KR101834829B1 - Organozinc compound and method for manufacturing thereof - Google Patents
Organozinc compound and method for manufacturing thereof Download PDFInfo
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- KR101834829B1 KR101834829B1 KR1020160031186A KR20160031186A KR101834829B1 KR 101834829 B1 KR101834829 B1 KR 101834829B1 KR 1020160031186 A KR1020160031186 A KR 1020160031186A KR 20160031186 A KR20160031186 A KR 20160031186A KR 101834829 B1 KR101834829 B1 KR 101834829B1
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 86
- 238000000034 method Methods 0.000 title claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 title description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 27
- 239000001257 hydrogen Substances 0.000 claims abstract description 27
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 25
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims description 46
- 150000003752 zinc compounds Chemical class 0.000 claims description 32
- 239000002904 solvent Substances 0.000 claims description 30
- 239000011701 zinc Substances 0.000 claims description 23
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 18
- -1 zinc halide compound Chemical class 0.000 claims description 18
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 11
- 229910052725 zinc Inorganic materials 0.000 claims description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 10
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 9
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims description 8
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 claims description 8
- 239000011777 magnesium Chemical group 0.000 claims description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 6
- 125000005843 halogen group Chemical group 0.000 claims description 6
- 150000002681 magnesium compounds Chemical class 0.000 claims description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- 239000001282 iso-butane Substances 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 55
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 51
- 239000004793 Polystyrene Substances 0.000 description 40
- 229920002223 polystyrene Polymers 0.000 description 34
- 239000000178 monomer Substances 0.000 description 31
- 229920006030 multiblock copolymer Polymers 0.000 description 29
- 150000001336 alkenes Chemical class 0.000 description 25
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 24
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 23
- 238000006116 polymerization reaction Methods 0.000 description 20
- 229920001400 block copolymer Polymers 0.000 description 17
- 229920000642 polymer Polymers 0.000 description 17
- 229920000098 polyolefin Polymers 0.000 description 16
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 14
- 239000003054 catalyst Substances 0.000 description 13
- 229920001519 homopolymer Polymers 0.000 description 13
- 239000000047 product Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 10
- 238000005481 NMR spectroscopy Methods 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 238000001914 filtration Methods 0.000 description 8
- 239000003999 initiator Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 229910052723 transition metal Inorganic materials 0.000 description 8
- 150000003624 transition metals Chemical class 0.000 description 8
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical class C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 7
- 239000005977 Ethylene Substances 0.000 description 7
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 7
- 239000000706 filtrate Substances 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 6
- 238000012718 coordination polymerization Methods 0.000 description 6
- 239000003446 ligand Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- GHWNLWBZRYPTCB-UHFFFAOYSA-N ClCC1=CC=C(C=C1)C(=CC)CC Chemical compound ClCC1=CC=C(C=C1)C(=CC)CC GHWNLWBZRYPTCB-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 5
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 5
- 229920005996 polystyrene-poly(ethylene-butylene)-polystyrene Polymers 0.000 description 5
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 4
- VSKJLJHPAFKHBX-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 VSKJLJHPAFKHBX-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 238000003917 TEM image Methods 0.000 description 4
- FACXGONDLDSNOE-UHFFFAOYSA-N buta-1,3-diene;styrene Chemical compound C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 FACXGONDLDSNOE-UHFFFAOYSA-N 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 150000002430 hydrocarbons Chemical group 0.000 description 4
- 238000005580 one pot reaction Methods 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 4
- RCOVTJVRTZGSBP-UHFFFAOYSA-N 4-(chloromethyl)benzoyl chloride Chemical compound ClCC1=CC=C(C(Cl)=O)C=C1 RCOVTJVRTZGSBP-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 150000004795 grignard reagents Chemical class 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- ZMSZCUFHPKUFSI-UHFFFAOYSA-N 1-(chloromethyl)-4-prop-1-en-2-ylbenzene Chemical compound CC(=C)C1=CC=C(CCl)C=C1 ZMSZCUFHPKUFSI-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 239000007818 Grignard reagent Substances 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical group CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- FRIJBUGBVQZNTB-UHFFFAOYSA-M magnesium;ethane;bromide Chemical compound [Mg+2].[Br-].[CH2-]C FRIJBUGBVQZNTB-UHFFFAOYSA-M 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 150000002900 organolithium compounds Chemical class 0.000 description 2
- 150000002902 organometallic compounds Chemical class 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- AQIXEPGDORPWBJ-UHFFFAOYSA-N pentan-3-ol Chemical compound CCC(O)CC AQIXEPGDORPWBJ-UHFFFAOYSA-N 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 238000007039 two-step reaction Methods 0.000 description 2
- 238000004009 13C{1H}-NMR spectroscopy Methods 0.000 description 1
- TXZFBHYDQGYOIT-UHFFFAOYSA-N 2-(chloromethyl)benzoyl chloride Chemical compound ClCC1=CC=CC=C1C(Cl)=O TXZFBHYDQGYOIT-UHFFFAOYSA-N 0.000 description 1
- BLDFSDCBQJUWFG-UHFFFAOYSA-N 2-(methylamino)-1,2-diphenylethanol Chemical compound C=1C=CC=CC=1C(NC)C(O)C1=CC=CC=C1 BLDFSDCBQJUWFG-UHFFFAOYSA-N 0.000 description 1
- JTNCEQNHURODLX-UHFFFAOYSA-N 2-phenylethanimidamide Chemical compound NC(=N)CC1=CC=CC=C1 JTNCEQNHURODLX-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000004708 Very-low-density polyethylene Substances 0.000 description 1
- 229910007926 ZrCl Inorganic materials 0.000 description 1
- BPKGOZPBGXJDEP-UHFFFAOYSA-N [C].[Zn] Chemical compound [C].[Zn] BPKGOZPBGXJDEP-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000010538 cationic polymerization reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 238000010960 commercial process Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 229920001795 coordination polymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000013013 elastic material Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- BXOUVIIITJXIKB-UHFFFAOYSA-N ethene;styrene Chemical group C=C.C=CC1=CC=CC=C1 BXOUVIIITJXIKB-UHFFFAOYSA-N 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- YNXURHRFIMQACJ-UHFFFAOYSA-N lithium;methanidylbenzene Chemical compound [Li+].[CH2-]C1=CC=CC=C1 YNXURHRFIMQACJ-UHFFFAOYSA-N 0.000 description 1
- NXPHGHWWQRMDIA-UHFFFAOYSA-M magnesium;carbanide;bromide Chemical compound [CH3-].[Mg+2].[Br-] NXPHGHWWQRMDIA-UHFFFAOYSA-M 0.000 description 1
- 229920001179 medium density polyethylene Polymers 0.000 description 1
- 239000004701 medium-density polyethylene Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 239000012038 nucleophile Substances 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- OSDBJMYIUDLIRI-UHFFFAOYSA-N oxo-[[1-[[4-[[4-(oxoazaniumylmethylidene)pyridin-1-yl]methoxy]cyclohexyl]oxymethyl]pyridin-4-ylidene]methyl]azanium;dichloride Chemical compound [Cl-].[Cl-].C1=CC(=C[NH+]=O)C=CN1COC1CCC(OCN2C=CC(=C[NH+]=O)C=C2)CC1 OSDBJMYIUDLIRI-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000012667 polymer degradation Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229910000343 potassium bisulfate Inorganic materials 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- ZAKVZVDDGSFVRG-UHFFFAOYSA-N prop-1-en-2-ylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CC(=C)C1=CC=CC=C1 ZAKVZVDDGSFVRG-UHFFFAOYSA-N 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 230000003381 solubilizing effect Effects 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 239000012745 toughening agent Substances 0.000 description 1
- 229920001866 very low density polyethylene Polymers 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
- C07F3/06—Zinc compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
- C07F3/02—Magnesium compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of zinc, cadmium or mercury
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Graft Or Block Polymers (AREA)
Abstract
An embodiment of the present invention relates to an organozinc compound represented by the following formula (3) and a process for producing the same.
(3)
In the general formula (3), R 11 to R 16 are each independently hydrogen or an alkyl group having 1 to 20 carbon atoms.
Description
The present invention relates to organozinc compounds and processes for their preparation.
Polyolefin-polystyrene block copolymers such as styrene-ethylene / butylene-styrene (SEBS) or styrene-ethylene / propylene-styrene (SEPS) They are also excellent in heat resistance and light fastness compared to styrene-butadiene-styrene (SBS) or styrene-isoprene-styrene (SIS), and are suitable for soft and strong touch feeling of grips and handles, elastic materials of diapers, An oil-gel used for communication materials, an impact reinforcing agent for engineering plastics, a plasticizer for flexible polypropylene or a toughener. Conventional SEBS is prepared by a two step reaction in which SBS obtained by anionic polymerization of styrene and butadiene is hydrogenated. Conventional SEPS is also produced through a two-step reaction in which SIS obtained by anionic polymerization of styrene and isoprene is hydrogenated. The process of saturating all of the double bonds contained in the polymer main chain by hydrogenation is highly costly, and the unit price of SEBS and SEPS is considerably higher than that of SBS and SIS before the hydrogenation reaction. This may limit the market expansion. In addition, it is virtually impossible to saturate all of the double bonds in the polymer chain through the hydrogenation reaction, so that commercialized SEBS and SEPS contain slightly residual double bonds, and its presence is often a problem (Journal of Polymer Science: Part A: Polymer Chemistry, 2002, 40, 1253; Polymer Degradation and Stability 2010, 95, 975).
It is an object of the present invention to provide organozinc compounds which can be usefully employed in the preparation of polyolefin-polystyrene multiblock copolymers.
It is another object of the present invention to provide a process for the preparation of an organozinc compound which can be directly applied to the preparation of the polyolefin-polystyrene multiblock copolymer from an olefin monomer and a styrene monomer directly, .
The above and other objects of the present invention can be achieved by the present invention described below.
An embodiment of the present invention relates to an organozinc compound represented by the following formula (3).
(3)
In the general formula (3), R 11 to R 16 are each independently hydrogen or an alkyl group having 1 to 20 carbon atoms.
In the above formula (1), R 11 to R 14 are hydrogen; R 15 and R 16 may be a methyl group;
In Formula 1, R 11 to R 16 may be hydrogen.
Another embodiment of the present invention relates to a process for preparing an organozinc compound represented by the following formula (3) by reacting a magnesium compound represented by the following formula (A) and a zinc halide compound represented by the following formula (3).
(A)
In the formula (A), R 11 to R 16 are each independently hydrogen or an alkyl group having 1 to 20 carbon atoms; X is a halogen atom; Mg is magnesium;
[Chemical Formula B]
ZnX 2
In the above formula (B), X is a halogen atom; Zn is zinc;
(3)
In the general formula (3), R 11 to R 16 are each independently hydrogen or an alkyl group having 1 to 20 carbon atoms.
The method may further include adding an aliphatic hydrocarbon solvent having 4 to 20 carbon atoms to the product prepared by the reaction to prepare a product solution, and then crystallizing and separating the organic zinc compound of Formula 3 from the product solution.
The aliphatic hydrocarbon solvent may include at least one of isobutane, hexane, cyclohexane, and methylcyclohexane.
The present invention relates to an organozinc compound useful for preparing commercially useful polyolefin-polystyrene multiblock copolymers in one-pot form from olefin monomers and styrene monomers and directly to the one-pot process The present invention provides a method for producing the organic zinc compound.
1 is a graph showing the results of GPC analysis of polystyrene additionally produced in Example 3 of the present invention.
2 is a TEM image of the multi-block copolymer prepared in Example 3 of the present invention.
3 is a 1 H NMR spectrum of a product obtained by reacting alpha-methylstyrene and CH 3 C 6 H 4 CH 2 Li (TMEDA) in Comparative Example 2 of the present invention.
Organozinc compound
One embodiment of the present invention relates to an organozinc compound represented by the following formula (1).
(3)
In Formula 3, R 11 to R 16 are each independently hydrogen or an alkyl group having 1 to 20 carbon atoms, and Zn is zinc.
When the organozinc compound of formula (3) is used, commercially useful polyolefin-polystyrene multiblock copolymers can be prepared from olefin monomers and styrene monomers by a one-pot process.
In one embodiment, R 11 to R 14 in Formula 3 are hydrogen, and R 15 and R 16 are methyl groups. In another embodiment, R 11 to R 16 in Formula 3 may all be hydrogen. In these embodiments, the organozinc compound of formula (III) may provide commercially more useful polyolefin-polystyrene multiblock copolymers.
Another embodiment of the present invention relates to a process for preparing an organozinc compound represented by the above-described general formula (3).
The organic zinc compound may be prepared by reacting a magnesium compound represented by the following formula (A) and a zinc halide compound represented by the following formula (B) to produce an organic zinc compound represented by the above formula (3).
(A)
In the formula (A), R 11 to R 16 are each independently hydrogen or an alkyl group having 1 to 20 carbon atoms; X is a halogen atom; Mg is magnesium.
[Chemical Formula B]
ZnX 2
In the above formula (B), X is a halogen atom; Zn is zinc.
In Formula (A) or Formula (B), X may each independently include any one of I, Cl and Br.
The method for producing the magnesium compound of the above formula (A) is not particularly limited. Specifically, the magnesium compound of formula (A) can be prepared by reacting 1-chloromethyl-4- (? -Methylethyl) benzene or 1- (chloromethyl) -4- - (1-ethylpropenyl) benzene) in anhydrous diethyl ether is added to a mixture of magnesium metal and diethyl ether, and the mixture is stirred at room temperature. The compound of formula (3) thus prepared can be used by filtration and washing with diethyl ether.
(1-chloromethyl) -4- (1-ethylpropenyl) benzene) (1-chloromethyl) benzene or 1- (chloromethyl) Can be prepared, for example, according to the method for preparing Grignard reagents from 4- (chloromethyl) benzoyl chloride (J. Org. Chem. 1987, 52, 3254-3263).
Specifically, the magnesium compound of formula (A) and the zinc halide compound of formula (B) react with each other in a diethyl ether solvent to form a solid organic zinc compound represented by formula (3) Washed with a diethyl ether solvent and then obtained in the form of a solid residue.
The organic zinc compound may be prepared by preparing a product solution by adding an aliphatic hydrocarbon solvent having 4 to 20 carbon atoms to a product prepared by the reaction and then crystallizing and separating the organic zinc compound of Formula 3 from the product solution .
In this case, the organic zinc compound represented by the general formula (3) contained in the product is a product solution in a state of being dissolved in an aliphatic hydrocarbon solvent having 4 to 20 carbon atoms. When the insoluble ferric sulphate is removed from the product solution by using celite or the like, and then the organic zinc compound represented by the formula (3) is crystallized from the filtrate, an organozinc compound of formula (3) with better purity can be obtained.
The aliphatic hydrocarbon solvent may include, for example, at least one of isobutane, hexane, cyclohexane, and methylcyclohexane. In this case, the effect of selectively solubilizing only the organozinc compound of Chemical Formula 3 is excellent.
Specifically, the filtrate is subjected to a process of gradually removing the solvent by using a vacuum pump or the like, then the solvent removal process is stopped at the beginning of the crystallization and the crystallization is promoted at a temperature of -50 ° C to -10 ° C, Can be used as a solid-form yield in isolation from a solvent.
Polyolefin-polystyrene multiblock copolymer
The organozinc compound represented by the general formula (3) of the present invention is useful for producing a multiblock copolymer including a repeating unit represented by the following general formula (1).
[Chemical Formula 1]
In Formula 1, R 1 and R 2 are each independently any one of hydrogen, methyl, ethyl, butyl, and hexyl; R 11 to R 16 are each independently hydrogen or an alkyl group having 1 to 20 carbon atoms; Ar is independently an aryl group having 6 to 20 carbon atoms; Z is an alkyl group having 1 to 20 carbon atoms or an arylalkyl group having 7 to 20 carbon atoms; p and 1-p are mole fractions of p and 1-p, which are each repeating unit constituting the repeating unit a, and p is 0 or more than 0 and not more than 1; the average value of a is from 10 to 10,000; the average value of b is independently 10 to 1,000; n is a natural number of 1 or 2.
The polyolefin-polystyrene multiblock copolymer including the repeating unit having the structure represented by the above-mentioned formula (1) is a compound disclosed for the first time by the production method of the present invention.
In the present specification, the repeating unit a represented by square brackets ([]) means a polyolefin block constituting a multiblock copolymer. Similarly, the repeating unit b represented by the square brackets ([]) in the formula means a polystyrene block constituting a multiblock copolymer. The repeating units may each be composed of repeating units derived from at least one monomer.
In the present specification, a and b can be used as a symbol for distinguishing the repeating unit (or each block), and can be used as a symbol indicating the number of repeating units of each repeating unit. In a typical polymer synthesis, the value of a is obtained as a mixture having a constant distribution rather than a single integer, and thus the average value thereof is measured and discussed.
The average value of a in the above formula (1) can be controlled depending on the content of the olefin monomer and the organic zinc compound introduced into the reaction material. The average value of a is not limited to the lower limit, but if the average value of a is more than 10,000, the viscosity is large and it is not easy to realize the compound having the structure of the formula (1). Specifically, a in Formula 1 may have an average value of 10 to 10,000.
The average value of b in the above formula (1) can be controlled according to the amount of styrene monomer added to the reaction material. When the average value of b is 10,000 or more, the viscosity is large and the production method is not easy. When the value of b is less than 10, it is not easy to obtain a multiblock copolymer having the structure of the above formula (1). Specifically, the average value of b in formula (1) may be 10 to 1,000. Within this range, the multiblock copolymer can be applied to a wide variety of fields, and the manufacturing method is more efficient.
The repeating unit a in the above formula (1) may contain olefin repeating units p and 1-p. In the present specification, p and 1-p are used as symbols for distinguishing the olefin repeating units constituting the repeating unit a, and the mole fractions of the repeating unit p and the repeating unit 1-p are present in the repeating unit a. The polyolefin block in which the two repeating units (p and 1-p) are randomly distributed is obtained by selecting two olefins such as ethylene, propylene, 1-butene, 1-hexene, . ≪ / RTI >
The value of n in the formula (1) is a value that can be determined by the amount of Z-Li introduced in the second step and the organozinc compound of formula (3) introduced in the first step of the multiblock copolymer production method described later, . Repeating units having an n value of more than 2 or 3 or more are usually difficult to produce because of the low ceiling temperature of the alpha-alkylstyrene.
Specifically, the repeating unit a may be prepared by using an olefin monomer including ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-decene and the like as a reaction material.
In the specific example, when p of the repeating unit a is 0, the repeating unit a is one in which one of the olefin monomers including ethylene, propylene, 1-butene, 1-hexene, , And when p of the repeating unit a is more than 0, the repeating unit a may be prepared by reacting two of the olefin monomers including ethylene, propylene, 1-butene, 1-hexene, ≪ / RTI > At this time, R 1 and R 2 may be randomly distributed in the repeating unit a (polyolefin block).
The repeating unit b in the above formula (1) can be prepared by using a styrene-based monomer as a reaction material. In embodiments, a styrenic monomer including ethylene substituted with an aryl group having 6 to 20 carbon atoms, ethylene substituted with a phenyl group, and the like can be produced by using the reaction material.
In one embodiment, R 1 in Formula 1 is hydrogen, and R 2 is any one of a methyl group, an ethyl group, a butyl group, and a hexyl group; Ar is a phenyl group; R 11 to R 16 are hydrogen; Z may be a butyl group or a benzyl group. In this case, it is possible to provide a polyolefin-polystyrene multi-block copolymer which realizes a more excellent reaction efficiency and has a large commercial ripple effect and a method for producing the same.
The multiblock copolymer represented by the above formula (1) may be, for example, a polystyrene-block-poly (ethylene-co-propylene) -block-polystyrene or a polystyrene- (Ethylene-co-1-hexene) -block-polystyrene, polystyrene-block-polystyrene, block-polystyrene-block-poly ) Copolymer.
The multiblock copolymer represented by the above formula (1) may be prepared, for example, by copolymerizing polystyrene-block- [poly (ethylene-co-propylene) -block-polystyrene] 2, polystyrene- (ethylene-co-1-hexene) -block-polystyrene] 2, polystyrene-block- [poly (ethylene- -block-polystyrene] 2 pentablock copolymers.
The organic zinc compound represented by the formula (3) of the present invention is also useful for preparing an organic zinc compound represented by the following formula (2).
(2)
In Formula 2, R 1 and R 2 are each independently any one of hydrogen, a methyl group, an ethyl group, a butyl group, and a hexyl group; R 11 to R 16 are each independently hydrogen or an alkyl group having 1 to 20 carbon atoms; p and 1-p are mole fractions of p and 1-p, which are each repeating unit constituting the repeating unit a, and p is 0 or more than 0 and not more than 1; The average value of a is 10 to 10,000.
The organic zinc compound represented by Formula 2 is a compound formed in the first step in the process for preparing a multiblock copolymer represented by Formula 1, which will be disclosed first through the present invention. The organozinc compound represented by the formula (2) is characterized in that the terminal contains a polyolefin group having an alpha-alkylstyryl group. The alpha-alkylstyryl group is derived from the organozinc compound represented by the above-mentioned formula (3) which is introduced in the process for preparing a compound represented by the following formula (1), and does not participate in the reaction during the olefin coordination polymerization but the anion polymerization, There are features that can be utilized in.
That is, the technique provided by the present invention can be easily used for production of a polystyrene-polyolefin block copolymer by forming an organic zinc compound represented by the general formula (2), followed by successive styrene anion polymerization.
Also, the organozinc compound of formula (2) reacts with water, oxygen or organic acid to desorb the zinc metal to convert the alpha-alkylstyrene group into a polyolefin having terminal groups, and then separates the anion- Polymerization, cationic polymerization, and the like, for the production of various polyolefin-based block copolymers.
Specifically, in Formula 2, R 1 is hydrogen; R 2 is any one of a methyl group, an ethyl group, a butyl group and a hexyl group; R 11 to R 16 may be hydrogen, and in this case, the zinc compound of formula (II) may be a poly (ethylene-co-propylene), poly (ethylene-co-1-butene), poly Ethylene-co-1-hexene), poly (ethylene-co-1-octene), and the like. In this case, polyolefin-polystyrene multi-block copolymers which are more commercially useful, low in unit cost and low in manufacturing cost and excellent in commercial value can be provided with higher productivity.
The organozinc compound of formula (2) may be prepared by olefin polymerization according to the present invention (first step described below). A process for producing an organozinc compound having a polyolefin group by introducing an olefin between zinc-ethyl groups in the presence of an olefin coordination polymer in the presence of an organic zinc compound such as diethyl zinc which is produced in large quantities in a commercially available manner is a process for preparing a precisely controlled polyolefin chain (J. Am. Chem. Soc. 2005, 127, 9913; Science 2006, 312, 714), but the reaction using an organozinc compound containing an alpha-alkylstyryl group, as in the present invention, There are no examples reported.
The polyolefin-polystyrene multi-block copolymer is prepared by coordinating an olefin monomer with a transition metal catalyst in the presence of an organic zinc compound represented by the formula (3) to prepare a compound represented by the following formula (2): And
A Z-Li compound (Z is an alkyl group having 1 to 20 carbon atoms or an arylalkyl group having 7 to 20 carbon atoms), an amine ligand represented by the following formula (4), and a styrene-based monomer are continuously added to the compound represented by the formula And a second step of performing anionic polymerization.
[Chemical Formula 4]
In the general formula (4), R 41 and R 42 are each independently a hydrocarbon group having 1 to 20 carbon atoms, and z is an integer of 2 or 3.
The first step of preparing the organozinc compound represented by the general formula (2)
The compound represented by the general formula (2) prepared in the first step can be prepared by coordination polymerization of an olefin monomer with a transition metal catalyst in the presence of an organic zinc compound represented by the general formula (3) as described later.
Specifically, the olefin monomer to be charged as the reaction material in the first step may be exemplified by monomers formed of ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-decene or a mixture thereof. These olefin monomers may be used singly or in combination of two or more.
The olefin monomer in embodiments can be a monomer formed from a mixture of ethylene and any one of propylene, 1-butene, 1-hexene and 1-octene. Such a polyolefin prepared from any one of propylene, 1-butene, 1-hexene and 1-octene and ethylene can be, for example, HDPE, MDPE, LLDPE, VLDPE, POE, EP and the like.
In the specific examples, when ethylene, propylene, 1-butene or the like having a relatively low boiling point is used as the olefin monomer, the polymerization reaction can proceed under a certain pressure.
Specifically, the organic zinc compound represented by Formula 3 may be a compound in which R 11 to R 16 are both hydrogen. In this case, the organic zinc compound represented by Formula 3 can be easily prepared, and purified by recrystallization And is therefore suitable for incorporation into olefin polymerization.
The transition metal catalyst used in the first step is not limited, but is usually a homogeneous (metallocene) catalyst comprising a transition metal catalyst and / or a cocatalyst which is a main catalyst and an organoaluminum or boron compound, Ziegler catalysts can be used. In embodiments, when a homogeneous catalyst is used, the catalyst activity may be better and better.
Specifically, the transition metal catalyst may include a compound represented by the following formula (5).
[Chemical Formula 5]
In
When the compound represented by
In the production method of one embodiment, the coordination polymerization of the first step can be carried out in a homogeneous solution state. At this time, as the solvent, a hydrocarbon solvent or an olefin monomer itself can be used as a medium. Examples of the hydrocarbon solvent include aliphatic hydrocarbon solvents having 4 to 20 carbon atoms, specifically, isobutane, hexane, cyclohexane, methylcyclohexane, and the like. These solvents may be used alone or in combination of two or more.
The polymerization temperature in the first step may vary depending on the reactants, reaction conditions and the like, but may be specifically performed at 70 to 170 degrees Celsius. Within the above range, the catalyst can be thermally stabilized while increasing the solubility of the polymer.
The polymerization of the first stage may be carried out batchwise, semicontinuously or continuously and may also be carried out in two or more stages having different reaction conditions.
The compound represented by Formula 2, prepared by the first step of the above-described Examples, can be prepared by preparing a polyolefin-polystyrene-polyolefin multiblock copolymer represented by Formula 1 described above by anion polymerization in the second step Lt; / RTI > precursor.
The second step of performing anionic polymerization
The polyolefin-polystyrene multi-block copolymer of the above-mentioned formula (1) can be prepared by continuously performing the second step in the first step of preparing the compound represented by the following formula (2).
In the second step, the styrenic monomer between the zinc-carbon bonds contained in the compound of formula (2) formed by the first step described above can be continuously inserted, and at the same time, the alpha-alkyl The styrene-based monomer can be continuously inserted through the styrene group. Thus, an organometallic compound containing the multiblock copolymer of the present invention can be prepared by a one-pot preparation method. In addition, the polymer compound produced through the above process is converted into an industrially useful polyolefin-polystyrene multi-block copolymer by reacting with water, oxygen or an organic acid as an organometallic compound represented by * in the formula 1 as Zn or Li.
Specifically, the styrenic monomer may be an alpha styrene monomer (ArCH = CH 2 ) having 6 to 20 carbon atoms. More specifically, it may be a styrenic monomer including ethylene substituted with an aryl group having 6 to 20 carbon atoms, ethylene substituted with a phenyl group, and the like, for example, styrene.
It is noteworthy that the organozinc compound (Formula 2 or Formula 3) itself does not act as an initiator in styrene polymerization. That is, when only the styrene monomer is added after the coordination polymerization in the first step, polymerization reaction does not proceed at all. Further, when styrene polymerization is carried out using an alkyl lithium compound (Z-Li) as an initiator in the presence of an organic zinc compound in a hydrocarbon solvent, the polymer chain is formed only from an alkyl lithium compound (Z-Li) Styrene-based monomer is not inserted. In this case, the organic zinc compound does not participate in the polymer chain formation reaction and remains as it is (Polymer, 2009, 50, 3057).
In the second step of the present invention, the anionic polymerization is carried out by introducing an alkyl lithium compound (Z-Li) after the coordination polymerization in the first step and an amine ligand of the following formula (4) as an initiator. (Z-Li), an amine ligand represented by the following general formula (4), and a styrene-based monomer are continuously added to the compound represented by the above-mentioned general formula (3), whereby the styrene- 2 and the alpha-alkylstyrene group present in the terminal of formula (2), resulting in a multiblock copolymer of formula (1).
It is disclosed for the first time through the present invention that an amine ligand of the general formula (4) is further added to continuously introduce a styrene monomer into a space between zinc-carbon bonds to grow a polymer chain.
Reaction Scheme 1 illustrates that in the second step, when the amine ligand of Formula 4 (e. G., R 41 is methyl and R 42 is hydrogen and z is 2, TMEDA) The process of growing polystyrene chains between carbon bonds is illustrated. Typically, when the amine ligand in the form of the formula (4) is coordinated to lithium, the reactivity of the organolithium compound is increased. Due to the increased reactivity, a zincate-type compound is reversibly formed and an exchange reaction takes place between the alkyl of the alkyllithium compound (Z-Li) where the polymer chain grows and the alkyl group of the dialkyl zinc. As a result of this exchange reaction, the polymer chain is grown from the organozinc compound.
[Reaction Scheme 1]
The alpha-alkylstyryl group attached to the terminal of the compound of formula (2) formed by the first step does not participate in the reaction during the coordination polymerization but can participate in the reaction during the second step anion polymerization. An example of this is shown in Scheme 2. (6) of Reaction Scheme 2 by reacting the Z-Li or Z-Li charged as an initiator in the reaction scheme 2 and the mixture of the
[Reaction Scheme 2]
The polystyrene chain in which the Z-Li charged as an anion initiator in the second step is not reacted with the alpha-alkyl styrene group contained in the formula (2) in the formula (2) It is desirable to minimize the amount of PS (polystyrene) -homopolymer produced by-products which are not used.
For example, in order to minimize the amount of PS-homopolymer produced, an initiator (a mixture of Z-Li or Z-Li and a compound of Formula 4) is added prior to the styrene monomer introduction in the second step, Alkylstyrene groups of formula (2) produced in the first step. The reaction product (the compound wherein n is 1 in (2) in Scheme 2) itself also reacts with alpha-alkylstyrene in the reaction of the alpha-alkylstyrene and the mixture of Z-Li and the compound of
Usually, the transition metal catalyst used in the first stage olefin polymerization does not affect the second stage anionic polymerization in a trace amount relative to the alkyllithium compound to be introduced in the second stage. On the other hand, when the organoaluminum-based co-catalyst added to the first stage olefin polymerization is further used, the amount thereof is not negligible compared to the alkyllithium compound to be added in the second stage. Typically, organoaluminum compounds form a complex with an alkyl lithium compound in a 1: 1 ratio (Al: Li ratio), which does not initiate anionic polymerization. However, when the Li / Al ratio is 1 or higher, anionic polymerization starts, and the styrene chain grows from all the alkyllithium compounds including alkyllithium complexed at 1: 1 (Polymer, 2009, 50, 3057). That is, when the first step is carried out using the organoaluminum compound as a cocatalyst and then the second step anionic polymerization is carried out, the molar number of the alkyllithium compound to be added is controlled by the molar amount of aluminum Moles. Considering the reaction rate, the number of Z-Li moles (i.e., 'Li molar number-Al molar number') remaining after reacting with the organoaluminum in order to efficiently grow the polystyrene chain between the organic- May be more than 0.2 times the number. In order to reduce the amount of the PS-homopolymer produced by inserting the styrene monomer into the remaining Z-Li without reacting with the alpha-alkylstyrene group contained in the formula (2), the molar ratio of the remaining moles (I.e., 'Li molar number - Al molar number') should be smaller than the number of moles of alpha-alkylstyrene group (that is, the number of moles of Zn x 2) contained in the formula (2).
For example, when the value of 'Li molar number-Al molar number' is in the range of 0.5 to 0.7 times the value of 'Zn molar number × 2', the compound of the formula (5) wherein n is 1 and the compound wherein n is 2 Lt; / RTI >
When the value of 'Li molar number -Al molar number' is a small value within the above range, the amount of Li molar number-Al mole Is reacted with an alpha-alkylstyrene of formula (2) to be consumed, and a certain amount of alpha-alkylstyrene group remains unreacted, and then styrene monomer is added to participate in anion polymerization. Typically, 100% conversion of monomers is possible during anionic polymerization, and the remaining alpha-alkylstyrene groups can participate in anion polymerization. The alpha-alkylstyrene has a ceiling temperature of 66 DEG C, and the polymerization reaction itself does not proceed at a polymerization temperature of 100 DEG C or higher as in the embodiment of the present invention, but copolymerization with styrene proceeds (US Patent 4704431). When the remaining alpha-alkylstyrene group participates in the second stage styrene anion polymerization reaction, a multiblock copolymer having two or more repeating units of formula (1) may be produced.
Specifically, the Z-Li compound may be butyllithium or benzyllithium. Such an organolithium compound is widely used as an initiator for anionic polymerization and is easily available for use in the present invention.
Specifically, the compound of
In one embodiment, the compound of
Specifically, the alkyllithium compound and the compound of
The polymerization temperature in the second step may vary depending on the reactants, reaction conditions and the like, but may be specifically performed at 70 to 170 degrees Celsius. Within the above range, the multiblock copolymer represented by formula (1) is efficiently produced.
The polymerization of the second step may be carried out batchwise, semicontinuously or continuously, and may also be carried out in two or more stages having different reaction conditions.
The polymerization time in the second step may vary depending on the reactants, the reaction conditions, and the like, but may be specifically 0.5 to 10 hours, 0.5 to 8 hours, 0.5 to 5 hours, or 0.5 to 2 hours. Within this range, the entire amount of the styrene-based monomer to be charged can be converted into a multiblock copolymer.
It is a feature of the present invention that styrene anion polymerization is continuously carried out successively after the first stage olefin polymerization to simplify the method for producing a multiblock copolymer, thereby lowering the manufacturing cost and facilitating the application to a commercial process.
Hereinafter, the configuration and operation of the present invention will be described in more detail with reference to preferred embodiments of the present invention. It is to be understood, however, that the same is by way of illustration and example only and is not to be construed in a limiting sense.
Example 1: Synthesis of Compound (3) (R 11 To R 16 = H) Manufacturing
1-Chloromethyl-4-isopropenylbenzene was prepared from 4- (chloromethyl) benzoyl chloride according to the same experimental procedure and conditions (J. Org. Chem. 1987, 52, 3254-3263).
(1.73 g, 71.2 mmol) and anhydrous diethyl ether (30 mL) were added to a solution of 1-Chloromethyl-4-isopropenylbenzene (7.90 g, 47.4 mmol) in anhydrous diethyl ether It was slowly added to the flask. Diethyl ether self - refluxed by exothermic reaction during the addition. After stirring for 4 hours at room temperature, the Grignard reagent prepared by filtration and washing (diethyl ether, 10 mL × 2) was separated from the excess Mg metal without loss. ZnCl 2 (3.23 g, 23.7 mmol) was dissolved in diethyl ether (25 mL) for 6 hours at room temperature with stirring. A small amount of insoluble solid compound was prepared by filtration, and then slowly added at room temperature to the Grignard reagent prepared above. After stirring at room temperature for 1 day, MgCl 2 produced as a by-product was removed by filtration using Celite. The compound prepared by washing with diethyl ether (20 mL x 2) was filtered without loss. The filtrate was taken out, the solvent was removed by using a vacuum pump, and the resulting solid residue (8.00 g) was added with methylcyclohexane (200 g). Insoluble impurities were removed by filtration using Celite. The solvent was gradually removed from the filtrate by a vacuum pump, and the solvent removal process was stopped at the point of time when the crystallization was started (half of the solvent was removed), and the solution was stored in a -30 freezer for 5 hours to induce crystallization. The precipitated crystals were separated off with gentle stirring of the solvent (3.8 g). The mother liquor was removed and the solvent was further removed. The solution was further stored in a -30 freezer to induce crystallization (3.2 g, total 7.0 g, 90%).
1 H NMR (400 MHz, C 6 D 6: δ 7.36 (d, J = 8.0 Hz, 4H), 6.86 (d, J = 8.0 Hz, 4H), 5.44 (s, 2H), 5.00 (s, 2H) , 2.04 (s, 6H), 1.55 (s, 4H) ppm 13 C {1 H} NMR (C 6 D 6):. δ 144.21, 143.42, 127.24, 126.19, 110.63, 23.91, 22.28 ppm.
Example 2: a compound represented by the formula (3) (R 11 To R 14 = H, R 15 = R 16 = CH 3 ) Produce
(Chloromethyl) benzoyl chloride was obtained in the same manner as in Experimental procedure and conditions of J. Org . Chem. 1987, 52, 3254-3263 mentioned above in Example 1 using EtMgBr instead of MeMgBr . (1- (chloromethyl) -4- (1-ethylpropenyl) benzene)) was prepared. To a 1-necked flask, 4- (chloromethyl) benzoyl chloride (6.00 g, 31.7 mmol) was dissolved in diethyl ether (80 mL) and EtMgBr (diethyl ether solution 3.00 M, 21.6 g, 63.5 mmol) . The temperature was gradually raised to room temperature and then stirred for 4 hours. After lowering the temperature to 0, add NH 4 Cl aqueous solution (20 mL), add HCl aqueous solution (1 M, 80 mL), and take a diethyl ether layer. The organic layer of the water layer was further extracted with diethyl ether (40 mL × 2). The diethyl ether layer was collected and dried using anhydrous MgSO 4. The solvent was removed with a rotary evaporator to obtain 3- (4-chloromethylphenyl) 3-ol (6.3 g, 94%). 1 H NMR (400 MHz, CDCl3 ): δ 7.36 (s, 4H), 4.60 (s, 2H), 1.91-1.75 (m, 4H), 1.63 (s, 1H), 0.76 (t, J = 7.2 Hz, 6H) ppm. Of the above prepared 3- (4-chloromethylphenyl) in pentan-3-ol compound hydroquinone (36.9 mg, 0.335 mmol) and potassium bisulfate (0.351 g, 2.56 mmol ) 130 ℃ then gave put ~ 140 ℃ immersed in a constant temperature bath H 2 O Removal reaction. The resulting water was depressurized with an aspirator and reacted for 2 hours while being continuously removed. After the reaction, the temperature of the thermostat bath was lowered to 70 ° C and then distilled under reduced pressure using a vacuum pump to obtain 1- (chloromethyl) -4- (α-ethyl-β-methylethenyl) benzene )) Compound (4.52 g, 77%). 1 H NMR analysis revealed that the two stereoisomers were present at a ratio of 1.00: 0.19. 1 H NMR (400 MHz, C 6 D 6): δ major isomer signals 7.38-7.31 (m, 4H), 5.76 (quintet, J = 6.8 Hz, 1H), 4.60 (s, 2H), 2.53 (quintet, J = 8.0 Hz, 2H), 1.81 (d, J = 7.2 Hz, 3H), 1.00 (t, J = 7.2 Hz, 3H); minor isomer signals 7.17-7.15 (m, 4H ), 5.56 (quintet, J = 6.8 Hz, 1H), 4.62 (s, 2H), 2.34 (quintet, J = 8.0 Hz, 2H), 1.56 (d, J = 8.0 Hz, 3H), 0.90 (t, J = 7.2 Hz, 3H) ppm. (1-chloromethyl) -4- (1-ethylpropenyl) benzene) was used instead of 1- (Chloromethyl) -4- Nyde reagent was prepared and reacted with ZnCl 2 (0.70 g, 5.15 mmol) to synthesize the desired organozinc compound. The residue (1.8 g) obtained by removing the solvent of diethyl ether was dissolved in hexane (100 mL) and the undissolved impurities were removed by filtration using Celite. The filtrate was taken and the solvent was removed by using a vacuum pump. Hexane (100 mL) was added to the obtained residue (1.4 g), and the undissolved impurities were removed once again through filtration using Celite. The filtrate was taken and the solvent was removed by using a vacuum pump to obtain pure 3 (1.20 g, 61%). 1 H NMR analysis revealed that the two stereoisomers were present at a ratio of 1.00: 0.18. 1 H NMR (400 MHz, C 6 D 6): δ major isomer signals 7.29 (d, J = 8.4 Hz, 4H), 6.89 (d, J = 8.4 Hz, 4H), 5.76 (quintet, J = 7.2 Hz, 2H), 2.48 (quintet, J = 7.6 Hz, 4H), 1.68 (d, J = 6.8 Hz, 6H), 1.55 (s, 4H), 1.02 (t, J = 7.2 Hz, 6H); minor isomer signals 1 H NMR (400 MHz, C 6 D 6: δ 7.22 (d, J = 8.0 Hz, 4H), 7.09 (d, J = 7.6 Hz, 4H), 5.51 (quintet, J = 7.2 Hz, 2H ), 2.39 (quintet, J = 7.2 Hz, 4H), 1.68 (d, J = 6.8 Hz, 6H), 1.53 (s, 4H), 1.03 (t, J = 7.2 Hz, 6H) ppm.
Preparation of polystyrene multiblock copolymer (Ar = Ph, R 11 - - polyolefin represented by the general formula 1 R 16 = H, R 1 = H, R 2 = hexyl, A = C 6
Step 1: To a reactor (3) (R 11 - R 16 = H) (47.1 mg, 200 μmol) and 1-octene (10 g) were dissolved in methylcyclohexane (20 g), and the temperature was raised to 80 ° C. rac- [Me 2 Si (2-methylindenyl)] 2 ZrCl 2 (1.0 μmol, Formula 5) and MMAO (200 μmol) in methylcyclohexane (1 mL) was injected into the reactor and immediately filled with ethylene at 30 bar. After 1 minute, the reaction was carried out at a rate of 230 mL / min For one hour. The pressure was adjusted at a level of 5 to 10 atmospheres.
Step 2: A solution of PhCH 2 -Li (TMEDA) (85.7 mg, 400 μmol) dissolved in methylcyclohexane (20 g) was added to the reactor and the temperature was adjusted to 110 ° C. over 60 minutes. Styrene (10.4 g, 100 mmol, [styrene] / [Zn] = 500) was injected in a syringe and 2.0 mL was injected at the beginning. The reaction temperature was adjusted to 116 ° C to 120 ° C, and the reaction was further performed for 1 hour to confirm that the styrene monomer was exhausted by 1 H NMR analysis.
After the temperature was lowered to room temperature, the organic zinc compound containing the multiblock copolymer produced was transferred into a flask, and chloroform (80 mL) and 2N hydrochloric acid (2 mL) were added and stirred for 2 hours while refluxing. After decomposition, methanol (80 mL) was poured in to precipitate the polymer substance. The polymer was dispersed in a mixture of ethyl acetate and acetone (150 mL, v / v = 1: 1), cooled to room temperature while refluxing for 1 hour, and filtered to separate the polystyrene homopolymer and the multiblock copolymer . The solvent was removed from the filtrate, and the polymeric material remained was dried in a vacuum oven (130) to obtain a polystyrene homopolymer (1.7 g). The solid material separated by filtration was dispersed again in a mixture of ethyl acetate and acetone (150 mL, v / v = 1: 1), stirred for 1 hour while refluxing, cooled to room temperature and filtered to obtain a polystyrene homopolymer (0.6 g, 2.3 g in total, 22% of converted PS). The filtered multi-block copolymer was dried in a vacuum oven (130) to obtain a multiblock copolymer (36.7 g).
The results of the GPC analysis of the polystyrene prepared in Example 3 are shown in FIG. a curve is the molecular weight distribution of the polyolefin sample taken after the first step and b curve is the molecular weight distribution of the multiblock copolymer obtained by performing both the first and second steps. Also, TEM images of the multi-block copolymers finally prepared above are shown in FIG.
FIG. 1 shows the molecular weight distribution curve obtained by GPC analysis of the polyolefin sample obtained after the first step and the multi-block copolymer prepared through both the first step and the second step in Example 3 of the present invention. It can be confirmed that the molecular weight increased in all the molecular weight regions after the second stage anionic polymerization.
FIG. 2 shows a TEM image of the multi-block copolymer prepared in Example 3. FIG. The TEM image can be stained with RuO 4 to reveal the polystyrene domain as black. It can be confirmed that a multi-block copolymer is formed because the polystyrene domains are uniformly distributed.
Examples 4 and 5
Polymerization was carried out in the same manner as in Example 2, except that the amount of PhCH 2 -Li (TMEDA) was reduced to 350 μmol and 250 μmol in the second step, and the multi-block copolymer and PS-homopolymer I separated it.
Comparative Example 1
The first step and the second step polymerization were carried out in the same manner as in Example 3, except that (benzyl) 2 Zn (200 μmol) was used instead of the compound represented by the formula (3) as the organic zinc compound, Block copolymers and PS-homopolymers were separated.
The results of the preparation of the multiblock copolymers of Examples 3 to 5 and Comparative Example 1 are summarized in Tables 1 and 2 below.
(g (%))
(PDI) (kDa)
(PDI) (kDa)
(PDI) (kDa)
In Table 2, in Examples 3 to 5, the weight average molecular weight of the polymer obtained after performing the second-stage anionic polymerization in succession to the weight average molecular weight (PO-Mw) of the polyolefin sample taken after the first step, Mw) was increased to confirm that a desired multi-block copolymer was formed. In particular, the molecular weight increment (? Mw, 32 kDa, 43 kDa, 67 kDa) of Examples 3 to 5 was about twice or more as large as the molecular weight increment (? Mw, 18 kDa) of Comparative Example 1, block is formed. Also, as the amount of anionic initiator (Z-Li) was smaller, the pentablock chain having an n value of 2 was more likely to be formed than the triblock chain having an n value of 1 in the formula (1). In Examples 3 to 5, a multi-block having at least two styrene blocks, which is a feature of the present invention, was produced and the PS-homopolymer molecular weights (12 kDa, 14 kDa, 43 kDa, 67 kDa) , 14 kDa), respectively.
(Styrene feed amount (g) / PS-Mn) of the anion polymerization reaction point calculated in terms of the molecular weight of the extracted PS-homopolymer was 846, 753, 759 and 759 μmol in Examples 3 to 5 and Comparative Example 1, It can be seen that the polystyrene chain was efficiently grown not only on the alkyllithium but also on the zinc-carbon point of the organozinc compound in accordance with the expected value (number of Li moles added + number of Zn x 2 = 800 μmol, 750 μmol, 650 μmol, and 800 μmol) .
([Al]) of the PS-homopolymer extracted from the whole PS (PS after the reaction with the organoaluminum among the added Z-Li) accounted for 22, 28 and 28% Most of the remaining Z-Li compounds reacted with the organoaluminum introduced from the molar ratio of [(Li) + 2 x [Zn]) = 25, 27, 31% It can be seen that the reaction has been completed. On the other hand, in the case of Comparative Example 1, there was no alpha-methylstyrene group, and PS-homopolymer was generated from all the Z-Li added, and the fraction of PS-homopolymer extracted from the entire PS was very high. 3 to 5 had a remarkable effect as compared with Comparative Example 1.
Comparative Example 2: Synthesis of alpha-methylstyrene and CH 3 C 6 H 4 CH 2 Reaction with Li (TMEDA)
A sealable NMR cells in the dry box CH 3 C 6 H 4 CH 2 Li · (TMEDA) , insert a (9.17 mg, 40.0 · mol) and deutrated-cyclohexane (0.3 mL) and then dipped in a water bath (90) alpha-methylstyrene Styrene (4.73 mg, 40.0 μmol) was added. The reaction was carried out for 1 hour in a constant temperature bath (90), and 1 H NMR spectrum was obtained. The results are shown in FIG. 3 (a). In the same way, the amount of alpha-methylstyrene was as it was and the amount of CH3C6H4CH2Li (TMEDA) (8.26 mg, 36.0 μmol), 7.34 mg (32.0 μmol), 6.42 mg (28.0 μmol), 5.50 mg (24.0 μmol); 3, b, c, d] was reduced and 1 H NMR spectrum was obtained and analyzed.
Further, the reaction result obtained on the basis of the 1 H NMR analysis obtained through the 1 H NMR spectrum in FIG. 3 is shown in the following reaction formula (3). It was confirmed that two compounds of the formulas (7a) and (7b) in which alpha-methylstyrene was inserted into CH 3 C 6 H 4 CH 2 Li (TMEDA) in one or two places were produced and no more than three insertions proceeded. The product was reacted with alpha-methylstyrene and CH 3 C 6 H 4 CH 2 Li (TMEDA) at a molar ratio of 1: 0.6 for 1.0 hour, and the reaction was terminated with water. The product was purified by silica gel chromatography It was confirmed that only two compounds of formulas 8a and 8b were produced.
[Reaction Scheme 3]
FIG. 3 is a graph showing the relationship between the ratio of alpha-methylstyrene and CH 3 C 6 H 4 CH 2 Li (TMEDA) of Comparative Example 2 at 1: 1 (a), 1: 0.9 (b) : 0.7 (d), 1: 0.6 (e) shows a 1 H NMR spectrum of the product was the reaction molar ratio. '*', '#', '^', A signal labeled as "&" are each formula 7a, alpha of formula 7b, and unreacted methyl styrene, CH 3 C 6 H 4 CH 2 Li · (TMEDA) .
It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (6)
(3)
In the general formula (3), R 11 to R 16 are each independently hydrogen or an alkyl group having 1 to 20 carbon atoms.
(A)
In the formula (A), R 11 to R 16 are each independently hydrogen or an alkyl group having 1 to 20 carbon atoms; X is a halogen atom; Mg is magnesium;
[Chemical Formula B]
ZnX 2
In the above formula (B), X is a halogen atom; Zn is zinc;
(3)
In the general formula (3), R 11 to R 16 are each independently hydrogen or an alkyl group having 1 to 20 carbon atoms.
A product solution is prepared by adding an aliphatic hydrocarbon solvent having 4 to 20 carbon atoms to the product prepared by the reaction,
Further comprising crystallizing and separating the organic zinc compound of Formula 3 from the product solution.
Wherein the aliphatic hydrocarbon solvent comprises at least one of isobutane, hexane, cyclohexane, and methylcyclohexane.
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