CN105860407B - A kind of olefin polymer and its preparation method and application - Google Patents
A kind of olefin polymer and its preparation method and application Download PDFInfo
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- CN105860407B CN105860407B CN201510026493.0A CN201510026493A CN105860407B CN 105860407 B CN105860407 B CN 105860407B CN 201510026493 A CN201510026493 A CN 201510026493A CN 105860407 B CN105860407 B CN 105860407B
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- China
- Prior art keywords
- olefin polymer
- conjugated diene
- weight
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- monovinylarene
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- 229920000098 polyolefin Polymers 0.000 title claims abstract description 85
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 150000001993 dienes Chemical class 0.000 claims abstract description 52
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000009826 distribution Methods 0.000 claims abstract description 20
- 229920001577 copolymer Polymers 0.000 claims abstract description 19
- 229920001519 homopolymer Polymers 0.000 claims abstract description 9
- 239000000178 monomer Substances 0.000 claims description 47
- 238000000034 method Methods 0.000 claims description 38
- 238000006243 chemical reaction Methods 0.000 claims description 35
- 238000010276 construction Methods 0.000 claims description 30
- 238000005859 coupling reaction Methods 0.000 claims description 30
- 239000007822 coupling agent Substances 0.000 claims description 23
- 239000003999 initiator Substances 0.000 claims description 23
- 229920000642 polymer Polymers 0.000 claims description 22
- -1 vinyl arenes Chemical class 0.000 claims description 21
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 claims description 17
- 239000005049 silicon tetrachloride Substances 0.000 claims description 17
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 16
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 16
- 229910052744 lithium Inorganic materials 0.000 claims description 16
- 230000008878 coupling Effects 0.000 claims description 14
- 238000010168 coupling process Methods 0.000 claims description 14
- 229920002554 vinyl polymer Polymers 0.000 claims description 14
- 229910003978 SiClx Inorganic materials 0.000 claims description 13
- 241001120493 Arene Species 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- 239000007795 chemical reaction product Substances 0.000 claims description 10
- QNRMTGGDHLBXQZ-UHFFFAOYSA-N buta-1,2-diene Chemical compound CC=C=C QNRMTGGDHLBXQZ-UHFFFAOYSA-N 0.000 claims description 9
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 9
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 230000001174 ascending effect Effects 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 230000014759 maintenance of location Effects 0.000 claims description 6
- QPBYLOWPSRZOFX-UHFFFAOYSA-J tin(iv) iodide Chemical compound I[Sn](I)(I)I QPBYLOWPSRZOFX-UHFFFAOYSA-J 0.000 claims description 6
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 5
- 239000003112 inhibitor Substances 0.000 claims description 5
- VUFKMYLDDDNUJS-UHFFFAOYSA-N 2-(ethoxymethyl)oxolane Chemical compound CCOCC1CCCO1 VUFKMYLDDDNUJS-UHFFFAOYSA-N 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 235000014121 butter Nutrition 0.000 claims description 4
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 claims description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 229910021623 Tin(IV) bromide Inorganic materials 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 229940077388 benzenesulfonate Drugs 0.000 claims description 2
- DIKBFYAXUHHXCS-UHFFFAOYSA-N bromoform Chemical compound BrC(Br)Br DIKBFYAXUHHXCS-UHFFFAOYSA-N 0.000 claims description 2
- 150000004820 halides Chemical class 0.000 claims description 2
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 claims description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- HVOCMPMAOLOKRK-UHFFFAOYSA-N potassium;pentan-1-olate Chemical group [K+].CCCCC[O-] HVOCMPMAOLOKRK-UHFFFAOYSA-N 0.000 claims description 2
- AIFMYMZGQVTROK-UHFFFAOYSA-N silicon tetrabromide Chemical compound Br[Si](Br)(Br)Br AIFMYMZGQVTROK-UHFFFAOYSA-N 0.000 claims description 2
- JHGCXUUFRJCMON-UHFFFAOYSA-J silicon(4+);tetraiodide Chemical compound [Si+4].[I-].[I-].[I-].[I-] JHGCXUUFRJCMON-UHFFFAOYSA-J 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- LTSUHJWLSNQKIP-UHFFFAOYSA-J tin(iv) bromide Chemical compound Br[Sn](Br)(Br)Br LTSUHJWLSNQKIP-UHFFFAOYSA-J 0.000 claims description 2
- YUOWTJMRMWQJDA-UHFFFAOYSA-J tin(iv) fluoride Chemical compound [F-].[F-].[F-].[F-].[Sn+4] YUOWTJMRMWQJDA-UHFFFAOYSA-J 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims 1
- 125000001033 ether group Chemical group 0.000 claims 1
- 150000002240 furans Chemical class 0.000 claims 1
- 229910052700 potassium Inorganic materials 0.000 claims 1
- 239000011591 potassium Substances 0.000 claims 1
- MLSXQSHQPJCECC-UHFFFAOYSA-K trifluoro(methyl)stannane Chemical compound [F-].[F-].[F-].[Sn+3]C MLSXQSHQPJCECC-UHFFFAOYSA-K 0.000 claims 1
- 229920005989 resin Polymers 0.000 abstract description 32
- 239000011347 resin Substances 0.000 abstract description 32
- 238000006116 polymerization reaction Methods 0.000 description 34
- 229920001971 elastomer Polymers 0.000 description 27
- 239000005060 rubber Substances 0.000 description 27
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 18
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 14
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 13
- 238000012360 testing method Methods 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 241000894007 species Species 0.000 description 8
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 7
- 239000003963 antioxidant agent Substances 0.000 description 7
- 239000003292 glue Substances 0.000 description 7
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 7
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 7
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 6
- 150000001336 alkenes Chemical class 0.000 description 6
- 230000003078 antioxidant effect Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229920002857 polybutadiene Polymers 0.000 description 6
- 229920005990 polystyrene resin Polymers 0.000 description 6
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- GAODDBNJCKQQDY-UHFFFAOYSA-N 2-methyl-4,6-bis(octylsulfanylmethyl)phenol Chemical compound CCCCCCCCSCC1=CC(C)=C(O)C(CSCCCCCCCC)=C1 GAODDBNJCKQQDY-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000005062 Polybutadiene Substances 0.000 description 4
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 4
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical compound CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 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
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000004513 sizing Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 239000005064 Low cis polybutadiene Substances 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
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- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- KUFFULVDNCHOFZ-UHFFFAOYSA-N 2,4-xylenol Chemical class CC1=CC=C(O)C(C)=C1 KUFFULVDNCHOFZ-UHFFFAOYSA-N 0.000 description 1
- VBCKYDVWOPZOBA-UHFFFAOYSA-N 2-(oxolan-2-ylmethoxymethyl)oxolane Chemical compound C1CCOC1COCC1CCCO1 VBCKYDVWOPZOBA-UHFFFAOYSA-N 0.000 description 1
- IKEHOXWJQXIQAG-UHFFFAOYSA-N 2-tert-butyl-4-methylphenol Chemical class CC1=CC=C(O)C(C(C)(C)C)=C1 IKEHOXWJQXIQAG-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
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 102100022299 All trans-polyprenyl-diphosphate synthase PDSS1 Human genes 0.000 description 1
- KIKDPIYHXZFGGH-UHFFFAOYSA-N B(F)(F)F.[Sn] Chemical compound B(F)(F)F.[Sn] KIKDPIYHXZFGGH-UHFFFAOYSA-N 0.000 description 1
- 101150115672 DPS1 gene Proteins 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- HSRJKNPTNIJEKV-UHFFFAOYSA-N Guaifenesin Chemical compound COC1=CC=CC=C1OCC(O)CO HSRJKNPTNIJEKV-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 101150063720 PDSS1 gene Proteins 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- CLBRCZAHAHECKY-UHFFFAOYSA-N [Co].[Pt] Chemical compound [Co].[Pt] CLBRCZAHAHECKY-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
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- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
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- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- WJTCGQSWYFHTAC-UHFFFAOYSA-N cyclooctane Chemical compound C1CCCCCCC1 WJTCGQSWYFHTAC-UHFFFAOYSA-N 0.000 description 1
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- DIOQZVSQGTUSAI-NJFSPNSNSA-N decane Chemical compound CCCCCCCCC[14CH3] DIOQZVSQGTUSAI-NJFSPNSNSA-N 0.000 description 1
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- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 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 1
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- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 1
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- 239000003607 modifier Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
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- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002900 organolithium compounds Chemical class 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000036314 physical performance Effects 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
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- XTVMZZBLCLWBPM-UHFFFAOYSA-N tert-butylcyclohexane Chemical compound CC(C)(C)C1CCCCC1 XTVMZZBLCLWBPM-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
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Abstract
The invention discloses a kind of olefin polymer and its preparation method and application.The olefin polymer contains star-like conjugated diolefin homopolymerization thing, linear conjugated diene homopolymers and linear conjugated diene monovinylarene copolymer, the molecular weight distribution of the olefin polymer is tri-modal distribution, Mooney viscosity ML of the olefin polymer at 100 DEG C1+4For 50 70, and viscosity of the styrene solution for the olefin polymer that concentration is 5 weight % at 25 DEG C is 0.02 0.04Pas.The olefin polymer that the present invention obtains can assign the high impact strength of resin and high glossiness at the same time.
Description
Technical field
The present invention relates to a kind of olefin polymer, a kind of preparation method of olefin polymer, it is prepared by this method
Olefin polymer and the olefin polymer change as polystyrene resin and/or acrylonitrile-butadiene-styrene resin
The application of property agent.
Background technology
It is existing to improve the impact resistance of polystyrene (PS) resin and acrylonitrile-butadiene-styrene (ABS) (ABS) resin
Technology usually introduces modification rubber thereto.In general larger rubber size can make resin strong with higher impact
Degree, but the glossiness of resin can be reduced, although less rubber size ensure that the high gloss of resin, but easily embedment stress is split
In seam, resin impact resistance is caused to decline.Therefore, it is necessary to by rubber size control, in certain size, reaching to improve
The glossiness of resin, and the purpose of the impact resistance of resin can be kept.In general, control rubber particle size can pass through control
The mode of the SV values (viscosity of the styrene solution of the modified rubber containing 5 weight % at 25 DEG C) of resin modified rubber processed is real
It is existing.
In addition, introducing the equal poly structure of monovinylarene in modified rubber strand, it can not only improve modified rubber and exist
Intermiscibility in resin, while the index of refraction of modified rubber can be also improved, make the index of refraction of modified rubber and the folding of resin matrix
Light rate is close, and then eliminates the light scattering inside resin, and the glossiness of resin is improved, while the transparency of resin also obtains
To raising.
In order to improve the impact resistance of acrylonitrile-butadiene-styrene (ABS) (ABS) resin, and holding surface glossiness is basic
Constant, US4524180 discloses a kind of monovinylarene composition, wherein be dispersed with dience rubber (polybutadiene) and
Butadiene and mono vinyl arenes monomer and/or the mixture of ethylenic unsaturated nitrile copolymer.US4587294 discloses one kind
The preparation method of the rubber with impact energy is continuously prepared, this method includes aromatic hydrocarbon monomer, acrylonitrile monemer and gathers
The mixture of butadiene is introduced into first reactor with initiator, and carries out polymerisation under high shear stirring, so that rubber
Component inversion of phases is discrete particles, and then the first reaction product is introduced into second reactor and more reactors into traveling
Single step reaction.
US4639494 discloses a kind of preparation method of the resin with impact energy, and this method includes existing styrene
Raolical polymerizable is carried out in the presence of butadiene rubber, the butadiene rubber is by 1,3-butadiene homopolymerization or logical
Cross 1,3-butadiene and styrene copolymerized obtained highly-branched polymers, then by obtained polymer further with it is multifunctional
Halogen contained compound reaction is spent, wherein branched structure content is more than or equal to 60%, and 1,2 structure accounts for the 18-32 of polybutadiene segments
Weight %, the content of styrene block is 8-10 weight %, and Mooney viscosity of rubber 40-90, SV value are 0.06-0.09Pas.
Although this rubber, which is used for modified resin, has high impact strength, the SV values of rubber are still higher, can so cause to be modified
The decline of resinous luster degree.
US4421895 disclose in the preparation of ABS using SV values be equal to or less than 0.08Pas line style styrene-
Butadiene block dience rubber, obtains the rubber grain being dispersed in matrix with less than 0.7 μ m in size, and therefore obtains
Must have high performance attractive in appearance, the ABS of high glaze.However, the physical mechanical feature of ABS resin is but compromised, particularly impact resistance
Property.
In the prior art, Star-shaped Low-cis-Polybutadiene rubber and line style butylbenzene block rubber are more molten using lithium series anionic
Liquid polymerization technique synthesizes, obtained polymerization glue must through agglomeration process remove solvent therein, after through two-shipper is dry, vulcanization bed
Forced air drying, briquetting, be packaged into finished product.In view of the performance of above-described aftertreatment technology and rubber product, it polymerize glue
Mooney viscosity (ML1+4, 100 DEG C) be production control leading indicator, if product Mooney viscosity is excessive, sizing material easy powder during cohesion
Change, cause before two-shipper that leak adhesive is serious at glue grain sieves, while two-shipper material feeding is difficult, product is not easy by compound stalk forming；If production
Product Mooney viscosity is too low, then agglomerate when sizing material between bad dispersibility, easily assemble it is blocking, on the one hand be easy to cause condensing field, discharging
On the other hand pump and discharging pump, be easy to cause sizing material in two-shipper and embrace roller, not only influence drying to the blocking of process pipelines between two-shipper
Effect, is also also easy to produce plasticizing glue, causes product gel content higher, influences resin property.
In the prior art, when preparing resin modified rubber of the SV values between 0.02-0.40Pas, for design
Molecular weight is 50,000-60,000, for the Star-shaped Low-cis-Polybutadiene rubber of coupling efficiency 70-80%, its Mooney viscosity
Generally between 30-40, Mooney viscosity is relatively low, and cohesion and post processing are difficult.And be 10,000-15 for design molecular weight,
000th, for line style butylbenzene block rubber of the styrene-content for 20-40 weight % or so, its Mooney viscosity is typically in the range of 110-
Between 150, under the Mooney viscosity, rubber dusting is serious during cohesion, and post processing is difficult.
In conclusion it is badly in need of developing a kind of impact strength that can either ensure modified resin and resinous luster can be improved
That spends is polymer-modified.
The content of the invention
The purpose of the invention is to overcome using existing modification rubber to polystyrene resin and/or acrylonitrile-
When butadiene styrene resin is modified processing, single variety modified rubber cannot meet resin impact strength and tree at the same time
The defects of fat glossiness requirement, and a kind of new alkene that can assign the high impact strength of resin and high glossiness at the same time is provided
Hydrocarbon polymer, the preparation method of the olefin polymer, the olefin polymer that is prepared by this method and the alkene gather
Application of the compound as polystyrene resin and/or the modifying agent of acrylonitrile-butadiene-styrene resin.
A kind of present invention offer olefin polymer, wherein, the olefin polymer contains star-like conjugated diolefin homopolymerization
Thing, linear conjugated diene homopolymers and linear conjugated diene-monovinylarene copolymer, the molecule of the olefin polymer
Amount is distributed as tri-modal distribution, Mooney viscosity ML of the olefin polymer at 100 DEG C1+4For 50-70, and concentration is 5 weight %
Viscosity of the styrene solution at 25 DEG C of the olefin polymer be 0.02-0.04Pas.
Present invention also offers a kind of preparation method of olefin polymer, this method includes：
(1) in an inert atmosphere, by single functionality organic lithium initiator and conjugated diene monomer in atent solvent
The first polymerisation of middle progress；
(2) when the conversion ratio >=97% of the conjugated diene monomer, by the first polymeric reaction product and polyfunctionality
Coupling agent carries out coupling reaction；Total coupling group and the single functionality organic lithium initiator in the polyfunctionality coupling agent
Molar ratio be 0.40-0.55：1；
(3) in the presence of terminator, the product that step (2) obtains is carried out second with mono vinyl arenes monomer and is polymerize instead
Should so that the conversion ratio of the mono vinyl arenes monomer is >=97%；The terminator draws with the single functionality organolithium
The molar ratio for sending out agent is 0.1-0.15：1.
Present invention also offers the olefin polymer being prepared by the above method.
In addition, present invention also offers the olefin polymer as polystyrene resin and/or acrylonitrile-butadiene-
The application of the modifying agent of styrene resin.
The present inventor has found after further investigation, in nonpolar solvent, is had using stable single functionality
Machine lithium initiator triggers conjugate diene monomer polymerization, after polyfunctionality coupling agent moiety, adds terminator and single ethene
Base aromatic monomer is further polymerize, you can prepares while has star-like conjugated diene homopolymers, linear conjugated alkadienes
The olefin polymer of homopolymer and linear conjugated alkadienes-monovinylarene copolymer, the molecular weight point of the olefin polymer
Cloth is tri-modal distribution, which has suitable Mooney viscosity (the Mooney viscosity ML at 100 DEG C1+4For 50-70) and suitable
SV values (0.02-0.04Pas), and when the olefin polymer is modified resin, ensureing the mechanical property of resin
Under the premise of, the glossiness of resin can be effectively improved.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
Olefin polymer provided by the invention contain star-like conjugated diolefin homopolymerization thing, linear conjugated diene homopolymers and
Linear conjugated diene-monovinylarene copolymer, the molecular weight distribution of the olefin polymer are tri-modal distribution, the alkene
Mooney viscosity ML of the polymer at 100 DEG C1+4For 50-70, and the styrene for the olefin polymer that concentration is 5 weight %
Viscosity of the solution at 25 DEG C is 0.02-0.04Pas.
The present invention is to star-like conjugated diolefin homopolymerization thing, linear conjugated diene homopolymers and line in the olefin polymer
The content of type conjugated diene-monovinylarene copolymer is not particularly limited, for example, the gross weight with the olefin polymer
On the basis of amount, the content of the star-like conjugated diolefin homopolymerization thing can be 40-55 weight %, and the linear conjugated alkadienes is equal
The content of polymers can be 10-15 weight %, and the content of the linear conjugated diene-monovinylarene copolymer can be
35-45 weight %.
According to the present invention, in order to preferably improve the light of resin when enabling the olefin polymer as modifier
Damp degree, it is preferable that on the basis of the gross weight of the olefin polymer, the linear conjugated diene-monovinylarene copolymerization
The content of monovinylarene homopolymerization section is 20-40 weight % in thing, more preferably 25-35 weight %.In the present invention, it is described
Monovinylarene homopolymerization section refers to continuously contain six on the linear conjugated diene-monovinylarene copolymer strand
And more than six monovinylarene construction units.In addition, single second in the linear conjugated diene-monovinylarene copolymer
The content of the micro- block of alkenyl arene is theoretically more low better, but from the ready availability angle of raw material, it is preferable that with described
On the basis of the gross weight of olefin polymer, monovinylarene is micro- in the linear conjugated diene-monovinylarene copolymer
The content of block is 0-3 weight %, more preferably 0-2 weight %.In the present invention, the micro- block of the monovinylarene refers to
Continuously contain five and less than five monovinylarenes on the linear conjugated diene-monovinylarene copolymer strand
Construction unit.
According to the present invention, in the olefin polymer, conjugated diene construction unit can be in the form of 1,2- structures
In the presence of can also exist in the form of Isosorbide-5-Nitrae-structure (including cis-Isosorbide-5-Nitrae-structure and anti-form-1,4- structures).The present invention is to institute
1,2- construction units in conjugated diene construction unit, cis -1,4- construction units and anti-form-1,4- construction units is stated to contain
Amount is not particularly limited, for example, on the basis of the content of conjugated diene construction unit in the olefin polymer, it is described
The content of 1,2- construction units can be 5-15 weight % in conjugated diene construction unit, the content of cis-Isosorbide-5-Nitrae-construction unit
Can be 25-40 weight %, anti-form-1, the content of 4- construction units can be 45-65 weight %；Preferably, with the alkene
In polymer on the basis of the content of conjugated diene construction unit, 1,2- construction units contains in the conjugated diene construction unit
Amount can be 8-12 weight %, and the content of cis-Isosorbide-5-Nitrae-construction unit can be 30-35 weight %, anti-form-1,4- construction units
Content can be 55-60 weight %.
According to the present invention, the conjugated diene construction unit is the construction unit derived from conjugated diene, i.e., by altogether
The construction unit that yoke diene polymerization is formed.The conjugated diene refers to contain conjugated double bond (that is ,-C=C- in molecular structure
C=C- various unsaturated acyclic hydrocarbons).The species of the conjugated diene can be the conventional selection of this area, without especially
Limit, for example, the conjugated diene can be selected from C4-C12Straight or branched conjugated diene, is preferably C4-C8Straight or branched
One kind in conjugated diene, more preferably butadiene, isoprene and pentadiene.
According to the present invention, the monovinylarene construction unit is the construction unit derived from monovinylarene, i.e.,
It polymerize the construction unit formed by monovinylarene.The species of the monovinylarene can be the conventional choosing of this area
Select, be not particularly limited, for example, the monovinylarene can be selected from C8-C20Monovinylarene, is preferably C8-C12
One kind in monovinylarene, more preferably styrene, p-methylstyrene and α-methylstyrene.
The present invention does not limit the molecular size range and peak area size at three peaks of the olefin polymer especially
It is fixed, for example, the peak molecular weight (Mp) at three peaks is ascending according to retention time in weight of otefi pi polymer distribution
Can be respectively 150,000-190,000,100,000-150,000 He, the peak area percentage at 50,000-60,000, three peaks
More ascending than according to retention time can be respectively 40-55%, 35-45% and 10-15%；Preferably, the olefinic polymerization
In thing molecular weight distribution the peak molecular weight at three peaks according to retention time it is ascending be respectively 125,000-155,000,
115,000-145,000 and 45,000-55,000, the peak area percent at three peaks is ascending according to retention time to be respectively
42-53%, 36-40% and 11-14%.In addition, the molecular weight distribution at three peaks refers in the weight of otefi pi polymer distribution
Number is both preferably 1.05-1.2.
The preparation method of olefin polymer provided by the invention comprises the following steps：
(1) in an inert atmosphere, by single functionality organic lithium initiator and conjugated diene monomer in atent solvent
The first polymerisation of middle progress；
(2) when the conversion ratio >=97% of the conjugated diene monomer, by the first polymeric reaction product and polyfunctionality
Coupling agent carries out coupling reaction；Total coupling group and the single functionality organic lithium initiator in the polyfunctionality coupling agent
Molar ratio be 0.40-0.55：1；
(3) in the presence of terminator, the product that step (2) obtains is carried out second with mono vinyl arenes monomer and is polymerize instead
Should so that the conversion ratio of the mono vinyl arenes monomer is >=97%；The terminator draws with the single functionality organolithium
The molar ratio for sending out agent is 0.1-0.15：1.
The preparation method of the above-described olefin polymer of the present invention is the method for batchwise polymerization, and the batchwise polymerization refers to
Carry out above-mentioned first polymerisation, coupling reaction and the second polymerisation successively in same polymerization reaction kettle.According to this hair
A kind of bright embodiment, the preparation method of the olefin polymer can include：By solvent, conjugated diene monomer,
Initiator and other reaction promoters are added in polymerization reaction kettle, and after reacting a period of time, coupling agent is added into polymerization reaction kettle,
After certain residence time, terminator and single vinylaromatic monomer are added into polymerization reaction kettle, through certain residence time
After discharge.
According to the present invention, the species of the inert gas can be the conventional selection of this area, for example, the inert gas
It can include but is not limited at least one of nitrogen, argon gas and helium.
The species of the atent solvent can be the conventional selection of this area, for example, can be with 5-12 carbon atom
Hydro carbons and their cyclic analogs, be preferably propane, butane, pentane, hexane, heptane, octane, decane, pentamethylene, first
Cyclopentane, hexamethylene, cycloheptane, raffinate oil, at least one of n-hexane and cyclooctane, more preferably raffinate oil, just oneself
At least one of alkane and hexamethylene.
According to the present invention, the single functionality organic lithium initiator can be to be usually used in triggering list in anionic polymerisation field
The single functionality organo-lithium compound of body polymerization, it is preferable that the single functionality organic lithium initiator can be as shown in formula (I)
Compound：
RLi (I)
Wherein, R be straight or branched alkyl, cycloalkyl or aryl, be preferably ethyl, propyl group, isopropyl, normal-butyl,
Sec-butyl, amyl group, hexyl, cyclohexyl, phenyl, aminomethyl phenyl or naphthyl, more preferably normal-butyl or sec-butyl.
There is no particular limitation for dosage of the present invention to the single functionality organic lithium initiator, can obtain as needed
The molecular size range of the first polymerization reaction monomer make choice.Usually, when need acquisition molecular weight larger first polymerize
During reaction monomers, then it can reduce the dosage of single functionality organic lithium initiator；And working as needs to obtain molecular weight less first
During polymerization reaction monomer, then it can increase the dosage of single functionality organic lithium initiator.Usually, relative to the conjugation of 100g
Diolefinic monomer, the dosage of the single functionality organic lithium initiator can be 1.66-2.00mmol.
According to the present invention, the polyfunctionality coupling agent can be selected from polyfunctionality coupling agent commonly used in the art,
As long as so that contain star-like conjugated diolefin homopolymerization thing in olefin polymer.For example, the polyfunctionality coupling agent can be with
It is preferably methyl trifluoro SiClx, methyl trichlorosilicane, methyl tribromo SiClx, methyl triiodo SiClx, first for polyfunctionality halide
The borontrifluoride tin of base, tin methyltrichloride, methyl tribromide tin, methyl triiodide tin, butyl trifluoro SiClx, butyl trichlorosilicane,
Butyl tribromo SiClx, butyl triiodo SiClx, ocratation, silicon tetrachloride, silicon bromide, silicon tetraiodide, tin tetrafluoride, four chlorinations
At least one of tin, tin tetrabromide, tin tetraiodide, butter of tin, butter of tin, more preferably silicon tetrachloride and/or tetrachloro
Change tin, be most preferably silicon tetrachloride.
According to the present invention, in order to control only the first polymeric reaction product of part to carry out coupling reaction, and the of remainder
One polymeric reaction product still is able to carry out follow-up termination reaction or the second polymerisation, so that in the olefin polymer made
Contain star-like conjugated diolefin homopolymerization thing, linear conjugated diene homopolymers and linear conjugated diene-monovinylarene at the same time
Copolymer, the molar ratio of total coupling group in the polyfunctionality coupling agent and the single functionality organic lithium initiator can be with
For 0.40-0.55：1, it is preferably 0.45-0.54：1.In the present invention, total coupling group in the polyfunctionality coupling agent is
Refer to the total content of coupling group in polyfunctionality coupling agent.
According to the present invention, the species of the terminator can be selected from terminator commonly used in the art, for example, can be
Water and/or alcohols, are preferably at least one of water, methanol, ethanol, isopropanol, more preferably water.In addition, in order to enable institute
State the polymer part not being coupled in coupling reaction product and carry out termination reaction, and another part carries out the second polymerization instead
Should, the molar ratio of the terminator and the single functionality organic lithium initiator can be 0.1-0.15：1, it is preferably 0.11-
0.14：1.
The present invention is not particularly limited the dosage of the conjugated diene monomer and mono vinyl arenes monomer, example
Such as, relative to the conjugated diene monomer of 100 parts by weight, the dosage of the mono vinyl arenes monomer is 20-40 parts by weight, more
Preferably 25-35 parts by weight.In addition, the species of the conjugated diene monomer and mono vinyl arenes monomer is hereinbefore
It is described, then this is not repeated.
According to the present invention, this method, which is additionally included in step 1), adds structure regulator and/or gel inhibitor.The knot
The species of structure conditioning agent can be the conventional selection of this area, for example, nitrogenous, oxygen-containing, sulfur-bearing, phosphorous polarity can be selected from
At least one of compound, is preferably ether, butyl oxide, dioxane, tetrahydrofuran, glycol dimethyl ether, two dry alcohol diformazans
Ether, diphenyl ether, triethylamine, tetramethylethylenediamine, hexamethylphosphoramide, potassium tert-butoxide, sodium alkyl benzene sulfonate and ethyl tetrahydrochysene
At least one of furfuryl group ether, more preferably tetrahydrofuran and/or ethyl tetrahydrofurfuryl ether.Further, when using tetrahydrochysene furan
When muttering as structure regulator, the dosage of the tetrahydrofuran can be the 80-150ppm of polymerization system concentration；When using ethyl
When tetrahydrofurfuryl ether is as structure regulator, the ethyl tetrahydrofurfuryl ether can be the 3-9ppm of polymerization system concentration.
The species of the gel inhibitor can be the conventional selection of this area, for example, 1,2- butadiene, uncle can be selected from
Amoxy potassium (KTA)/silicon tetrachloride (SiCl4), tetramethylethylenediamine (TMEDA)/1,2- butadiene and THF/1,2- butadiene
At least one of.In addition, the dosage of the gel inhibitor can be the 60-150ppm of polymerization system concentration, it is preferably 80-
120ppm。
The present invention is not particularly limited the condition of first polymerisation, as long as enabling to the conjugated diene
Hydrocarbon monomer is polymerize and the conversion ratio of monomer is reached >=97%, for example, the condition of first polymerisation includes：
Polymerization temperature can be 40-130 DEG C, be preferably 70-110 DEG C；Polymerization pressure can be 0.1-1.5MPa, be preferably 0.2-
0.5MPa；Polymerization time can be 10-70 minutes, be preferably 30-60 minutes.
The present invention is also not particularly limited the condition of coupling reaction described in step (2), as long as enabling to part
With the coupling agent coupling reaction occurs for first polymeric reaction product, for example, the condition of the coupling reaction includes：
It can be 40-130 DEG C to be coupled temperature, be preferably 70-110 DEG C；It can be 0.1-1.5MPa to be coupled pressure, be preferably 0.2-
0.5MPa；；Coupling time can be 20-70 minutes, be preferably 30-60 minutes.
The present invention is also not particularly limited the condition of second polymerisation, as long as enabling to step (2) to obtain
To coupling reaction product in a part in non-coupling polymer reacted with terminator, and another part continues and single ethene
Base aromatic monomer carries out polymerisation and mono vinyl arenes monomer conversion ratio is reached >=97%, for example, described second
The condition of polymerisation includes：Polymerization temperature can be 40-130 DEG C, be preferably 70-110 DEG C；Polymerization pressure can be 0.1-
1.5MPa, is preferably 0.2-0.5MPa；Polymerization time can be 20-70 minutes, be preferably 30-60 minutes.
In the present invention, the pressure refers both to gauge pressure.
In addition, in order to improve the ageing-resistant performance of the olefin polymer, usually after the second polymerisation is completed, also
Need to contact second polymeric reaction product with antioxidant.The antioxidant can be that existing various can prevent rubber
The material of aging, for example, can be phenol antiager and/or amines antioxidants, can specifically be selected from 2,6- di-t-butyls to first
Phenol (abbreviation Irganox 264), tert-butyl catechol, 2,2 '-methylene-bis- (4- methyl-6-tert-butylphenols) are (referred to as
Irganox 2246) and one kind in (the n-octylthiomethylene) -6- of 2,4- bis- methylphenols (abbreviation Irganox 1520) or
It is a variety of.On the basis of the total monomer weight added in whole polymerization process, the dosage typically 0.1-2 weights of the antioxidant
Measure %.
After polymerisation is completed, it is necessary to by the solvent removal in the olefin polymer finally obtained.Remove solvent
Method is known to the skilled person, for example, can pass through alcoholization precipitation, centrifugation, filtering, decantation, vapor cohesion
Etc. mode by olefin polymer the Precipitation from solvent, can also use stripping mode the volatility in olefin polymer is molten
Agent is separated off.This those skilled in the art can be known, will not be described in great detail herein.
Present invention also offers the olefin polymer being prepared by the above method.
In addition, present invention also offers the diene polymer as polystyrene resin and/or acrylic nitrile-butadiene two
The application of the modifying agent of alkene-styrene resin.
The present invention will be described in detail by way of examples below.
In following embodiments and comparative example：
1st, conjugated diene monomer, the conversion ratio of mono vinyl arenes monomer use Shimadzu GC- in polymerization process
14A flame gas chromatographs measure, and internal standard method calculates, and specific calculating process is as follows：
St%=1- [(s/h)/(S/H)] × 100
Bd%=1- [(b/h)/(B/H)] × 100
Wherein, s is the peak area of styrene in the polymeric kettle outlet sample that GC is measured；
B is the peak area of butadiene in the polymeric kettle outlet sample that GC is measured；
H is the sum of peak area of solvent in the polymeric kettle outlet sample that GC is measured；
The unit inlet amount of styrene monomer, units/kg/h when S is polymerization；
The unit inlet amount of divinylic monomer, units/kg/h when B is polymerization；
H be into paradigmatic system solvent unit inlet amount, units/kg/h.
2nd, the SV values of polymer refer to the styrene solution for the olefin polymer that concentration is 5 weight % at 25 DEG C
Viscosity, it uses Cannon-Fenske type viscosimeters to be tested.
3rd, using Japan's Shimudzu ML testers, (preheating 1 minute, 4 are rotated at 100 DEG C to the Mooney viscosity of polymer
Minute, value) tested.
4th, the measure of gel content (Gel%)：Polymer samples are dry to constant weight in 50 DEG C in vacuum drying chamber, claim
Weight, is denoted as W1, then dissolving dried copolymer with styrene, (dosage of styrene make it that the concentration of polymer is 5 weights
Measure %), in 135 DEG C of vibrations fully dissolving, then using 300 mesh stainless (steel) wire filtered polymeric solution, by stainless (steel) wire not
The polymer of dissolving when 100 DEG C of dryings 4 are small, weigh in vacuum drying chamber, is denoted as W2, calculate gel content value, gel
Content value calculation formula is as follows：Gel content value (weight %)=(W2/W1) × 100 (weight %).
5th, concentration is the measure of the styrene solution colourity of the olefin polymer of 5 weight %：Using GB/T
9282.1-2008 standards, using platinum-cobalt titer as reference colour, with optical colorimetry measured concentration.
6th, 1,2- structures (vinyl structure), cis -1,4- structures, anti-form-1,4- structures contain in polymer monomer unit
Amount is tested using Switzerland Bruker AVANCE-400 types nuclear magnetic resonance chemical analyser, room temperature measure, liquid pool method, solvent CS2.
7th, polymer molecular weight and molecular weight distribution are carried out using Japanese Shimadzu LC-10A series gel permeation chromatographs GPC
Test.
Embodiment 1
The embodiment is used to illustrate olefin polymer provided by the invention and preparation method thereof.
Reaction unit used in the embodiment includes a polymerization reaction kettle.Under high pure nitrogen protective atmosphere, successively to 5
Rise and raffinate oil 2730g, 1,3-butadiene 559g, 1,2- butadiene 0.395g, tetrahydrofuran 0.329g are added in polymeric kettle, open
Stirring, adds n-butyl lithium initiator 0.716g at a temperature of 50 DEG C, carries out the first polymerisation, reaction pressure 0.1-
0.3MPa, reaction mass start to warm up, and 90 DEG C of maximum temperature is reached when reacting 8 minutes, measures divinylic monomer conversion ratio
Up to 97%；Silicon tetrachloride is added into polymerization reaction kettle again, and (total coupling group of silicon tetrachloride and the molar ratio of n-BuLi are
0.55:1) coupling agent 0.261g, and temperature control is controlled into coupling reaction 30 minutes at 0.2 mpa in 70 DEG C, pressure；Coupling
After reaction, adding water containing 0.020g, (molar ratio of terminator water and n-BuLi is 0.1:1) styrene 373g, and will
Temperature control carries out the second polymerisation at 0.2 mpa in 70 DEG C, pressure control, and polyase 13 measures styrene monomer after 0 minute
Conversion ratio is up to 97%；Then add terminator isopropanol 0.235g and terminate reaction, and add the antioxidant of monomer weight 0.2%
Irganox1520, then carries out devaporation desolventizing processing to glue, obtains olefin polymer J1, olefin polymer J1
Molecular weight distribution be tri-modal distribution, its make a concrete analysis of test result it is as shown in table 1.
Embodiment 2
The embodiment is used to illustrate olefin polymer provided by the invention and preparation method thereof.
Reaction unit used in the embodiment includes a polymerization reaction kettle.Under high pure nitrogen protective atmosphere, successively to 5
Rise and hexamethylene 2730g, 1,3-butadiene 444g, 1,2- butadiene 0.381g, tetrahydrofuran 0.317g are added in polymeric kettle, in 53
N-butyl lithium initiator 0.517g is added at a temperature of DEG C and carries out the first polymerisation, reaction pressure 0.1-0.3MPa, reactant
Material starts to warm up, and 85 DEG C of maximum temperature is reached when reacting 10 minutes, measures divinylic monomer conversion ratio up to 97%；Again to poly-
Close and silicon tetrachloride is added in kettle (total coupling group of silicon tetrachloride and the molar ratio of n-BuLi are 0.45:1) coupling agent
0.154g, and by temperature control 80 DEG C, pressure control coupling reaction 40 minutes under 0.3MPa；After coupling reaction, add
Entering water containing 0.019g, (molar ratio of terminator water and n-BuLi is 0.13:1) styrene 190g, and by temperature control 80
DEG C, pressure control carry out the second polymerisation under 0.3MPa, polymerization measures styrene monomer conversion rate up to 97% after forty minutes；
Then add terminator isopropanol 0.204g and terminate reaction, and add the antioxidant Irganox 1520 of monomer weight 0.2%, so
Devaporation desolventizing processing is carried out to glue afterwards, obtains olefin polymer J2, the molecular weight distribution of olefin polymer J2 is
Tri-modal distribution, it is as shown in table 1 that it makes a concrete analysis of test result.
Embodiment 3
The embodiment is used to illustrate olefin polymer provided by the invention and preparation method thereof.
Reaction unit used in the embodiment includes a polymerization reaction kettle.It is poly- to 5 liters successively under high pure nitrogen protection
Close and hexamethylene/n-hexane mixed solvent (weight ratio 82/18) 2730g, 1,3- butadiene 337g, 1,2- butadiene is added in kettle
0.368g, ethyl tetrahydrofurfuryl ether 0.028g, at a temperature of 55 DEG C, add n-BuLi 0.360g and carry out the first polymerisation,
Reaction pressure is 0.1-0.3MPa；Reaction mass starts to warm up, and 80 DEG C of maximum temperature, high temperature 10 are reached when reacting 12 minutes
Minute after measure monomer conversion up to 100%, then into polymeric kettle add silicon tetrachloride (total coupling group of silicon tetrachloride with just
The molar ratio of butyl lithium is 0.50:1) coupling agent 0.119g, and temperature control is controlled under 0.25MPa occasionally in 75 DEG C, pressure
Connection reaction 35 minutes；After coupling reaction, (the molar ratio of terminator isopropanol and n-BuLi of isopropanol containing 0.051g is added
For 0.15:1) styrene 84g, and temperature control is subjected to the second polymerisation in 75 DEG C, pressure control under 0.25MPa,
Polyase 13 measures styrene monomer conversion rate up to 97% after five minutes；Then add terminator isopropanol 0.118g and terminate reaction, and
The antioxidant Irganox 1520 of monomer weight 0.2% is added, devaporation desolventizing processing then is carried out to glue, obtains alkene
The molecular weight distribution of hydrocarbon polymer J3, olefin polymer J3 are tri-modal distribution, and it is as shown in table 1 that it makes a concrete analysis of test result.
Comparative example 1
The comparative example is used to illustrate olefin polymer of reference and preparation method thereof.
Method according to embodiment 1 prepares the olefin polymer of reference, the difference is that four chlorinations in the coupling reaction
(total coupling group of silicon tetrachloride and the molar ratio of n-BuLi are 0.80 to silicon:1) dosage of coupling agent is 0.380g, and in idol
Connection is added without the styrene containing water and carries out the second polymerisation after reaction, but is directly added into isopropanol and terminate instead
Should, reference olefin polymer DJ1 is obtained, it is as shown in table 1 that it analyzes test result.
Comparative example 2
The comparative example is used to illustrate olefin polymer of reference and preparation method thereof.
Method according to embodiment 1 prepares the olefin polymer of reference, the difference is that being added in the first polymerisation
0.511g butyl lithiums, are added without polyfunctional group coupling agent silicon tetrachloride, and the benzene second for not containing water is added in the second polymerisation
Alkene 372g, obtains reference olefin polymer DJ2, and it is as shown in table 1 that it analyzes test result.
Table 1
Test case
Test case is used for the test for illustrating olefinic polymerization physical performance.
In 2 liters of stainless steel cauldrons with stirring, impact-resistant polystyrene resin is prepared using mass suspension method.Tool
Body, 1232 grams of styrene are firstly added, then be separately added into the olefin polymer J1-J3 and reference olefin polymer of 70g
DJ1-DJ2, is subsequently added into 70 grams of ethylbenzene, and the bulk-suspension polymerization of radical initiator initiation is carried out after 28 grams of white oils.Trigger anti-
It is 110 DEG C to answer temperature, and initiator uses 1,1- diperoxies t-butylcyclohexane (DP-275B), initiator amount 450ppm,
Speed of agitator is 350 revs/min.Modified polystyrene PS1-PS3 and DPS1-DPS2 are respectively obtained, it is anti-to it in accordance with the following methods
Impact strength and glossiness are tested：
(1) impact strength：Surveyed using U.S. CE AST companies RESIL IMPACTOR instrument and according to ASTM D256 standards
Examination, wherein, test temperature is 25 DEG C.Acquired results are as shown in table 2.
(2) surface gloss (45 °)：Using Switzerland's ZLR1050 vancometers and according to ASTM D1003 standard testings, its
In, the numerical value of glossiness is the higher the better.Acquired results are as shown in table 2.
Table 2
| Modified polystyrene | Olefin polymer | Impact strength (kJ/m2) | Glossiness |
| PS1 | J1 | 74 | 76 |
| PS2 | J2 | 74 | 74 |
| PS3 | J3 | 73 | 73 |
| DPS1 | DJ1 | 70 | 65 |
| DPS2 | DJ2 | 70 | 69 |
The olefin polymer obtained it can be seen from the data of above-described embodiment and comparative example using the method for the present invention is had
Suitable Mooney viscosity (the Mooney viscosity ML at 100 DEG C1+4For 50-70), it is easy to follow-up processing, and there is suitable SV values
(0.02-0.04Pas), olefin polymer using the present invention are modified resin, are ensureing the mechanical property of resin
Under the premise of, the glossiness of resin can be effectively improved.
The preferred embodiment of the present invention described in detail above, still, during present invention is not limited to the embodiments described above
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (23)
1. a kind of preparation method of olefin polymer, wherein, this method includes：
(1) in an inert atmosphere, by single functionality organic lithium initiator and conjugated diene monomer in atent solvent into
The first polymerisation of row；
(2) when the conversion ratio >=97% of the conjugated diene monomer, the first polymeric reaction product and polyfunctionality are coupled
Agent carries out coupling reaction；Total coupling group in the polyfunctionality coupling agent is rubbed with the single functionality organic lithium initiator
Your ratio is 0.40-0.55：1；
(3) in the presence of terminator, product and mono vinyl arenes monomer that step (2) is obtained carry out the second polymerisation,
So that the conversion ratio of the mono vinyl arenes monomer is >=97%；The terminator and the single functionality organic lithium initiator
Molar ratio be 0.1-0.15：1.
2. according to the method described in claim 1, wherein, the polyfunctionality coupling agent is polyfunctionality halide.
3. according to the method described in claim 2, wherein, the polyfunctionality coupling agent is methyl trifluoro SiClx, methyl trichlorine
SiClx, methyl tribromo SiClx, methyl triiodo SiClx, methyl trifluoro tin, tin methyltrichloride, methyl tribromide tin, methyl three
Stannic iodide, butyl trifluoro SiClx, butyl trichlorosilicane, butyl tribromo SiClx, butyl triiodo SiClx, ocratation, silicon tetrachloride,
At least one of silicon bromide, silicon tetraiodide, tin tetrafluoride, butter of tin, tin tetrabromide, tin tetraiodide.
4. according to the method described in claim 3, wherein, the polyfunctionality coupling agent is silicon tetrachloride and/or butter of tin.
5. according to the method described in claim 4, wherein, the polyfunctionality coupling agent is silicon tetrachloride.
6. method according to claim 1 or 5, wherein, relative to the conjugated diene monomer of 100 parts by weight, the list
The dosage of vinyl aromatic monomer is 20-40 parts by weight.
7. according to the method described in claim 6, wherein, relative to the conjugated diene monomer of 100 parts by weight, the list ethene
The dosage of base aromatic monomer is 25-35 parts by weight.
8. method according to claim 1 or 5, wherein, this method further includes middle addition structure regulator in step (1)
And/or gel inhibitor.
9. according to the method described in claim 8, wherein, the structure regulator is selected from nitrogenous, oxygen-containing, sulfur-bearing, phosphorous pole
At least one of property compound.
10. according to the method described in claim 9, wherein, the structure regulator is ether, butyl oxide, dioxane, tetrahydrochysene
Furans, glycol dimethyl ether, diethylene glycol dimethyl ether, diphenyl ether, triethylamine, tetramethylethylenediamine, hexamethylphosphoramide, tertiary fourth
At least one of potassium alcoholate, sodium alkyl benzene sulfonate and ethyl tetrahydrofurfuryl ether.
11. according to the method described in claim 10, wherein, the structure regulator is tetrahydrofuran and/or ethyl tetrahydrochysene chaff
Base ether.
12. according to the method described in claim 8, wherein, the gel inhibitor be selected from 1,2- butadiene, tertiary amoxy potassium/
Silicon tetrachloride, tetramethylethylenediamine/at least one of 1,2- butadiene and THF/1,2- butadiene.
13. method according to claim 1 or 5, wherein, the condition of first polymerisation includes：Temperature is 40-
130 DEG C, pressure 0.1-1.5MPa, the time is 10-70 minutes.
14. according to the method for claim 13, wherein, the condition of the coupling reaction includes：Temperature is 40-130 DEG C, pressure
Power is 0.1-1.5MPa, and the time is 20-70 minutes.
15. according to the method for claim 13, wherein, the condition of second polymerisation includes：Temperature is 40-130
DEG C, pressure 0.1-1.5MPa, the time is 20-70 minutes.
16. the olefin polymer being prepared as the method described in any one in claim 1-15.
17. olefin polymer according to claim 16, wherein, it is equal that the olefin polymer contains star-like conjugated diene
Polymers, linear conjugated diene homopolymers and linear conjugated diene-monovinylarene copolymer, point of the olefin polymer
Son amount is distributed as tri-modal distribution, Mooney viscosity ML of the olefin polymer at 100 DEG C1+4For 50-70, and concentration is 5 weights
It is 0.02-0.04Pas to measure viscosity of the styrene solution of the olefin polymer of % at 25 DEG C.
18. olefin polymer according to claim 17, wherein, on the basis of the gross weight of the olefin polymer, institute
The content for stating star-like conjugated diolefin homopolymerization thing is 40-55 weight %, and the content of the linear conjugated diene homopolymers is 10-
15 weight %, the content of the linear conjugated diene-monovinylarene copolymer is 35-45 weight %.
19. the olefin polymer according to claim 17 or 18, wherein, using the gross weight of the olefin polymer as base
Standard, the content of monovinylarene homopolymerization section is 20-40 weights in the linear conjugated diene-monovinylarene copolymer
% is measured, the monovinylarene homopolymerization section refers to connect on the linear conjugated diene-monovinylarene copolymer strand
The continuous content containing six and more than six monovinylarene construction units.
20. olefin polymer according to claim 19, wherein, on the basis of the gross weight of the olefin polymer, institute
The content for stating the micro- block of monovinylarene in linear conjugated diene-monovinylarene copolymer is 0-3 weight %, the list
The micro- block of vinyl-arene refers to continuously contain five on the linear conjugated diene-monovinylarene copolymer strand
And the content of less than five monovinylarene construction units.
21. the olefin polymer according to claim 17 or 18, wherein, with conjugated diene knot in the olefin polymer
On the basis of the content of structure unit, the content of 1,2- construction units is 5-15 weight % in the conjugated diene construction unit.
22. olefin polymer according to claim 21, wherein, with conjugated diene hydrocarbon structure list in the olefin polymer
On the basis of the content of member, the content of cis in the conjugated diene construction unit-Isosorbide-5-Nitrae-construction unit is 25-40 weight %, instead
The content of formula -1,4- construction units is 45-65 weight %.
23. olefin polymer according to claim 17, wherein, three peaks in the weight of otefi pi polymer distribution
It is respectively 150,000-190,000,100,000-150,000 and 50,000- that peak molecular weight is ascending according to retention time
60,000, the peak area percent at three peaks according to retention time it is ascending be respectively 40%-55%, 35%-45% and
10%-15%；The molecular weight distributing index at three peaks is 1.05-1.2 in the weight of otefi pi polymer distribution.
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