolymer has a liquid ordered phase as a major phase and a lamellar phase as a minor phase.
3. The multi-block copolymer of claim 1, wherein the alpha-olefin based monomer is an alpha-olefin based monomer having from 5 to 20 carbon atoms.
4. The multi-block copolymer of claim 1, wherein the alpha-olefin based monomer is one or more selected from the group consisting of 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-eicosene, 4-dimethyl-1-pentene, 4-diethyl-1-hexene, and 3, 4-dimethyl-1-hexene.
5. The multiblock copolymer of claim 1, wherein the domain size (R) of the liquid ordered phase of the multiblock copolymer is 15.0nm to 20.0nm.
6. The multiblock copolymer according to claim 1, wherein the liquid-like ordered phase of the multiblock copolymer has an inter-domain distance (D1) of 43.0nm to 56.0nm.
7. The multiblock copolymer of claim 1, wherein the domain size (T) of the lamellar phase of the multiblock copolymer is 2.0nm to 5.0nm.
8. The multiblock copolymer according to claim 1, wherein the inter-domain distance (D2) of the lamellar phase of the multiblock copolymer is 12.0nm to 43.0nm.
9. A process for preparing the multi-block copolymer of claim 1, the process comprising:
(S1) a step of reacting ethylene with an α -olefin-based monomer in the presence of a catalyst composition comprising a transition metal compound using an organozinc compound as a chain transfer agent to prepare a polyolefin-based block; and
(S2) a step of reacting an aromatic vinyl-based monomer and the polyolefin-based block in the presence of an anionic polymerization initiator to prepare a multiblock copolymer.
10. The method for producing a multiblock copolymer according to claim 9, wherein the transition metal compound is a compound represented by the following formula 1:
[ 1]
In the formula 1, the components are mixed,
m is Ti, zr or Hf,
R 1 To R 4 Each independently is hydrogen, a substituted or unsubstituted alkyl group of 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group of 3 to 20 carbon atoms, or a substituted or unsubstituted aryl group of 6 to 20 carbon atoms, wherein two or more adjacent ones of them may be linked to form a ring;
R 5 and R is 6 Each independently is hydrogen, a substituted or unsubstituted alkyl group of 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group of 3 to 20 carbon atoms, or a substituted or unsubstituted aryl group of 6 to 20 carbon atoms, wherein the substitution is performed with an alkyl group of 1 to 12 carbon atoms;
each R 7 Independently is a substituted or unsubstituted alkyl group of 4 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group of 4 to 20 carbon atoms, or a substituted or unsubstituted aryl group of 6 to 20 carbon atoms;
n is 1 to 5; and
Y 1 and Y 2 Each independently is a halogen group, an alkyl group of 1 to 20 carbon atoms, an alkenyl group of 2 to 20 carbon atoms, an alkynyl group of 2 to 20 carbon atoms, a cycloalkyl group of 3 to 20 carbon atoms, an aryl group of 6 to 20 carbon atoms, an alkylaryl group of 7 to 20 carbon atoms, an arylalkyl group of 7 to 20 carbon atoms, a heteroaryl group of 5 to 20 carbon atoms, an alkoxy group of 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group of 5 to 20 carbon atoms, an alkylamino group of 1 to 20 carbon atoms, an arylamino group of 5 to 20 carbon atoms, an alkylthio group of 1 to 20 carbon atoms, an arylthio group of 5 to 20 carbon atoms, an alkylsilyl group of 1 to 20 carbon atoms, an arylsilyl group of 5 to 20 carbon atoms, a hydroxyl group, an amino group, a mercapto group, a silyl group, a cyano group or a nitro group.
11. The method of preparing a multiblock copolymer according to claim 9, wherein the organozinc compound is represented by the following formula 5:
[ 5]
In the formula 5, the components are,
R 8 and R is 10 Each independently is a single bond or an alkylene group of 1 to 10 carbon atoms, R 9 Alkylene of 1 to 10 carbon atoms or-SiR 11 R 12 -, and R 11 And R is 12 Each independently is an alkyl group of 1 to 10 carbon atoms.
12. The method for preparing a multiblock copolymer according to claim 9, wherein the anionic polymerization initiator comprises an alkyl lithium compound including an allyl group, and the allyl group is combined with lithium.
13. The method for preparing a multiblock copolymer according to claim 12, wherein the alkyl lithium compound is represented by the following formula 11:
[ 11]
In formula 11, R 13 Is hydrogen or a hydrocarbon group of 1 to 20 carbon atoms
A is an amine-based compound represented by the following formula 12:
[ 12]
In the formula 12, the components are,
R 14 to R 18 Each independently hydrogen or a hydrocarbyl group of 1 to 20 carbon atoms, and
a and b are each independently integers from 0 to 3, wherein a and b are not both 0.
14. A thermoplastic resin composition comprising polypropylene and the multiblock copolymer of claim 1.
15. The thermoplastic resin composition of claim 14, wherein said polypropylene and said multiblock copolymer are contained in a weight ratio of 1:0.1 to 1:9.
16. The thermoplastic resin composition of claim 14, wherein the thermoplastic resin composition satisfies the following conditions a) to c):
a) The height of the stress variation (tan delta) peak according to temperature, derived by dynamic viscoelasticity analysis, is 0.02 to 0.13;
b) The radius (Rv) of the dispersed phase is 0.10 μm to 0.50 μm; and
c) The glass transition temperature (Tg) is from-60℃to-30 ℃.
17. The thermoplastic resin composition of claim 16, wherein said thermoplastic resin composition satisfies b) that the radius (Rv) of the dispersed phase is from 0.10 μιη to 0.27 μιη.
Applications Claiming Priority (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR10-2021-0130758 | 2021-10-01 | ||
KR10-2021-0130757 | 2021-10-01 | ||
KR10-2022-0124449 | 2022-09-29 | ||
KR1020220124449A KR20230047916A (en) | 2021-10-01 | 2022-09-29 | Thermoplastic resin composition |
KR10-2022-0124448 | 2022-09-29 | ||
PCT/KR2022/014838 WO2023055208A1 (en) | 2021-10-01 | 2022-09-30 | Multi-block copolymer, resin composition, and method for manufacturing same |
Publications (1)
Publication Number | Publication Date |
---|---|
CN117794998A true CN117794998A (en) | 2024-03-29 |
Family
ID=90380213
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202280055468.3A Pending CN117794998A (en) | 2021-10-01 | 2022-09-30 | Multiblock copolymer, resin composition, and method for preparing the same |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN117794998A (en) |
-
2022
- 2022-09-30 CN CN202280055468.3A patent/CN117794998A/en active Pending
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN113661187B (en) | Polypropylene composite material and preparation method thereof | |
CN113677723A (en) | Polyolefin-polystyrene multi-block copolymer and preparation method thereof | |
WO2017213216A1 (en) | Thermoplastic elastomer composition, method for producing same and molded body | |
JP6668023B2 (en) | Propylene resin composition, method for producing the same, and molded article | |
KR20230047916A (en) | Thermoplastic resin composition | |
JP7308011B2 (en) | PROPYLENE-BASED RESIN COMPOSITION, METHOD FOR PRODUCING SAME, AND MOLDED PRODUCT USING THE PROPYLENE-BASED RESIN COMPOSITION | |
US20230287207A1 (en) | Thermoplastic Resin Composition | |
TW202219164A (en) | Thermoplastic resin composition | |
CN117794998A (en) | Multiblock copolymer, resin composition, and method for preparing the same | |
TW202222958A (en) | Thermoplastic resin composition | |
US20240182693A1 (en) | Thermoplastic Resin Composition | |
TW202330776A (en) | Thermoplastic resin composition | |
CN117858911A (en) | Multiblock copolymer, resin composition comprising the same, and method of preparing the same | |
EP4372046A1 (en) | Multi-block copolymer, resin composition, and method for manufacturing same | |
TW202332706A (en) | Multiblock copolymer, resin composition and method for preparing thereof | |
CN117098804A (en) | Thermoplastic resin composition | |
KR20230047913A (en) | Multiblock copolymer, resin composition comprising the same and method for manufacturing the same | |
JP2020158652A (en) | Propylene-based polymer composition and molding thereof | |
EP4169981A1 (en) | Thermoplastic resin composition | |
US20230287208A1 (en) | Thermoplastic Resin Composition | |
KR20230047915A (en) | Multiblock copolymer and method for manufacturing the same | |
KR20240112215A (en) | Block copolymer, method for preparing block compolymer and resin composition | |
KR20240064575A (en) | Resin composition and method for preparing resin composition | |
CN112204055A (en) | Polypropylene composition and molded article | |
CN117881710A (en) | Multiblock copolymers and methods of making the same |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination |