CN114539478A - Preparation method of comb-shaped polyolefin thermoplastic elastomer based on feeding strategy regulation and control - Google Patents
Preparation method of comb-shaped polyolefin thermoplastic elastomer based on feeding strategy regulation and control Download PDFInfo
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- CN114539478A CN114539478A CN202210005417.1A CN202210005417A CN114539478A CN 114539478 A CN114539478 A CN 114539478A CN 202210005417 A CN202210005417 A CN 202210005417A CN 114539478 A CN114539478 A CN 114539478A
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- 229920002725 thermoplastic elastomer Polymers 0.000 title claims abstract description 50
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 230000033228 biological regulation Effects 0.000 title claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 148
- 239000005977 Ethylene Substances 0.000 claims abstract description 88
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 86
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 77
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 58
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 58
- -1 polyethylene Polymers 0.000 claims abstract description 52
- 239000004711 α-olefin Substances 0.000 claims abstract description 47
- 238000009826 distribution Methods 0.000 claims abstract description 30
- 239000003960 organic solvent Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000004743 Polypropylene Substances 0.000 claims abstract description 19
- 229920001155 polypropylene Polymers 0.000 claims abstract description 19
- 239000000203 mixture Substances 0.000 claims abstract description 18
- 239000004698 Polyethylene Substances 0.000 claims abstract description 12
- 229920000573 polyethylene Polymers 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 9
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 62
- 238000006116 polymerization reaction Methods 0.000 claims description 45
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 32
- LWNGJAHMBMVCJR-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenoxy)boronic acid Chemical compound OB(O)OC1=C(F)C(F)=C(F)C(F)=C1F LWNGJAHMBMVCJR-UHFFFAOYSA-N 0.000 claims description 18
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 18
- VPGLGRNSAYHXPY-UHFFFAOYSA-L zirconium(2+);dichloride Chemical compound Cl[Zr]Cl VPGLGRNSAYHXPY-UHFFFAOYSA-L 0.000 claims description 18
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 15
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 15
- 229910052726 zirconium Inorganic materials 0.000 claims description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 11
- 238000002844 melting Methods 0.000 claims description 11
- 230000008018 melting Effects 0.000 claims description 11
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 10
- 239000012968 metallocene catalyst Substances 0.000 claims description 10
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 8
- BHTKQUGPJWEUOJ-UHFFFAOYSA-N C[SiH](C)C[Ti](C)(NC(C(C)(C)C)(CC)C)C1C=CC=C1 Chemical compound C[SiH](C)C[Ti](C)(NC(C(C)(C)C)(CC)C)C1C=CC=C1 BHTKQUGPJWEUOJ-UHFFFAOYSA-N 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 239000012005 post-metallocene catalyst Substances 0.000 claims description 6
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 claims description 4
- GXDHCNNESPLIKD-UHFFFAOYSA-N 2-methylhexane Natural products CCCCC(C)C GXDHCNNESPLIKD-UHFFFAOYSA-N 0.000 claims description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052735 hafnium Inorganic materials 0.000 claims description 4
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 claims description 4
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 claims description 4
- 238000011084 recovery Methods 0.000 claims description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 4
- VMZMXDNPNZSQOM-UHFFFAOYSA-N C[SiH](C)C[Ti](C)(NC(C)(C)C)C1C=C(C2=CC=CC=C12)C=1NC=CC1 Chemical compound C[SiH](C)C[Ti](C)(NC(C)(C)C)C1C=C(C2=CC=CC=C12)C=1NC=CC1 VMZMXDNPNZSQOM-UHFFFAOYSA-N 0.000 claims description 3
- JZZIHCLFHIXETF-UHFFFAOYSA-N dimethylsilicon Chemical compound C[Si]C JZZIHCLFHIXETF-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 claims description 3
- YNZVRGAKCHKLMI-UHFFFAOYSA-N C1(=CC=CC=C1)P(C=1C=CC=C2CCC(NC=12)[Zr](CC1=CC=CC=C1)(CC1=CC=CC=C1)CC1=CC=CC=C1)C1=CC=CC=C1 Chemical compound C1(=CC=CC=C1)P(C=1C=CC=C2CCC(NC=12)[Zr](CC1=CC=CC=C1)(CC1=CC=CC=C1)CC1=CC=CC=C1)C1=CC=CC=C1 YNZVRGAKCHKLMI-UHFFFAOYSA-N 0.000 claims description 2
- LMUAVDCECJHDHS-UHFFFAOYSA-L CC(C)(C)C(C=CC=C1C=C(CCC2)C2=[Zr+2]=C(CCC2)C2=CC2=CC=CC(C(C)(C)C)=C2O)=C1O.[Cl-].[Cl-] Chemical compound CC(C)(C)C(C=CC=C1C=C(CCC2)C2=[Zr+2]=C(CCC2)C2=CC2=CC=CC(C(C)(C)C)=C2O)=C1O.[Cl-].[Cl-] LMUAVDCECJHDHS-UHFFFAOYSA-L 0.000 claims description 2
- KGWXYUFIQHXOIL-UHFFFAOYSA-K CC(C)C1=CC=CC(C(C)C)=C1O[Ti](Cl)(Cl)C1(C)C(C)=C(C)C(C)=C1C Chemical compound CC(C)C1=CC=CC(C(C)C)=C1O[Ti](Cl)(Cl)C1(C)C(C)=C(C)C(C)=C1C KGWXYUFIQHXOIL-UHFFFAOYSA-K 0.000 claims description 2
- ZGKIJGFCSPUSAA-UHFFFAOYSA-L CC1(C(C)=C(C)C(C)=C1C)[Hf+2]C1C(C)=C(C)C(C)=C1C.[Cl-].[Cl-] Chemical compound CC1(C(C)=C(C)C(C)=C1C)[Hf+2]C1C(C)=C(C)C(C)=C1C.[Cl-].[Cl-] ZGKIJGFCSPUSAA-UHFFFAOYSA-L 0.000 claims description 2
- GDBLZKMJBVGZTR-UHFFFAOYSA-K Cl[Ti](OC1=C(C=CC=C1)C1=CC=CC=C1)(C1(C(=C(C(=C1C)C)C)C)C)Cl Chemical compound Cl[Ti](OC1=C(C=CC=C1)C1=CC=CC=C1)(C1(C(=C(C(=C1C)C)C)C)C)Cl GDBLZKMJBVGZTR-UHFFFAOYSA-K 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 claims description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 claims description 2
- LEGYQRMZHKKGMR-UHFFFAOYSA-N NC(C(F)=C(C(F)=C1F)F)=C1F.NC(C(F)=C(C(F)=C1F)F)=C1F.NC(C(F)=C(C(F)=C1F)F)=C1F.OB(O)O Chemical compound NC(C(F)=C(C(F)=C1F)F)=C1F.NC(C(F)=C(C(F)=C1F)F)=C1F.NC(C(F)=C(C(F)=C1F)F)=C1F.OB(O)O LEGYQRMZHKKGMR-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- YQRRFEPNTPQQHU-UHFFFAOYSA-L [Cl-].[Cl-].C(C=1C(O)=CC=CC1)=C1C(C=CC=C1)N=[Ti+2]=NC1C(C=CC=C1)=CC=1C(O)=CC=CC1 Chemical compound [Cl-].[Cl-].C(C=1C(O)=CC=CC1)=C1C(C=CC=C1)N=[Ti+2]=NC1C(C=CC=C1)=CC=1C(O)=CC=CC1 YQRRFEPNTPQQHU-UHFFFAOYSA-L 0.000 claims description 2
- FIIWCKZTOMVIDX-UHFFFAOYSA-L [Cl-].[Cl-].C12=CC=CC=C2C(CCC)=C(C)C1[Hf+2]([SiH](C)C)C1C2=CC=CC=C2C(CCC)=C1C Chemical compound [Cl-].[Cl-].C12=CC=CC=C2C(CCC)=C(C)C1[Hf+2]([SiH](C)C)C1C2=CC=CC=C2C(CCC)=C1C FIIWCKZTOMVIDX-UHFFFAOYSA-L 0.000 claims description 2
- SGJOMARGPMMNKC-UHFFFAOYSA-L [Cl-].[Cl-].C1=CC2=CC=CC=C2C1[Hf+2]([SiH](C)C)C1C2=CC=CC=C2C=C1 Chemical compound [Cl-].[Cl-].C1=CC2=CC=CC=C2C1[Hf+2]([SiH](C)C)C1C2=CC=CC=C2C=C1 SGJOMARGPMMNKC-UHFFFAOYSA-L 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 2
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 claims description 2
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 claims description 2
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 claims description 2
- IPZJQDSFZGZEOY-UHFFFAOYSA-N dimethylmethylene Chemical compound C[C]C IPZJQDSFZGZEOY-UHFFFAOYSA-N 0.000 claims description 2
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 2
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 claims description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 2
- ZMANZCXQSJIPKH-UHFFFAOYSA-O triethylammonium ion Chemical compound CC[NH+](CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-O 0.000 claims description 2
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 2
- OBAJXDYVZBHCGT-UHFFFAOYSA-N tris(pentafluorophenyl)borane Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1B(C=1C(=C(F)C(F)=C(F)C=1F)F)C1=C(F)C(F)=C(F)C(F)=C1F OBAJXDYVZBHCGT-UHFFFAOYSA-N 0.000 claims description 2
- OLFPYUPGPBITMH-UHFFFAOYSA-N tritylium Chemical compound C1=CC=CC=C1[C+](C=1C=CC=CC=1)C1=CC=CC=C1 OLFPYUPGPBITMH-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- QMBQEXOLIRBNPN-UHFFFAOYSA-L zirconocene dichloride Chemical compound [Cl-].[Cl-].[Zr+4].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 QMBQEXOLIRBNPN-UHFFFAOYSA-L 0.000 claims description 2
- AQZWEFBJYQSQEH-UHFFFAOYSA-N 2-methyloxaluminane Chemical compound C[Al]1CCCCO1 AQZWEFBJYQSQEH-UHFFFAOYSA-N 0.000 claims 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims 2
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims 1
- LMEUPNMVGMAVEF-UHFFFAOYSA-L CC(C=CC=C1C=[Ti+2]=NC(C(F)=C(C(F)=C2F)F)=C2F)=C1O.[Cl-].[Cl-] Chemical compound CC(C=CC=C1C=[Ti+2]=NC(C(F)=C(C(F)=C2F)F)=C2F)=C1O.[Cl-].[Cl-] LMEUPNMVGMAVEF-UHFFFAOYSA-L 0.000 claims 1
- XLCYGAPESVMMLC-UHFFFAOYSA-L CC1=CC(C(=CC=C2)C=3C=CC=CC=3)=C2C1[Hf](Cl)(Cl)([SiH](C)C)C1C(C)=CC2=C1C=CC=C2C1=CC=CC=C1 Chemical compound CC1=CC(C(=CC=C2)C=3C=CC=CC=3)=C2C1[Hf](Cl)(Cl)([SiH](C)C)C1C(C)=CC2=C1C=CC=C2C1=CC=CC=C1 XLCYGAPESVMMLC-UHFFFAOYSA-L 0.000 claims 1
- XLMHRUKPJFDOAS-UHFFFAOYSA-N CCC(C)(C(C)(C)C)N[Ti](C)(C[SiH](C)C)C1C=CC=C1.Cl.Cl Chemical compound CCC(C)(C(C)(C)C)N[Ti](C)(C[SiH](C)C)C1C=CC=C1.Cl.Cl XLMHRUKPJFDOAS-UHFFFAOYSA-N 0.000 claims 1
- 239000010941 cobalt Substances 0.000 claims 1
- 229910017052 cobalt Inorganic materials 0.000 claims 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims 1
- 150000001924 cycloalkanes Chemical class 0.000 claims 1
- 229910052742 iron Inorganic materials 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 34
- 239000002904 solvent Substances 0.000 abstract description 28
- 229920001577 copolymer Polymers 0.000 abstract description 27
- 239000000178 monomer Substances 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 22
- 238000006243 chemical reaction Methods 0.000 description 18
- 238000002474 experimental method Methods 0.000 description 16
- 229920000642 polymer Polymers 0.000 description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 230000014759 maintenance of location Effects 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 229920001971 elastomer Polymers 0.000 description 8
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 8
- 238000003860 storage Methods 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
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- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
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- 244000043261 Hevea brasiliensis Species 0.000 description 1
- WMLXMUJSZPURRZ-UHFFFAOYSA-L [Cl-].[Cl-].C(C)(C)(C)C1=C(C(C=C2C(CCC2)N=[Zr+2]=NC2C(CCC2)=CC=2C(O)=C(C=CC2)C(C)(C)C)=CC=C1)O Chemical compound [Cl-].[Cl-].C(C)(C)(C)C1=C(C(C=C2C(CCC2)N=[Zr+2]=NC2C(CCC2)=CC=2C(O)=C(C=CC2)C(C)(C)C)=CC=C1)O WMLXMUJSZPURRZ-UHFFFAOYSA-L 0.000 description 1
- FJMJPZLXUXRLLD-UHFFFAOYSA-L [Cl-].[Cl-].C1=CC2=CC=CC=C2C1[Zr+2]([SiH](C)C)C1C2=CC=CC=C2C=C1 Chemical compound [Cl-].[Cl-].C1=CC2=CC=CC=C2C1[Zr+2]([SiH](C)C)C1C2=CC=CC=C2C=C1 FJMJPZLXUXRLLD-UHFFFAOYSA-L 0.000 description 1
- UCIKZESDXASJNG-UHFFFAOYSA-L [Cl-].[Cl-].C1=CC=C2C([Zr+2])C=CC2=C1 Chemical compound [Cl-].[Cl-].C1=CC=C2C([Zr+2])C=CC2=C1 UCIKZESDXASJNG-UHFFFAOYSA-L 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- IVTQDRJBWSBJQM-UHFFFAOYSA-L dichlorozirconium;indene Chemical compound C1=CC2=CC=CC=C2C1[Zr](Cl)(Cl)C1C2=CC=CC=C2C=C1 IVTQDRJBWSBJQM-UHFFFAOYSA-L 0.000 description 1
- 238000009510 drug design Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229920005636 ethylene/1-octene copolymer elastomer Polymers 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- WHJXGGISJBFSJJ-UHFFFAOYSA-N iron;pyridine Chemical compound [Fe].C1=CC=NC=C1 WHJXGGISJBFSJJ-UHFFFAOYSA-N 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920006124 polyolefin elastomer Polymers 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 238000007613 slurry method Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000004154 testing of material Methods 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 238000009757 thermoplastic moulding Methods 0.000 description 1
- ZWYDDDAMNQQZHD-UHFFFAOYSA-L titanium(ii) chloride Chemical compound [Cl-].[Cl-].[Ti+2] ZWYDDDAMNQQZHD-UHFFFAOYSA-L 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention discloses a preparation method of comb-shaped polyolefin thermoplastic elastomer based on feeding strategy regulation, which comprises the steps of mixing an organic solvent, ethylene (or propylene), an ethylene homopolymerization catalyst (or a propylene homopolymerization catalyst) and a cocatalyst, and polymerizing to obtain a polyethylene macromonomer (or a polypropylene macromonomer); mixing alpha-olefin, a copolymerization catalyst and the prepared polyethylene macromonomer to synthesize a comb-shaped polyolefin thermoplastic elastomer; the method of the invention takes the designed molecular weight and distribution of the polyolefin thermoplastic elastomer, and the composition and distribution of the copolymer as the targets, and controls the feeding strategies of the feeding amounts of the materials such as monomers, catalysts, cocatalysts, solvents and the like at different feeding positions or feeding time, thereby realizing the customization of the molecular weight and distribution of the comb-shaped polyolefin thermoplastic elastomer, the composition and distribution of the copolymer and improving the mechanical property of the thermoplastic elastomer.
Description
Technical Field
The invention belongs to the technical field of preparation of thermoplastic elastomers, and particularly relates to a preparation method of a comb-shaped polyolefin thermoplastic elastomer, which relates to chain structure design of the thermoplastic elastomer and customization of the chain structure of the thermoplastic elastomer by a regulation and control feeding strategy.
Background
The traditional rubber needs to be subjected to vulcanization crosslinking in order to obtain better mechanical properties, and the chemical crosslinking makes the rubber difficult to recycle, thereby causing serious environmental pollution. Thermoplastic elastomers (TPEs) have emerged in the last 40 s and are distinguished from vulcanized rubbers by physical crosslinking. TPE has rubber elasticity at normal temperature, can be subjected to thermoplastic molding at high temperature, and becomes a 'third generation rubber' following natural rubber and synthetic rubber. Among them, the polyolefin type thermoplastic elastomer, which accounts for about 30% of the total yield of TPE, has the advantages of good chemical resistance, good weather resistance, light weight, continuous production and the like, and is widely used in the fields of automobiles, electronics, electrics, daily necessities and the like.
High alpha-olefin insertion ethylene/alpha-olefin copolymer-polyolefin elastomer (POE) is an industrial product with high added value. It was first prepared by the Dow company of America by the INSITE process using a constrained geometry metallocene catalyst (CGC) (EP 0416815) under the trade name ENGAGETMThe product has the advantages of narrow molecular weight distribution, uniform comonomer distribution, excellent processability and the like. Subsequently Exxonmobil (ExxonMobil) also independently developed ethylene/1-butene, ethylene/1-hexene, ethylene/1-octene copolymer elastomers POE under the trade name Exact using a bridged metallocene catalystTM. Also, POE products were introduced in Mitusui, LG and SK, Lyondelbasell, the Netherlands, and the Mitusui. In addition, DOW company invented a chain shuttling polymerization technology in 2005 and successfully industrialized a brand-new polyolefin thermoplastic elastomer-Olefin Block Copolymer (OBC) with the product trademark InfuseTM(Science 2006, 312, 714-719). The main chain of the product has a multi-block structure with hard segments and soft segments alternating, not only can keep a melting point similar to LLDPE, but also has the elasticity of POE, and can keep better elasticity at higher temperature, and the heat resistance is far greater than that of a POE elastomer. Based on the fact that DOW developed a propylene-based block copolymer in 2013, the trade name was INTUNETM. The commodity can be polyethylene andthe excellent compatilizer among the polypropylene is applied to the recovery of polyethylene and polypropylene materials.
Compared with polyethylene, the polypropylene has a more complex structure, and the metallocene catalysts with different structures can be used for producing the polypropylene with three different structures of isotactic, syndiotactic and high melting point, and the three polypropylenes have different product properties, such as the isotactic polypropylene melting point can reach 165 ℃ and is higher than the HDPE melting point, so that the polypropylene can be applied at a higher temperature, and the application range of the material is widened; the high melting point polypropylene exhibits a completely amorphous structure and is elastic. By inserting a certain amount of 1-octene segments in isotactic polypropylene, the polymer will gradually change from thermoplastic to thermoplastic elastomer. When the mole fraction of 1-octene insertions reaches 20%, the material exhibits the properties typical of elastomers. (Journal of Polymer Science: Part B: Polymer Physics,2004,42,4357-
Therefore, crystallizable polyethylene or polypropylene hard segments are concentrated on the side chains of the copolymer, and ethylene/alpha-olefin random copolymer soft segments are used as the main chain of the copolymer, the hard segments of the side chains can form a crystallized plastic phase, and the main chain forms a rubber phase, so that the materials are subjected to phase separation, and finally, the polyolefin thermoplastic elastomer with a comb-shaped structure is synthesized.
Currently, there are three industrial methods for producing ethylene/α -olefin copolymers, namely, a solution method, a gas phase method and a slurry method (prog. polym. sci.2001, 26, 1287-1336.). However, in the production of POE with high alpha-olefin content, each company adopts a high-temperature solution process. The performance, including toughness and elasticity, of the POE products obtained by the solution method are obviously superior to those of products obtained by the gas phase method. Although there is a patent report (US5770664) for producing POE by a slurry process, since POE has a low melting point, it is easily swollen in a solvent, and the product is easily melted and agglomerated, there is no industrial example of producing POE by a slurry process. In addition, the chain structure can be better controlled in the polymerization process by using solution polymerization.
However, the properties of the polymer are determined by the chain structure, and the rational design of the chain structure can significantly improve the properties of the polymer. The dosage of raw materials and the time of homopolymerization and copolymerization, the molecular weight and distribution of the copolymer, the composition and distribution of the copolymer and the like are influenced, and the chain structure of the copolymer is influenced. Therefore, the molecular weight and distribution of the copolymer and the composition and distribution of the copolymer are accurately regulated and controlled by a feeding strategy of controlling the feeding amounts of materials such as monomers, catalysts, cocatalysts, solvents and the like at different feeding positions or feeding time, so that the performance of the copolymer is improved.
Disclosure of Invention
The invention aims to overcome the defects of the existing products and technologies, and provides a preparation method of a comb-shaped polyolefin thermoplastic elastomer based on regulation and control of a feeding strategy, which aims at designing the molecular weight and distribution of the polyolefin thermoplastic elastomer and the composition and distribution of a copolymer, controls the feeding strategy of the addition of materials such as a monomer, a catalyst, a cocatalyst, a solvent and the like at different feeding positions or feeding time, realizes the customization of the molecular weight and distribution of the comb-shaped polyolefin thermoplastic elastomer and the composition and distribution of the copolymer, and improves the mechanical property of the thermoplastic elastomer.
The purpose of the invention is realized by the following technical scheme: a preparation method of comb-shaped polyolefin thermoplastic elastomer based on feeding strategy regulation comprises the following steps:
(1) mixing an organic solvent, ethylene, an ethylene homopolymerization catalyst and a cocatalyst, and polymerizing under the polymerization pressure of 0.1-12 MPa and at the polymerization temperature of 50-180 ℃ for 5-60 min to synthesize a polyethylene macromonomer; based on the volume of the organic solvent, the concentration of the ethylene homopolymerization catalyst is 0.1-100 mu mol/L, and the molar ratio of the cocatalyst to the ethylene homopolymerization catalyst is 10-50000: 1, the feeding concentration of ethylene is 0.1-20 mol/L, the weight average molecular weight of the prepared polyethylene macromonomer is 500-50000 g/mol, the molecular weight distribution index is 1.0-5.0, and the proportion of terminal double bonds is controlled to be more than 50%;
(2) mixing an organic solvent, alpha-olefin, a copolymerization catalyst and all the polyethylene macromonomers prepared in the step (1), polymerizing under the polymerization pressure of 0.1-12 MPa and the polymerization temperature of 50-180 ℃ for 5-120 min to synthesize the comb-shaped polyolefin thermoplastic elastomer; based on the volume of the organic solvent, the concentration of the copolymerization catalyst is 0.1-100 mu mol/L, the concentration of the ethylene homopolymerization catalyst is 0.1-50 mu mol/L, and the molar ratio of the total amount of the copolymerization catalyst to the total amount of the ethylene homopolymerization catalyst is 25: 1-1: 15, the molar ratio of the cocatalyst to the copolymerization catalyst is 10-50000: 1, the concentration of the alpha-olefin feed is 0.1-40 mol/L; the weight average molecular weight of the prepared comb-shaped polyolefin thermoplastic elastomer is 20000-500000 g/mol, the molecular weight distribution index is 1.0-10.0, and the mole content of alpha-olefin is 1-70%.
The invention provides a preparation method of a comb-shaped polyolefin thermoplastic elastomer based on feeding strategy regulation, which comprises the following steps:
(1) mixing an organic solvent, propylene, a propylene homopolymerization catalyst and a cocatalyst, and polymerizing under the polymerization pressure of 0.1-12 MPa and at the polymerization temperature of 50-180 ℃ for 5-60 min to synthesize a crystalline polypropylene macromonomer; based on the volume of the organic solvent, the concentration of the propylene homopolymerization catalyst is 0.1-100 mu mol/L, and the molar ratio of the cocatalyst to the propylene homopolymerization catalyst is 10-50000: 1, the feeding concentration of propylene is 0.1-20 mol/L, the weight average molecular weight of the prepared crystalline polypropylene macromonomer is 500-50000 g/mol, the molecular weight distribution index is 1.0-5.0, and the proportion of terminal double bonds is controlled to be more than 50%;
(2) mixing an organic solvent, alpha-olefin, a copolymerization catalyst and all the crystalline polypropylene macromonomers prepared in the step (1), polymerizing under the polymerization pressure of 0.1-12 MPa and the polymerization temperature of 50-180 ℃ for 25-120 min to synthesize the comb-shaped polyolefin thermoplastic elastomer; based on the volume of the organic solvent, the concentration of the copolymerization catalyst is 0.1-100 mu mol/L, the concentration of the propylene homopolymerization catalyst is 0.1-50 mu mol/L, and the molar ratio of the total amount of the copolymerization catalyst to the total amount of the propylene homopolymerization catalyst is 25: 1-1: 15, the molar ratio of the cocatalyst to the copolymerization catalyst is 10-50000: 1, the concentration of the alpha-olefin feed is 0.1-40 mol/L; the weight average molecular weight of the prepared comb-shaped polyolefin thermoplastic elastomer is 20000-500000 g/mol, the molecular weight distribution index is 1.0-10.0, and the mole content of alpha-olefin is 1-70%.
Further, in a tubular reactor or a batch stirred tank reactor; the feed inlet of the tubular reactor is positioned between the inlet and the outlet of the reactor and at different positions of the axial lateral line, and the number of the feed inlet is 1, 2, 3, 4 or more than 4.
Further, the ethylene homopolymerization catalyst is a single-active-center metallocene catalyst or a post-metallocene catalyst, and comprises zirconocene dichloride, dimethylcarbocangenyl-biscyclopentadienyl-zirconium dichloride, a 2, 6-diimidazine pyridine iron catalyst and a 2, 6-diiminopyridine cobalt catalyst, bis (4-methylphenyl) carbon bridged-cyclopentadienyl-indenyl-zirconium dichloride, bis (3-tert-butylsalicylidene-cyclopentylidene) zirconium dichloride, bis (5-methyl-3-tert-butylsalicylidene-cyclobutaneimino) zirconium dichloride, bis (3-tert-butylsalicylidene-cyclohexanimino) zirconium dichloride, dimethylsilyl-tetramethylcyclopentadienyl-tert-butylamino-dimethyltitanium or ethylenebridged bis-indenyl zirconium dichloride.
Further, the propylene homopolymerization catalyst for generating the high melting point polypropylene macromonomer is a single-site metallocene catalyst or a post-metallocene catalyst, and comprises rac-dimethylsilylbis (2-methyl-3-propylindenyl) hafnium dimethyl, rac-dimethylsilylbis (2-methyl-3-propylindenyl) hafnium dichloride, rac-dimethylsilylbis (2-methyl-4-phenylindenyl) zirconium dimethyl, rac-dimethylsilylbis indenyl hafnium dichloride, dimethylcarbobridged-cyclopentadienyl-fluorenyl-zirconium dimethyl, and, rac-dimethylsilicon bridged- (2-methyl-4-tert-butylpentyl) -dimethylaminobutylazium, ansa-ethylene bridged- (2-methyl-3-benzyl-5, 6-cyclopentoindenyl) -fluorenylzirconium dichloride, ansa-ethylene bridged- (2-methyl-3-benzyl-5, 6-cyclopentoindenyl) -fluorenyldimethylzirconium, ansa-ethylene bridged- (2-methyl-3-benzyl-5, 6-cyclopentoindenyl) -3, 6-di-tert-butylfluorenylzirconium dichloride, ansa-ethylene bridged- (2-methyl-3-benzyl-5, 6-cyclopentoindenyl) -3, 6-di-tert-butylfluorenylzirconium dimethyl, ansa-ethylene bridged- (2-methyl-3-benzyl-5, 6-cyclopentoindenyl) -fluorenylhafnium dichloride, ansa-ethylene bridged- (2-methyl-3-benzyl-5, 6-cyclopentoindenyl) -fluorenylhafnium dimethyl, rac-propenyl bridged bisindenyldimethylaminobenzylzirconium or hafnium, methyl-alkyl-hafnocene or zirconium, ethylene bridged-5, 6-cyclopentoindenyl-fluorenylzirconium dichloride, ethylene bridged-5, 6-cyclopentoindenyl-fluorenylzirconium dimethyl, ethylene bridged-5, 6-cyclopentoindenyl-2, 7-di-n-butylfluorenylzirconium dichloride, ethylene bridged-5, 6-cyclopentoindenyl-2, 7-di-n-butylfluorenylzirconium dimethyl, ethylene bridged- (3-benzyl-5, 6-cyclopentoindenyl) -2, 7-di-n-butylfluorenylzirconium dichloride, ethylene bridged- (3-benzyl-5, 6-cyclopentoindenyl) -2, 7-di-n-butylfluorenylzirconium dimethyl, ethylene bridged- (3-benzyl-5, 6-cyclopentoindenyl) -2, 7-di-tert-butylfluorenylhafnium dichloride, ethylene bridged- (3-benzyl-5, 6-cyclopentoindenyl) -2, 7-di-tert-butylfluorenylhafnium dimethyl, di-tetramethyl-substituted cyclopentadienyl-hafnium dichloride, di-tetramethyl-substituted cyclopentadienyl-hafnium dimethyl, zirconium dimethyl, and mixtures thereof, Tetramethylcyclopentadienyl-pentamethylcyclopentadienyl-hafnium dichloride, tetramethylcyclopentadienyl-pentamethylcyclopentadienyl-hafnium dimethyl, zirconocene dimethyl, diphenylcarbon-bridged-cyclopentadienyl-fluorenyl zirconium dichloride, diphenylcarbon-bridged-cyclopentadienyl-fluorenyl zirconium dimethyl or biscyclopentadienyl-methyl-neopentyl-zirconium.
Further, the copolymerization catalyst is a single-site metallocene catalyst or post-metallocene catalyst, including biscyclopentadienyl hafnium dimethyl, bisindenyl zirconium dimethyl, ethylenebridged bisindenyl zirconium dichloride, dimethylsilyl-bisindenyl, diphenylcarbabridged-cyclopentadienyl-fluorenyl zirconium dichloride, dimethylsilyl-tetramethylcyclopentadienyl-tert-butylamino-dimethyltitanium, bisindenyl zirconium dichloride, bis [2- (3', 5' -di-tert-butylphenyl) -indenyl ] zirconium dichloride, bis (2-methyl-4, 5-phenyl-indenyl) zirconium dichloride, biscyclopentadienyl-bisphenoxy zirconium, dimethylsilyl bisindenyl zirconium dichloride, diphenylcarbabridged-cyclopentadienyl-fluorenyl-zirconiumdichloride, diphenylcarbabridged-cyclopentadienyl-fluorenyl zirconium dichloride, and, Diphenylcarbaryl-cyclopentadienyl- (2-dimethylamino-fluorenyl) zirconium dichloride, dimethylsilyl-tetramethylcyclopentadienyl-tert-butylamino-dimethyltitanium, dimethylsilyl-3-pyrrolylindenyl-tert-butylamino-dimethyltitanium, pentamethylcyclopentadienyl- (2-phenylphenoxy) -titanium dichloride, pentamethylcyclopentadienyl- (2, 6-diisopropylphenoxy) -titanium dichloride, bis (3-methylsalicylidene-pentafluoroimido) titanium dichloride, bis (salicylidene-phenylimino) titanium dichloride, dimethylsilyl-3-pyrrolylindenyl-tert-butylamino-dimethyltitanium trichloride, [ N- (3, 5-di-tert-butylsalicylidene) -2-diphenylphosphinophenylimine ] titanium trichloride And (2, 3, 4-trihydro-8-diphenylphosphino-quinolinyl) tribenzylzirconium.
Further, the co-catalyst includes methylaluminoxane, modified methylaluminoxane, triisobutylaluminum, triethylaluminum, trimethylaluminum, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, triphenylcarbenium tetrakis (pentafluorophenyl) borate, tris (pentafluorophenyl) borane, 4-isopropyl-4' -methyldiphenyliodonium tetrakis (pentafluorophenyl) borate, tri (N-butyl) ammonium tetrakis (pentafluorophenyl) borate, N-diethylanilinium tetrakis (pentafluorophenyl) -borate, triethylammonium tetrakis (pentafluorophenyl) borate, dimethylanilinium tetrakis (pentafluorophenyl) borate, N-octacosyl-N-methyltetrakis (pentafluorophenyl) ammonium borate, tripropylamine tetrakis (pentafluorophenyl) borate, di (isopropyl) ammonium tetrakis (pentafluorophenyl) borate, tri (isopropyl) borate, tri (N, N-octadecyl-N-methyl-N-pentafluorophenyl) borate, tri (N-propyl) borate, tri (isopropyl) borate, N-propyl borate, N-N, One or more of triphenylphosphine tetrakis (pentafluorophenyl) borate may be mixed in any proportion.
Further, the organic solvent is straight-chain alkane, isoparaffin, cycloparaffin or arene with 4-10 carbon atoms; the alpha-olefin is a straight chain or branched chain alpha-olefin with 4-20 carbon atoms.
Further, the organic solvent is Isopar E, n-pentane, isopentane, n-hexane, cyclohexane, n-heptane, isoheptane, n-octane, isooctane, n-decane, toluene or xylene; the alpha-olefin is 1-butene, 1-pentene, 1-hexene, 1-octene or 1-decene.
Further, the elongation at break of the comb-shaped polyolefin thermoplastic elastomer is more than 100%, the breaking strength is more than 1Mpa, and the elastic recovery rate is more than 40%.
The invention has the beneficial effects that: based on the high-temperature and high-pressure cascade solution polymerization technology of a cascade metallocene catalyst system with high activity, high selectivity and high copolymerization capacity, the invention realizes the customization of the molecular weight and the distribution of the novel comb-shaped polyolefin thermoplastic elastomer and the composition and the distribution of the copolymer by taking the designed molecular weight and the distribution of the thermoplastic elastomer and the composition and the distribution of the copolymer as targets and regulating and controlling the feeding strategies of materials such as monomers, catalysts, cocatalysts, solvents and the like, improves the mechanical property of the polyolefin thermoplastic elastomer, realizes the high quality of polymer materials and has high industrial value.
Detailed Description
Exemplary embodiments will be described in detail herein. The embodiments described in the following exemplary embodiments do not represent all embodiments consistent with the present invention. Rather, they are merely examples of apparatus and methods consistent with certain aspects of the invention, as detailed in the appended claims.
The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used in this specification and the appended claims, the singular forms "a", "an", and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise. It should also be understood that the term "and/or" as used herein refers to and encompasses any and all possible combinations of one or more of the associated listed items.
The present invention will be described in detail with reference to specific examples. The features of the following examples and embodiments may be combined with each other without conflict.
Examples 1 to 6 and comparative examples 1 and 2 were carried out in a tubular reactor having an inner diameter of 12.7mm and a length of 20 m. The feed molarity to be used in the present invention means: initial concentration of ethylene into the reactor based on volume of organic solvent; the feed molar ratio refers to the initial molar concentration ratio of alpha-olefin to ethylene as it enters the reactor.
Example 1
In the experiment, bis (3-tert-butylsalicylidene-cyclopentylimino) zirconium dichloride is used as an ethylene homopolymerization catalyst, dimethyl-methyl-cyclopentadienyl-tert-butylamino-dimethyl titanium is used as a copolymerization catalyst, dried methylaluminoxane is used as a cocatalyst, Isopar E is used as a solvent, 1-octene is used as alpha-olefin, the polymerization experiment is carried out in a high-temperature and high-pressure continuous solution system, 1 side-line feed inlet is arranged at each 1m position of a tubular reactor, and the tubular reactor is respectively positioned to be a number consistent with the length according to the length meter from an inlet to the feed inlet, for example, a feed inlet 5m away from the inlet is determined as a fifth feed inlet. The reactor and piping were purged with a solution of triisobutylaluminum and Isopar E to remove water oxygen prior to polymerization. Transferring the ethylene homopolymerization catalyst, the copolymerization catalyst and the cocatalyst under the protection of nitrogen atmosphere, preparing solutions with Isopar E respectively, storing the solutions in respective storage tanks for later use, and storing the solvents Isopar E and alpha-olefin in a solvent storage tank.
The material feeding strategy of an inlet and a feeding port is designed by taking the aim of synthesizing a copolymer with the molecular weight of 300kD and the copolymerization composition of 17mol percent. Opening the oil bath, and raising the temperature from the inlet to the fifth feeding port of the tubular reactor to 100 ℃ and the temperature from the fifth feeding port to the outlet to 150 ℃; opening a feed valve and a discharge valve of the reactor, opening a high-pressure metering pump, continuously adding ethylene, an ethylene homopolymerization catalyst, a cocatalyst and a solvent into the tubular reactor from an inlet by the metering pump according to a set flow rate, and continuously feeding the ethylene, the copolymerization catalyst, the cocatalyst, 1-octene and the solvent into the reactor from a lateral line feed inlet of the tubular reactor. The pressure in the reactor is controlled by a proportional valve and is stabilized at 1 MPa. The feeding rate of the ethylene homopolymerization catalyst at an inlet is 2 mu mol/min, the feeding rate of the cocatalyst is 10mmol/min, and the molar ratio of the cocatalyst to the ethylene homopolymerization catalyst is 5000: 1, the feeding rate of ethylene is 1.30mol/min, and the retention time of the material from the inlet to the fifth feeding port is 32 min; at a fifth feed inlet, the feeding rate of the copolymerization catalyst is 20 mu mol/min, the feeding rate of the cocatalyst is 20mmol/min, the molar ratio of the cocatalyst to the copolymerization catalyst is 1000:1, the feeding rate of ethylene is 0.98mol/min, the feeding rate of 1-octene is 1.23mol/min, the feeding molar ratio of octene to ethylene is 1.26, and the retention time of the material from the fifth feed inlet to an outlet is 30 min; the continuously flowing-out material is washed several times by a large amount of acidified ethanol, filtered, drained and vacuum-dried at 60 ℃ for more than 8 hours.
Weight average molecular weight (Mw) of polymer and distribution index thereof
Measured by ASTM D6474-2012, high temperature gel permeation chromatography (PL-GPC220) with 1, 2, 4-trichlorobenzene as solvent at a flow rate of 1.0 ml/min; preparing 0.1-0.3 wt% polymer solution at 150 deg.C, calibrating at 150 deg.C with polystyrene with narrow molecular weight distribution as standard sample, and using parameter K of polystyrene standard sample as 1.21 × 10-4And alpha is 0.707, and the polyolefin thermoplastic elastomer K is 5.91X 10-4、α＝ 0.69。
Melting Point (T) of the copolymerm) Measured by TA Instruments Q200 according to GB/T19466.3-2004; taking 5.0-7.0 mg of polymer sample, heating to 190 ℃ at 30 ℃/min, keeping the temperature for 5min to eliminate thermal history, then cooling to-90 ℃ at 10 ℃/min, keeping the temperature for 3min, heating to 190 ℃ at the speed of 10 ℃/min, and obtaining the melting point of the polymer from the second heating curve.
Alpha-olefin composition and sequence distribution in copolymers Using carbon Spectroscopy Nuclear magnetism: (13C NMR) was measured at 125 ℃ with an instrument model Bruker AC 400; preparing a polymer into a deuterated o-dichlorobenzene solution with the mass fraction of 10% at 150 ℃, and dissolving the deuterated o-dichlorobenzene solution for 3 to 4 hours in advance to ensure that the sample solution is uniform; the instrument parameters are optimized to be pulse angle of 90 degrees, reverse proton decoupling, pulse delay time of 8s, collection time of 1.3s and spectrum width of 8000Hz, and the average scanning times are not less than 5000 times. The copolymer composition and distribution were calculated using astm d5017-96 method.
The uniaxial tensile test of the polymer is carried out on a universal material testing machine (INSTRON 2710-100), the test temperature is room temperature, and the tensile rate is 50 mm/min; the polymer sample strips were compression molded at 170 ℃ and quenched at room temperature to form 5-type sample strips having a shape and size according to GBT 1040.3-2006, cut by a cutter, and had a thickness of about 0.3 mm. To test the elastic recovery energy of the material, the strain was fixed at 300%, and the material was returned to 0 at 100mm/min to 300% strain and then stretched 10 times in cycles.
The Mw of the prepared polyolefin thermoplastic elastomer is 302kD,
Is 5.5, TmThe polymer had a temperature of 121 ℃, an alpha-olefin content of 17 mol%, a macromonomer number per chain of 4.4, an elastic modulus of 29.0MPa, an elongation at break of 1120%, and a breaking strength of 16.9 MPa.
Comparative example 1
The experimental conditions were: all of the ethylene homopolymerization catalyst, copolymerization catalyst, cocatalyst, ethylene and 1-octene introduced into the inlet and the feed port of example 1 were fed from the inlet of the reactor, and the reaction residence time was the same as that of example 1, and the temperature and pressure were the same as those of example 1.
The Mw of the prepared polyolefin thermoplastic elastomer is 178kD,
Is 6.5, TmThe polymer had a content of alpha-olefin of 16 mol% at 88 ℃ and a macromonomer number per chain of 2.2, an elastic modulus of 14.1MPa, an elongation at break of 750% and a breaking strength of 6.3 MPa.
Example 2
The experimental conditions were: the aim was to synthesize a copolymer having a molecular weight of 980kD and a 1-butene content of 31 mol%. In the experiment, ethylene bridged group bis indenyl zirconium dichloride is used as an ethylene homopolymerization catalyst, dicyclopentadienyl dimethyl hafnium is used as a copolymerization catalyst, dried methylaluminoxane is used as a cocatalyst, normal hexane is used as a solvent, and 1-butene is used as alpha-olefin. The feeding concentration of the ethylene homopolymerization catalyst at the inlet of the reactor is 95 mu mol/L, and the molar ratio of the cocatalyst to the ethylene homopolymerization catalyst is 10: 1, the feeding concentration of ethylene is 19mol/L, the polymerization temperature is 171 ℃, the polymerization pressure is 11.4MPa, and the retention time of the materials from the inlet to the fourth feeding port section is 8 min; at the fourth feed port, the feeding concentration of the copolymerization catalyst is 95 mu mol/L, and the molar ratio of the cocatalyst to the copolymerization catalyst is 50: 1, the ethylene feeding concentration is 19mol/L, the butene feeding concentration is 38mol/L, the polymerization temperature is 266 ℃, the polymerization pressure is 10MPa, the retention time of materials from the fourth feeding hole to the outlet is 11.5min, and the other reaction conditions are the same as those of the example 1.
Example 3
The experimental conditions were: the aim was to synthesize a copolymer having a molecular weight of 27kD and a 1.5 mol% hexene content. In the experiment, 2, 6-diiminopyridine cobalt catalyst is adopted as an ethylene homopolymerization catalyst, diphenyl carbon bridging group-cyclopentadienyl- (2-dimethylamino-fluorenyl) zirconium dichloride is adopted as a copolymerization catalyst, a 1:500 molar ratio mixture of tri (pentafluorobenzene) borane and triisobutylaluminum is adopted as a cocatalyst, toluene is used as a solvent, and 1-hexene is used as alpha-olefin. The feeding concentration of the ethylene homopolymerization catalyst at the inlet of the reactor is 0.1 mu mol/L, and the molar ratio of the cocatalyst to the ethylene homopolymerization catalyst is 25000: 1, the feeding concentration of ethylene is 0.1mol/L, the polymerization temperature is 50 ℃, the polymerization pressure is 0.2MPa, and the retention time of the materials from an inlet to a sixth feeding port section is 54 min; at the sixth feed port, the feeding concentration of the copolymerization catalyst is 0.1 mu mol/L, and the molar ratio of the cocatalyst to the copolymerization catalyst is 9500: 1, the ethylene feeding concentration is 0.1mol/L, the hexene feeding concentration is 0.1mol/L, the polymerization temperature is 100 ℃, the polymerization pressure is 0.2MPa, the retention time of the materials from the sixth feeding hole to the outlet is 35min, and the other reaction conditions are the same as those in example 1.
Examples 4 to 6 and comparative example 2 were carried out in a tubular reactor having an inner diameter of 12.7mm and a length of 20 m. The feed molarity to be used in the present invention means: initial concentration of propylene as it enters the reactor, based on volume of organic solvent; the feed molar ratio refers to the ratio of the alpha-olefin entering the reactor to the initial molar concentration of propylene.
Example 4
In the experiment, rac-dimethylsilanebis (2-methyl-4-phenylindenyl) zirconium dichloride is used as a propylene homopolymerization catalyst, dimethyl silicon bridging group-tetramethyl cyclopentadienyl-tert-butylamino-dimethyl titanium is used as a copolymerization catalyst, dried methylaluminoxane is used as a cocatalyst, Isopar E is used as a solvent, 1-octene is used as alpha-olefin, the polymerization experiment is carried out in a high-temperature and high-pressure continuous solution system, 1 side feed inlet is arranged at each 1m position of a tubular reactor, and the tubular reactor is respectively positioned to be a number consistent with the length according to the length meter from an inlet to the feed inlet, for example, a feed inlet 5m away from the inlet is determined as a fifth feed inlet. The reactor and piping were purged with a solution of triisobutylaluminum and Isopar E to remove water oxygen prior to polymerization. Transferring a propylene homopolymerization catalyst, a copolymerization catalyst and a cocatalyst under the protection of nitrogen atmosphere, preparing solutions with Isopar E respectively, and storing the solutions in respective storage tanks for later use, wherein the concentration of the ethylene homopolymerization catalyst is 200 mu mol/L, the concentration of the cocatalyst is 10mmol/L, and the concentration of the copolymerization catalyst is 200 mu mol/L. The solvents Isopar E and alpha-olefin were also stored in the solvent tank.
The feeding strategy of materials at an inlet and a feeding hole is designed by taking a copolymer with the molecular weight of 300kD and the copolymerization composition of 17mol percent as a target. Opening the oil bath, and raising the temperature from the inlet to the fifth feeding port of the tubular reactor to 100 ℃ and the temperature from the fifth feeding port to the outlet to 150 ℃; and opening a feed valve and a discharge valve of the reactor, opening a high-pressure metering pump, continuously adding propylene, a propylene homopolymerization catalyst, a cocatalyst and a solvent into the tubular reactor from an inlet by the metering pump according to a set flow rate, and continuously feeding the propylene, the copolymerization catalyst, the cocatalyst, 1-octene and the solvent into the reactor from a side feed inlet of the tubular reactor. The pressure in the reactor is controlled by a proportional valve and is stabilized at 1 MPa. The feeding concentration of the propylene homopolymerization catalyst at an inlet is 2 mu mol/L, the feeding concentration of the cocatalyst is 10mmol/L, the molar ratio of the cocatalyst to the propylene homopolymerization catalyst is 5000, the feeding concentration of the propylene is 1.30mol/L, and the retention time of the material from the inlet to a fifth feeding port section is 32 min; at a fifth feed inlet, the feeding concentration of the copolymerization catalyst is 20 mu mol/L, the feeding concentration of the cocatalyst is 20mmol/L, the molar ratio of the cocatalyst to the copolymerization catalyst is 1000, the feeding concentration of propylene is 0.98mol/L, the feeding concentration of 1-octene is 1.23mol/L, the feeding molar ratio of octene to propylene is 1.26, and the retention time of the material from the fifth feed inlet to an outlet is 30 min; the continuously flowing-out material is washed several times by a large amount of acidified ethanol, filtered, drained and vacuum-dried at 60 ℃ for more than 8 hours.
The Mw 295kD of the prepared polyolefin thermoplastic elastomer,
Is 5.2, TmAt 140 deg.C,The alpha-olefin content was 16.8 mol%, the number of macromonomers per chain was 4.1, the elastic modulus was 30.1MPa, the elongation at break was 1210%, and the breaking strength was 17.5 MPa.
Comparative example 2
The experimental conditions were: all of the propylene homopolymerization catalyst, copolymerization catalyst, cocatalyst, propylene and 1-octene introduced into the inlet and the feed inlet of example 1 were fed from the inlet of the reactor, the reaction residence time was the same as that of example 4, and the temperature and pressure were the same as those of example 4.
The Mw of the prepared polyolefin thermoplastic elastomer is 202kD,
Is 6.1, TmThe temperature was 95 ℃, the alpha-olefin content was 12.8 mol%, the number of macromonomers per chain was 1.2, the elastic modulus was 15.1MPa, the elongation at break was 680%, and the breaking strength was 12.5 MPa.
Example 5
The experimental conditions were: the aim was to synthesize a copolymer having a molecular weight of 980kD and a 1-butene content of 31 mol%. In the experiment, a propylene homopolymerization catalyst adopts bis [ N- (3-trimethylsilylsalicylalkylene) -3, 5-difluorophenylamino ] zirconium dichloride, a copolymerization catalyst adopts dicyclopentadienyl dimethyl hafnium, a cocatalyst adopts dry methylaluminoxane, a solvent is N-hexane, and alpha-olefin is 1-butene. The feeding concentration of the propylene homopolymerization catalyst at the inlet of the reactor is 95 mu mol/L, and the molar ratio of the cocatalyst to the propylene homopolymerization catalyst is 10: 1, the feeding concentration of propylene is 19mol/L, the polymerization temperature is 190 ℃, the polymerization pressure is 11.4MPa, and the retention time of the material from an inlet to a fourth feeding port section is 8 min; at the fourth feed port, the feeding concentration of the copolymerization catalyst is 95 mu mol/L, and the molar ratio of the cocatalyst to the copolymerization catalyst is 50: 1, the propylene feeding concentration is 19mol/L, the butylene feeding concentration is 38mol/L, the polymerization temperature is 270 ℃, the polymerization pressure is 10MPa, the retention time of materials from a fourth feeding hole to an outlet is 11.5min, and other reaction conditions are the same as those of the example 4.
Example 6
The experimental conditions were: the aim was to design a copolymer with a molecular weight of 27kD and a 1.5 mol% 1-hexene content. In the experiment, the propylene homopolymerization catalyst adopts dimethylcarbon bridged-cyclopentadienyl-3, 8-di-tert-butylfluorenyl zirconium dichloride, the copolymerization catalyst adopts diphenylcarbon bridged-cyclopentadienyl- (2-dimethylamino-fluorenyl) zirconium dichloride, the cocatalyst adopts a 1:500 molar ratio mixture of tri (pentafluorobenzene) borane and triisobutylaluminum, the solvent is toluene, and the alpha-olefin is 1-hexene. The feeding concentration of the propylene homopolymerization catalyst at the inlet of the reactor is 0.1 mu mol/L, and the molar ratio of the cocatalyst to the propylene homopolymerization catalyst is 25000: 1, the feeding concentration of propylene is 0.1mol/L, the polymerization temperature is 50 ℃, the polymerization pressure is 0.2MPa, and the retention time of the materials from an inlet to a sixth feeding port section is 54 min; at the sixth feed port, the feeding concentration of the copolymerization catalyst is 0.1 mu mol/L, and the molar ratio of the cocatalyst to the copolymerization catalyst is 9500: 1, the propylene feed concentration is 0.1mol/L, the hexene feed concentration is 0.1mol/L, the polymerization temperature is 120 ℃, the polymerization pressure is 0.2MPa, the residence time of the materials from the sixth feed inlet to the outlet is 35min, and the other reaction conditions are the same as those in example 4.
Examples 7 to 12 and comparative examples 3 and 4 were carried out in a 500ml olefin batch polymerization reactor, in which high-temperature high-pressure batch copolymerization was carried out.
Example 7
In the experiment, the ethylene homopolymerization catalyst adopts bis (3-tert-butylsalicylidene-cyclopentanoimino) zirconium dichloride, the copolymerization catalyst adopts dimethyl silicon bridge group-tetramethyl cyclopentadienyl-tert-butylamino-dimethyl titanium, the cocatalyst adopts dry methylaluminoxane, the solvent is Isopar E, the alpha-olefin is 1-octene, and the polymerization experiment is carried out in a high-temperature high-pressure solution system. The reactor and piping were purged with a solution of triisobutylaluminum and Isopar E before polymerization to remove water oxygen. Transferring the ethylene homopolymerization catalyst, the copolymerization catalyst, the cocatalyst and the alpha-olefin under the protection of nitrogen atmosphere, preparing solutions with Isopar E respectively, and storing the solutions in respective storage tanks for later use, wherein the solvent Isopar E is also stored in a solvent storage tank.
The material feeding strategies at different times are determined by taking the aim of synthesizing a copolymer with the molecular weight of 115kD and the copolymerization composition of 5.7mol percent. Firstly heating a reaction kettle to 100 ℃, then opening a liquid feed valve, adding 220ml of solvent Isopar E into the reaction kettle, then immediately closing the liquid feed valve, opening and stirring to 1000 revolutions per minute, adding an ethylene homopolymerization catalyst and a cocatalyst into the reaction kettle, controlling the pressure in the kettle to be 1.0MPa, and then continuously supplying the ethylene consumption in the kettle through a flow controller in the reaction process to ensure that the pressure in the kettle is constant. Reacting at constant temperature and constant pressure for 5min, adding copolymerization catalyst, cocatalyst and 1-octene into the reaction kettle by using a high-pressure metering pump, continuing to react for 25min, ending polymerization, and pouring the materials into a beaker filled with a large amount of acidified ethanol. The polymer was filtered and washed several times with ethanol and dried under vacuum at 60 ℃ for more than 8 hours. In the experiment, the concentration of the ethylene homopolymerization catalyst in the kettle is 1 mu mol/L, the concentration of the copolymerization catalyst is 10 mu mol/L, the concentration of ethylene is 1mol/L, the feeding molar ratio of 1-octene to ethylene is 1.26, and the molar ratio of the cocatalyst to the ethylene homopolymerization catalyst in the homopolymerization stage is 5000: 1, the molar ratio of the cocatalyst to the copolymerization catalyst in the copolymerization stage is 1000: 1. all materials used in the experiment were subjected to water removal and oxygen removal.
The Mw of the prepared polyolefin thermoplastic elastomer is 113kD,
Is 6.5, TmAt 125 deg.C, an alpha-olefin content of 5.7 mol%, a number of macromonomers per chain of 5.5, an elastic modulus of 42.6MPa, an elongation at break of 1035%, and a breaking strength of 29.2 MPa.
Comparative example 3
The experimental conditions were: all the ethylene homopolymerization catalyst, copolymerization catalyst, cocatalyst, ethylene and 1-octene fed in batches in example 7 were added to the kettle in one portion, the total reaction residence time was the same as in example 7, and the temperature and pressure were the same as the initial temperature and pressure in example 7.
The Mw of the prepared polyolefin thermoplastic elastomer is 97kD,
Is 6.0, TmThe alpha-olefin content is 5.2 mol percent at 100 ℃, the number of macromonomers on each chain is 2.7, the elastic modulus is 20.7MPa, the elongation at break is 525 percent, and the breaking strength is 13.8 MPa。
Example 8
The experimental conditions were: the method aims to synthesize a copolymer with the molecular weight of 846kD and the content of 1-octene of 31 mol%, and determines material feeding strategies at different times. After the system reaches a steady state, the temperature is kept at 160 ℃, 1-octene and a copolymerization catalyst are added after homopolymerization is carried out for 60min, the copolymerization reaction time is 120min, the pressure is maintained at 11.5MPa, the concentration of the ethylene homopolymerization catalyst is 47.5 mu mol/L, and the proportion of a cocatalyst to the ethylene homopolymerization catalyst in a homopolymerization stage is 10: 1; the concentration of the copolymerization catalyst is 95 mu mol/L, and the proportion of the cocatalyst to the copolymerization catalyst in the copolymerization stage is 10: 1, ethylene concentration 19mol/L, octene feed concentration 38mol/L, other experimental conditions were the same as in example 7.
Example 9
The experimental conditions were: the molecular weight is 22kD based on the synthesis, and the content of 1-octene is 2.7 mol%. Keeping the temperature at 120 ℃, adding 1-octene and a copolymerization catalyst after homopolymerization for 5min, wherein the copolymerization time is 5min, the pressure is maintained at 0.2MPa, the concentration of the ethylene homopolymerization catalyst is 0.1 mu mol/L, and the proportion of a cocatalyst and the ethylene homopolymerization catalyst in a homopolymerization stage is 20000: 1, the concentration of the copolymerization catalyst is 0.1 mu mol/L, and the proportion of the cocatalyst to the copolymerization catalyst in the copolymerization stage is 20000: 1, ethylene concentration 0.1mol/L, octene feed concentration 0.1mol/L, other experimental conditions were the same as in example 7.
Examples 10 to 12 and comparative example 4 were carried out in a 500ml olefin batch polymerization reactor, and were carried out by high-temperature high-pressure batch copolymerization.
Example 10
In the experiment, the propylene homopolymerization catalyst adopts rac-dimethylsilanebis (2-methyl-4-phenylindenyl) zirconium dichloride, the copolymerization catalyst adopts dimethylsilyl-tetramethylcyclopentadienyl-tert-butylamino-dimethyl titanium, the cocatalyst adopts dry methylaluminoxane, the solvent is Isopar E, the alpha-olefin is 1-octene, and the polymerization experiment is carried out in a high-temperature high-pressure solution system. The reactor and piping were purged with a solution of triisobutylaluminum and Isopar E to remove water oxygen prior to polymerization. Transferring the propylene homopolymerization catalyst, the copolymerization catalyst, the cocatalyst and the alpha-olefin under the protection of nitrogen atmosphere, preparing solutions with Isopar E respectively, and storing the solutions in respective storage tanks for later use, wherein the solvent Isopar E is also stored in a solvent storage tank.
The material feeding strategies at different times are determined by taking the aim of synthesizing a copolymer with the molecular weight of 115kD and the copolymerization composition of 5.7mol percent. Firstly heating a reaction kettle to 100 ℃, then opening a liquid feed valve, adding 220ml of solvent Isopar E into the reaction kettle, then immediately closing the liquid feed valve, opening and stirring to 1000 revolutions per minute, adding a propylene homopolymerization catalyst into the reaction kettle, controlling the pressure in the kettle to be 1.0MPa, and continuously supplying the consumed amount of propylene in the kettle through a flow controller in the reaction process to ensure that the pressure in the kettle is constant. Reacting at constant temperature and constant pressure for 5min, adding copolymerization catalyst, cocatalyst and 1-octene into the reaction kettle by using a high-pressure metering pump, continuing to react for 25min, ending polymerization, and pouring the materials into a beaker filled with a large amount of acidified ethanol. The polymer was filtered, washed several times with ethanol and dried under vacuum at 60 ℃ for more than 8 hours. In the experiment, the concentration of the propylene homopolymerization catalyst in the kettle is 1 mu mol/L, the concentration of the copolymerization catalyst is 10 mu mol/L, the concentration of propylene is 1mol/L, the feeding molar ratio of 1-octene to propylene is 1.26, and the molar ratio of the cocatalyst to the ethylene homopolymerization catalyst in the homopolymerization stage is 5000: 1, the molar ratio of the cocatalyst to the copolymerization catalyst in the copolymerization stage is 1000: 1. all materials used in the experiment were subjected to water removal and oxygen removal.
The Mw 118kD of the prepared polyolefin thermoplastic elastomer,
Is 6.2, TmThe temperature is 142 ℃, the alpha-olefin content is 5.6 mol%, the number of macromonomers on each chain is 5, the elastic modulus is 32.1MPa, the elongation at break is 1080%, and the breaking strength is 23.5 MPa.
Comparative example 4
The experimental conditions were: all the propylene homopolymerization catalyst, copolymerization catalyst, cocatalyst, propylene and 1-octene fed in batches in example 10 were added to the kettle in one portion, the total reaction residence time was the same as that in example 10, and the temperature and pressure were the same as the initial temperature and pressure in example 10.
The Mw 132kD of the prepared polyolefin thermoplastic elastomer,
Is 5.2, Tm105 ℃, 5.4 mol% of alpha-olefin content, 2.2 macromonomer number per chain, 18.2MPa elastic modulus, 510% elongation at break and 13.9 MPa breaking strength.
Example 11
The experimental conditions were: the synthesis of copolymer with molecular weight of 846kD and content of 1-octene of 31 mol% is used as target. After the system reaches a steady state, the temperature is kept at 160 ℃, 1-octene and a copolymerization catalyst are added after homopolymerization is carried out for 60min, the copolymerization reaction time is 120min, the pressure is maintained at 11.5MPa, the concentration of the propylene homopolymerization catalyst is 47.5 mu mol/L, and the proportion of a cocatalyst to the propylene homopolymerization catalyst in a homopolymerization stage is 10: 1, the concentration of the copolymerization catalyst is 95 mu mol/L, and the proportion of the cocatalyst to the copolymerization catalyst in the copolymerization stage is 10: 1, propylene concentration 19mol/L, octene feed concentration 38mol/L, other experimental conditions were the same as in example 10.
Example 12
The experimental conditions were: the aim was to synthesize a copolymer having a molecular weight of 22kD and a 1.7 mol% 1-octene content. Keeping the temperature at 120 ℃, adding 1-octene and a copolymerization catalyst after homopolymerization for 5min, wherein the copolymerization time is 5min, the pressure is maintained at 0.2MPa, the concentration of the propylene homopolymerization catalyst is 0.1 mu mol/L, and the proportion of the cocatalyst to the propylene homopolymerization catalyst in the homopolymerization stage is 20000: 1, the concentration of the copolymerization catalyst is 0.1 mu mol/L, and the proportion of the cocatalyst to the copolymerization catalyst in the copolymerization stage is 20000: 1, propylene concentration 0.1mol/L, octene feed concentration 0.1mol/L, other experimental conditions were the same as in example 10.
In summary, the above examples and comparative examples show that the comb-shaped polyolefin thermoplastic elastomers prepared by the method of the present invention under high temperature and high pressure conditions have higher melting point, elastic modulus, elongation at break and breaking strength than the products prepared without using the material feeding strategy.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. A preparation method of comb-shaped polyolefin thermoplastic elastomer based on feeding strategy regulation is characterized by comprising the following steps:
(1) mixing an organic solvent, ethylene, an ethylene homopolymerization catalyst and a cocatalyst, and polymerizing under the polymerization pressure of 0.1-12 MPa and at the polymerization temperature of 50-180 ℃ for 5-60 min to synthesize a polyethylene macromonomer; based on the volume of the organic solvent, the concentration of the ethylene homopolymerization catalyst is 0.1-100 mu mol/L, and the molar ratio of the cocatalyst to the ethylene homopolymerization catalyst is 10-50000: 1, the feeding concentration of ethylene is 0.1-20 mol/L, the weight average molecular weight of the prepared polyethylene macromonomer is 500-50000 g/mol, the molecular weight distribution index is 1.0-5.0, and the proportion of terminal double bonds is controlled to be more than 50%;
(2) mixing an organic solvent, alpha-olefin, a copolymerization catalyst and the polyethylene macromonomer prepared in the step (1), polymerizing under the polymerization pressure of 0.1-12 MPa and at the polymerization temperature of 50-180 ℃ for 5-120 min to synthesize a comb-shaped polyolefin thermoplastic elastomer; based on the volume of the organic solvent, the concentration of the copolymerization catalyst is 0.1-100 mu mol/L, the concentration of the ethylene homopolymerization catalyst is 0.1-50 mu mol/L, and the molar ratio of the total amount of the copolymerization catalyst to the total amount of the ethylene homopolymerization catalyst is 25: 1-1: 15, the molar ratio of the cocatalyst to the copolymerization catalyst is 10-50000: 1, the concentration of the alpha-olefin feed is 0.1-40 mol/L; the weight average molecular weight of the prepared comb-shaped polyolefin thermoplastic elastomer is 20000-500000 g/mol, the molecular weight distribution index is 1.0-10.0, and the mole content of alpha-olefin is 1-70%.
2. A preparation method of comb-shaped polyolefin thermoplastic elastomer based on feeding strategy regulation is characterized by comprising the following steps:
(1) mixing an organic solvent, propylene, a propylene homopolymerization catalyst and a cocatalyst, and polymerizing at 50-180 ℃ for 5-60 min under the polymerization pressure of 0.1-12 MPa to synthesize a crystalline polypropylene macromonomer; based on the volume of the organic solvent, the concentration of the propylene homopolymerization catalyst is 0.1-100 mu mol/L, and the molar ratio of the cocatalyst to the propylene homopolymerization catalyst is 10-50000: 1, the feeding concentration of propylene is 0.1-20 mol/L, the weight average molecular weight of the prepared crystalline polypropylene macromonomer is 500-50000 g/mol, the molecular weight distribution index is 1.0-5.0, and the proportion of terminal double bonds is controlled to be more than 50%;
(2) mixing an organic solvent, alpha-olefin, a copolymerization catalyst and the crystalline polypropylene macromonomer prepared in the step (1), and polymerizing under the polymerization pressure of 0.1-12 MPa and at the polymerization temperature of 50-180 ℃ for 25-120 min to synthesize the comb-shaped polyolefin thermoplastic elastomer; based on the volume of the organic solvent, the concentration of the copolymerization catalyst is 0.1-100 mu mol/L, the concentration of the propylene homopolymerization catalyst is 0.1-50 mu mol/L, and the molar ratio of the total amount of the copolymerization catalyst to the total amount of the propylene homopolymerization catalyst is 25: 1-1: 15, the molar ratio of the cocatalyst to the copolymerization catalyst is 10-50000: 1, the concentration of the alpha-olefin feed is 0.1-40 mol/L; the weight average molecular weight of the prepared comb-shaped polyolefin thermoplastic elastomer is 20000-500000 g/mol, the molecular weight distribution index is 1.0-10.0, and the mole content of alpha-olefin is 1-70%.
3. The production method according to claim 1 or 2, characterized by producing in a tubular reactor or a batch stirred tank reactor; the feed inlet of the tubular reactor is positioned between the inlet and the outlet of the reactor and at different positions of the axial lateral line, and the number of the feed inlet is 1, 2, 3, 4 or more than 4.
4. The method of claim 1, wherein the ethylene homopolymerization catalyst is a single-site metallocene catalyst or a post-metallocene catalyst, and comprises zirconocene dichloride, dimethylcarborenyl-biscyclopentadienyl-zirconium dichloride, 2, 6-diimidopyridine iron catalyst, 2, 6-diimidopyridine cobalt catalyst, bis (4-methylphenyl) carbon-bridged-cyclopentadienyl-indenyl-zirconium dichloride, bis (3-tert-butylsalicylidene-cyclopentylidene) zirconium dichloride, bis (5-methyl-3-tert-butylsalicylidene-cyclobutaneimino) zirconium dichloride, bis (3-tert-butylsalicylidene-cyclohexanylidene) zirconium dichloride, dimethylsilyl-tetramethylcyclopentadienyl-tert-butylamino-dimethyltitanium or ethylenebridged-bisindenyl Zirconium dichloride.
5. The process according to claim 2, wherein the propylene homopolymerization catalyst for producing the high melting point polypropylene macromonomer is a single site metallocene catalyst or a post metallocene catalyst, and comprises rac-dimethylsilylbis (2-methyl-3-propylindenyl) hafnium dimethyl, rac-dimethylsilylbis (2-methyl-3-propylindenyl) hafnium dichloride, rac-dimethylsilylbis (2-methyl-4-phenylindenyl) zirconium dimethyl, rac-dimethylsilylbis (2-methyl-4-phenylindenyl) hafnium dimethyl, rac-dimethylsilylbis indenyl hafnium dichloride, dimethylbridged carbon-cyclopentadienyl-fluorenyl-zirconium dichloride, rac-dimethylsilylbis (2-methyl-4-phenylindenyl) hafnium dichloride, and, Dimethylcarbon bridged-cyclopentadienyl-fluorenyl-zirconium dimethyl, rac-dimethylsilicon bridged- (2-methyl-4-tert-butylpentyl) -zirconium dimethyl, ansa-ethylene bridged- (2-methyl-3-benzyl-5, 6-cyclopentoindenyl) -fluorenyl zirconium dichloride, ansa-ethylene bridged- (2-methyl-3-benzyl-5, 6-cyclopentoindenyl) -fluorenyl zirconium dimethyl, ansa-ethylene bridged- (2-methyl-3-benzyl-5, 6-cyclopentoindenyl) -3, 6-di-tert-butylfluorenyl zirconium dichloride, 6-cyclopentoindenyl) -3, 6-di-tert-butylfluorenyldimethylzirconium, ansa-ethylene bridged- (2-methyl-3-benzyl-5, 6-cyclopentoindenyl) -fluorenylhafnium dichloride, ansa-ethylene bridged- (2-methyl-3-benzyl-5, 6-cyclopentoindenyl) -fluorenyldimethylhafnium, rac-propenyl bridged bisindenyldimethylaminobenzylzirconium or hafnium, methyl-alkyl-hafnocene or zirconium, ethylene bridged-5, 6-cyclopentoindenyl-fluorenylzirconium dichloride, ethylene bridged-5, 6-cyclopentoindenyl-fluorenyldimethylzirconium, ethylene bridged-5, 6-cyclopentoindenyl-2, 7-di-n-butylfluorenylzirconium dichloride, ethylene-bridged 5, 6-cyclopentoindenyl-2, 7-di-n-butylfluorenylzirconium dimethyl, ethylene-bridged- (3-benzyl-5, 6-cyclopentoindenyl) -2, 7-di-n-butylfluorenylzirconium dichloride, ethylene-bridged- (3-benzyl-5, 6-cyclopentoindenyl) -2, 7-di-n-butylfluorenylzirconium dimethyl, ethylene-bridged- (3-benzyl-5, 6-cyclopentoindenyl) -2, 7-di-tert-butylfluorenylhafnium dichloride, ethylene-bridged- (3-benzyl-5, 6-cyclopentoindenyl) -2, 7-di-tert-butylfluorenylhafnium dimethyl, di-tetramethyl-substituted cyclopentadienyl-hafnium dichloride, di-tetramethyl-substituted cyclopentadienyl-hafnium dimethyl, hafnium dimethyl, Tetramethylcyclopentadienyl-pentamethylcyclopentadienyl-hafnium dichloride, tetramethylcyclopentadienyl-pentamethylcyclopentadienyl-hafnium dimethyl, zirconocene dimethyl, diphenylcarbon-bridged-cyclopentadienyl-fluorenyl zirconium dichloride, diphenylcarbon-bridged-cyclopentadienyl-fluorenyl zirconium dimethyl or biscyclopentadienyl-methyl-neopentyl-zirconium.
6. The process according to claim 1 or 2, wherein the copolymerization catalyst is a single-site metallocene catalyst or post-metallocene catalyst comprising biscyclopentadienylhafnium dimethyl, bisindenyl zirconium dimethyl, ethylenebridged bisindenyl zirconium dichloride, dimethylsilyl-bisindenyl, diphenylcarbabridged-cyclopentadienyl-fluorenyl zirconium dichloride, dimethylsilyl-tetramethylcyclopentadienyl-tert-butylamino-dimethyltitanium, bisindenyl zirconium dichloride, bis [2- (3', 5' -di-tert-butylphenyl) -indenyl ] zirconium dichloride, bis (2-methyl-4, 5-phenyl-indenyl) zirconium dichloride, biscyclopentadienyl-bisphenoxy zirconium, dimethylsilbridged bisindenyl zirconium dichloride, bis (3', 5' -di-tert-butylphenyl) -indenyl) zirconium dichloride, Diphenylcarbocontin-cyclopentadienyl-fluorenyl-zirconiumdichloride, diphenylcarbocontin-cyclopentadienyl- (2-dimethylamino-fluorenyl) zirconiumdichloride, dimethylsilyl-tetramethylcyclopentadienyl-tert-butylamino-dimethyltitanium, dimethylsilyl-3-pyrrolylindenyl-tert-butylamino-dimethyltitanium, pentamethylcyclopentadienyl- (2-phenylphenoxy) -titanium dichloride, pentamethylcyclopentadienyl- (2, 6-diisopropylphenoxy) -titanium dichloride, bis (3-methylsalicylidene-pentafluorophenylimino) titanium dichloride, bis (salicylidene-phenylimino) titanium dichloride, dimethylsilyl-3-pyrrolylindenyl-tert-butylamino-dimethyltitanium, diphenylcarbocontin-cyclopentadienyl- (2-dimethylamino-fluorenyl) zirconium dichloride, dimethylsilyl-tetramethylcyclopentadienyl-tert-butylamino-dimethyltitanium dichloride, and mixtures thereof, [ N- (3, 5-di-tert-butylsalicylidene) -2-diphenylphosphinophenylimine ] titanium trichloride, (2, 3, 4-trihydro-8-diphenylphosphino-quinolyl) tribenzylzirconium.
7. The process according to claim 1 or 2, wherein the cocatalyst comprises methylalumoxane, modified methylalumoxane, triisobutylaluminum, triethylaluminum, trimethylaluminum, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, triphenylcarbenium tetrakis (pentafluorophenyl) borate, tris (pentafluorophenyl) borane, 4-isopropyl-4' -methyldiphenyliodonium tetrakis (pentafluorophenyl) borate, tri (N-butyl) ammonium tetrakis (pentafluorophenyl) borate, N-diethylanilinium tetrakis (pentafluorophenyl) -borate, triethylammonium tetrakis (pentafluorophenyl) borate, dimethylanilinium tetrakis (pentafluorophenyl) borate, N-dioctadecyl-N-methyltetrakis (pentafluorophenyl) ammonium borate, tripropylamine tetrakis (pentafluorophenyl) borate, tripropylamine, One or more of di (isopropyl) ammonium tetrakis (pentafluorophenyl) borate and triphenylphosphine tetrakis (pentafluorophenyl) borate may be mixed in any proportion.
8. The method according to claim 1 or 2, wherein the organic solvent is a linear alkane, an isoparaffin, a cycloalkane, or an arylalkane having 4 to 10 carbon atoms; the alpha-olefin is a straight chain or branched chain alpha-olefin with 4-20 carbon atoms.
9. The method according to claim 8, wherein the organic solvent is Isopar E, n-pentane, isopentane, n-hexane, cyclohexane, n-heptane, isoheptane, n-octane, isooctane, n-decane, toluene or xylene; the alpha-olefin is 1-butene, 1-pentene, 1-hexene, 1-octene or 1-decene.
10. The method for preparing the comb-shaped polyolefin thermoplastic elastomer, according to claim 1 or 2, is characterized in that the elongation at break of the comb-shaped polyolefin thermoplastic elastomer is more than 100%, the strength at break is more than 1MPa, and the elastic recovery rate is more than 40%.
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| CN115677885A (en) * | 2022-11-11 | 2023-02-03 | 山东京博石油化工有限公司 | Method for cooling raw materials in polymerization reaction process |
| CN115772240A (en) * | 2022-11-11 | 2023-03-10 | 山东京博石油化工有限公司 | Preparation method of thermoplastic polyolefin elastomer |
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| CN109384885A (en) * | 2018-09-29 | 2019-02-26 | 浙江大学 | A kind of pectination ethylene based polyolefin process for preparation of thermoplastic elastomer |
| CN109535323A (en) * | 2018-09-29 | 2019-03-29 | 浙江大学 | A kind of novel pectination propylene based polyolefm process for preparation of thermoplastic elastomer |
| CN111635494A (en) * | 2020-06-19 | 2020-09-08 | 浙江大学衢州研究院 | Preparation method of comb-shaped propenyl olefin polymer |
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| CN109384885A (en) * | 2018-09-29 | 2019-02-26 | 浙江大学 | A kind of pectination ethylene based polyolefin process for preparation of thermoplastic elastomer |
| CN109535323A (en) * | 2018-09-29 | 2019-03-29 | 浙江大学 | A kind of novel pectination propylene based polyolefm process for preparation of thermoplastic elastomer |
| CN111635494A (en) * | 2020-06-19 | 2020-09-08 | 浙江大学衢州研究院 | Preparation method of comb-shaped propenyl olefin polymer |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115677885A (en) * | 2022-11-11 | 2023-02-03 | 山东京博石油化工有限公司 | Method for cooling raw materials in polymerization reaction process |
| CN115772240A (en) * | 2022-11-11 | 2023-03-10 | 山东京博石油化工有限公司 | Preparation method of thermoplastic polyolefin elastomer |
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