CN109456445B - Preparation method of comb-shaped propenyl polyolefin thermoplastic elastomer - Google Patents
Preparation method of comb-shaped propenyl polyolefin thermoplastic elastomer Download PDFInfo
- Publication number
- CN109456445B CN109456445B CN201811148679.3A CN201811148679A CN109456445B CN 109456445 B CN109456445 B CN 109456445B CN 201811148679 A CN201811148679 A CN 201811148679A CN 109456445 B CN109456445 B CN 109456445B
- Authority
- CN
- China
- Prior art keywords
- propylene
- catalyst
- bis
- zirconium dichloride
- mol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229920002725 thermoplastic elastomer Polymers 0.000 title claims abstract description 23
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 title claims abstract description 8
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 60
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 60
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000005977 Ethylene Substances 0.000 claims abstract description 47
- -1 polypropylene Polymers 0.000 claims abstract description 39
- 239000004743 Polypropylene Substances 0.000 claims abstract description 24
- 229920001155 polypropylene Polymers 0.000 claims abstract description 24
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 21
- 229920001577 copolymer Polymers 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims description 68
- 238000006243 chemical reaction Methods 0.000 claims description 29
- 238000007334 copolymerization reaction Methods 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 15
- 229920000642 polymer Polymers 0.000 claims description 15
- 239000003960 organic solvent Substances 0.000 claims description 11
- VPGLGRNSAYHXPY-UHFFFAOYSA-L zirconium(2+);dichloride Chemical compound Cl[Zr]Cl VPGLGRNSAYHXPY-UHFFFAOYSA-L 0.000 claims description 10
- 238000009826 distribution Methods 0.000 claims description 8
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000012968 metallocene catalyst Substances 0.000 claims description 6
- 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 5
- DZETZMSAJDMAKS-UHFFFAOYSA-L Cl[Zr]Cl.[CH]1C(C)=CC2=C1C=CC=C2C1=CC=CC=C1 Chemical compound Cl[Zr]Cl.[CH]1C(C)=CC2=C1C=CC=C2C1=CC=CC=C1 DZETZMSAJDMAKS-UHFFFAOYSA-L 0.000 claims description 5
- 239000012005 post-metallocene catalyst Substances 0.000 claims description 5
- 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
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 4
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 claims description 4
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 4
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 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
- 239000000203 mixture Substances 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
- UINDPJOQTXRETJ-UHFFFAOYSA-N CC(C)C1=CC(C(C)C)=CC1[Zr](C1C=C(C(C)C)C=C1)([SiH](C)C)[SiH](C)C.Cl.Cl Chemical compound CC(C)C1=CC(C(C)C)=CC1[Zr](C1C=C(C(C)C)C=C1)([SiH](C)C)[SiH](C)C.Cl.Cl UINDPJOQTXRETJ-UHFFFAOYSA-N 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
- 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
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-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
- FFAYLXSITFDGCE-UHFFFAOYSA-L [Cl-].[Cl-].C[Si](C1=C(C(CC2=C(C=C(C=C2F)F)[Ti+2]C2=C(C(=CC(=C2)F)F)CC=2C(O)=C(C=CC2)[Si](C)(C)C)=CC=C1)O)(C)C Chemical compound [Cl-].[Cl-].C[Si](C1=C(C(CC2=C(C=C(C=C2F)F)[Ti+2]C2=C(C(=CC(=C2)F)F)CC=2C(O)=C(C=CC2)[Si](C)(C)C)=CC=C1)O)(C)C FFAYLXSITFDGCE-UHFFFAOYSA-L 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 150000001924 cycloalkanes Chemical class 0.000 claims description 2
- 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 claims description 2
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 claims description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-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
- 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
- 239000008096 xylene Substances 0.000 claims description 2
- AQZWEFBJYQSQEH-UHFFFAOYSA-N 2-methyloxaluminane Chemical compound C[Al]1CCCCO1 AQZWEFBJYQSQEH-UHFFFAOYSA-N 0.000 claims 2
- JIRPEKSHJWINPV-UHFFFAOYSA-J C1(C=CC=C1)[Zr](Cl)(Cl)(OC1=CC=CC=C1)OC1=CC=CC=C1 Chemical compound C1(C=CC=C1)[Zr](Cl)(Cl)(OC1=CC=CC=C1)OC1=CC=CC=C1 JIRPEKSHJWINPV-UHFFFAOYSA-J 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
- 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
- 229910052735 hafnium Inorganic materials 0.000 claims 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 abstract 1
- 229920002554 vinyl polymer Polymers 0.000 abstract 1
- 239000002904 solvent Substances 0.000 description 17
- 229920006124 polyolefin elastomer Polymers 0.000 description 12
- 238000002474 experimental method Methods 0.000 description 11
- 229920001971 elastomer Polymers 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 239000005060 rubber Substances 0.000 description 6
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical group C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 230000020477 pH reduction Effects 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- JZZIHCLFHIXETF-UHFFFAOYSA-N dimethylsilicon Chemical compound C[Si]C JZZIHCLFHIXETF-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 238000007613 slurry method Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000004711 α-olefin Substances 0.000 description 3
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical class ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 229920005604 random copolymer Polymers 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- HVTDCRJTBFNDKQ-UHFFFAOYSA-N CC(C)(C)N[Ti](C)(C[SiH](C)C)C1=CC=CC2=C1CC1=CC=CC=C21 Chemical compound CC(C)(C)N[Ti](C)(C[SiH](C)C)C1=CC=CC2=C1CC1=CC=CC=C21 HVTDCRJTBFNDKQ-UHFFFAOYSA-N 0.000 description 1
- CBMJKOYLPDINEX-UHFFFAOYSA-N CC(C)(C)N[Ti](C)(C[SiH](C)C)C1C2=CC=CC=C2C(C2=CC=CN2)=C1.Cl.Cl.Cl Chemical compound CC(C)(C)N[Ti](C)(C[SiH](C)C)C1C2=CC=CC=C2C(C2=CC=CN2)=C1.Cl.Cl.Cl CBMJKOYLPDINEX-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 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
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes 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
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- HEAMQYHBJQWOSS-UHFFFAOYSA-N ethene;oct-1-ene Chemical compound C=C.CCCCCCC=C HEAMQYHBJQWOSS-UHFFFAOYSA-N 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion 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
- 239000003921 oil Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000001228 spectrum Methods 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
- 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
- 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
-
- 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
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/02—Ethene
-
- 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
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/04—Monomers containing three or four carbon atoms
- C08F210/06—Propene
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a comb-shaped propenyl polyolefin thermoplastic elastomer and a preparation method thereof, the comb-shaped propenyl polyolefin thermoplastic elastomer takes a crystallized polypropylene hard segment as a side chain and an amorphous ethylene/propylene copolymer soft segment as a main chain, a first reactor is used for synthesizing a crystallized polypropylene macromonomer in a high-temperature high-pressure solution polymerization system through a cascade catalysis system, and the synthesized macromonomer enters a second reactor to carry out ternary polymerization with ethylene and propylene, so as to synthesize the comb-shaped propenyl polyolefin thermoplastic elastomer. The comb-shaped vinyl polyolefin thermoplastic elastomer prepared by the invention can be used for replacing the application field of the traditional polyolefin thermoplastic elastomer and has high industrial value.
Description
Technical Field
The invention belongs to the technical field of preparation of thermoplastic elastomers, and relates to a preparation method of a comb-shaped propenyl polyolefin thermoplastic elastomer.
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 comonomer incorporation ethylene/α -olefin copolymer polyolefin elastomer (POE) is a commercial product with high added value, which was first prepared by the Dow company of America (Dow) 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 using a bridged bis-metallocene catalystPOE copolymer of butene, ethylene/1-hexene, ethylene/1-octene, under the trade name ExactTMIn addition, the DOW company invented a chain shuttling polymerization technique in 2005 and succeeded in industrializing a brand new polyolefin thermoplastic elastomer-Olefin Block Copolymer (OBC) under the trademark InfuseTM(Science 2006,312, 714-719.) the product has a multi-block structure with hard blocks and soft blocks alternating on the main chain, which can maintain both the melting point similar to LL DPE and the elasticity of POE, and can maintain better elasticity at higher temperature, and the heat resistance is much higher than that of POE elastomer.2013, DOW developed a propylene-based block copolymer with the trade name of INTUNETM. The product can be used as an excellent compatilizer between polyethylene and polypropylene and applied to the recovery of polyethylene and polypropylene materials. Compared with polyethylene, the polypropylene has a more complex structure, and the isotactic, syndiotactic and atactic polypropylenes with three different structures can be produced by adopting metallocene catalysts with different structures, and the properties of the three polypropylenes are greatly different, for example, the melting point of the isotactic polypropylene can reach 165 ℃ and is higher than that of HDPE, so that the isotactic polypropylene can be applied at a higher temperature, and the application range of the material is widened; atactic polypropylene then exhibits a completely amorphous structure. By incorporating a certain amount of ethylene segments into isotactic polypropylene, the polymer will be transformed from a thermoplastic to a thermoplastic elastomer. When the mass fraction of ethylene insertion is between 10 and 15 wt%, the material exhibits excellent elastomeric properties. (Journal of applied Polymer Science,2007,104,489-499) for this purpose, we consider that the hard segment of the crystallizable polypropylene can be concentrated on the side chain of the copolymer and the soft segment of the random copolymer of ethylene/propylene as the main chain of the copolymer by the design of the topology of the copolymer chain, the hard segment of the side chain can form the crystallized plastic phase, the main chain forms the rubber phase, the material is phase separated, and finally, the acrylic polyolefin thermoplastic elastomer with comb structure is synthesized.
The current industrial production methods of ethylene/α -olefin copolymer comprise three methods of solution method, gas phase method and slurry method (prog. Polym. Sci.2001,26,1287-1336.) however, in the production of POE with high α -olefin content, all companies adopt high temperature solution method, the product performance of POE obtained by the solution method, including toughness and elasticity, are obviously superior to those of products obtained by the gas phase method, although there is a patent report (US5770664) for producing POE by the slurry method, because the melting point of POE is low, the POE is easy to swell in solvent, the product is easy to melt and agglomerate, at present, there is no industrial example for producing POE by the slurry method.
Disclosure of Invention
The invention aims to provide a preparation method of a comb-shaped propenyl polyolefin thermoplastic elastomer aiming at the defects of the existing production products and technologies.
The purpose of the invention is realized by the following technical scheme: a preparation method of a comb-shaped propylene-based polyolefin thermoplastic elastomer comprises the following steps:
(1) adding propylene, a propylene homopolymerization catalyst, a cocatalyst and an organic solvent into a first reactor under the anhydrous and anaerobic conditions, and carrying out polymerization reaction to obtain a polypropylene macromonomer, wherein the polymerization temperature is 60-300 ℃, the polymerization pressure is 0.1-10Mpa, the concentration of the propylene homopolymerization catalyst is 0.1-100 mu mol/L, the molar ratio of the cocatalyst to the propylene homopolymerization catalyst is 50-10000: 1, the feeding concentration of the propylene is 0.1-20 mol/L, the residence time of all materials in the first reactor is controlled to be 2-240 min, the weight average molecular weight of the prepared polypropylene macromonomer is 1000-50000 g/mol, the molecular weight distribution index is 1.0-5.0, the proportion of terminal double bonds is controlled to be more than 50%, and the isotacticity [ mmmm ] or the syndiotactic [ rrr ] of the polypropylene is controlled to be more than 50%;
(2) the method comprises the steps of enabling a polymer solution obtained through polymerization reaction in a first reactor to enter a second reactor, adding propylene, ethylene, a copolymerization catalyst, a cocatalyst and an organic solvent into the second reactor under the anhydrous and oxygen-free conditions, carrying out ternary copolymerization on ethylene/propylene/polypropylene macromonomer, enabling the polymerization temperature to be 60-300 ℃, the polymerization pressure to be 0.1-10MPa, enabling the concentration of the copolymerization catalyst to be 0.1-100 mu mol/L based on the volume of the organic solvent in a reaction kettle, enabling the molar ratio of the copolymerization catalyst to a propylene homopolymerization catalyst to be 20: 1-1: 10, enabling the molar ratio of the cocatalyst to the copolymerization catalyst to be 50-10000: 1, enabling the ethylene feeding concentration to be 0.1-20 mol/L, enabling the feeding molar ratio of the propylene to the ethylene to be 0.1-25: 1, controlling the residence time of all materials in the second reactor to be 2-240 min, and enabling the weight average molecular weight of the prepared copolymer to be 500000g/mol, the molecular weight distribution index to be 1.0.10-10, and the propylene content to be 0.1-10 mol/95-10 mol%.
Further, the propylene homopolymerization catalyst is a single-site metallocene catalyst or a post-metallocene catalyst, and is selected from rac-ethylene bridged bis-indenyl zirconium dichloride, rac-dimethylsilyl bridged-bis (2-methylindenyl) zirconium dichloride, rac-dimethylsilyl bridged-bis (2-methyl-4-phenyl-indenyl) zirconium dichloride, rac-dimethylsilyl bridged-bis-indenyl dimethyl hafnium, meso-diphenylmethyl bridged-cyclopentadienyl-fluorenyl-zirconium dichloride, bis (dimethylsilyl) - (3, 5-diisopropylcyclopentadienyl) - (4-isopropylcyclopentadienyl) zirconium dichloride, dimethylsilyl-fluorenyl-tert-butylamino-dimethyl titanium, and, Bis (3-trimethylsilylsalicyl-3, 5-difluorophenyl) titanium dichloride.
Further, the copolymerization catalyst is a single-site metallocene catalyst or post-metallocene catalyst selected from 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, dimethylsilyl-bisindenyl zirconium dichloride, diphenylcarbabridged-cyclopentadienyl-fluorenyl zirconium dichloride, 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 cocatalyst is selected from methylaluminoxane, modified methylaluminoxane, a tris (pentafluorophenyl) boron compound, triisobutylaluminum, triethylaluminum and trimethylaluminum.
Further, the organic solvent is straight-chain alkane, isoparaffin, cycloalkane or aralkane with 4-10 carbon atoms.
Further, the organic solvent is preferably n-pentane, isopentane, n-hexane, cyclohexane, n-heptane, isoheptane, n-octane, isooctane, n-decane, isoparaffin oil, toluene, xylene.
Further, the ratio of the terminal double bonds of the polypropylene macromonomer prepared in step 1 is preferably 80% or more. The isotactic or syndiotactic degree of polypropylene is preferably 80% or more.
Further, the elongation at break of the polymer prepared in the step 2 is more than 100%, and the breaking strength is more than 1 MPa.
The invention has the beneficial effects that: based on the high-temperature high-pressure cascade continuous solution polymerization technology of a cascade metallocene catalytic system with high activity, high selectivity and high copolymerization capacity, the novel polyolefin thermoplastic elastomer with the crystalline polypropylene hard segment as a side chain and the amorphous ethylene/propylene random copolymer as a main chain is prepared, can be used for replacing the application field of the traditional polyolefin thermoplastic elastomer and has high industrial value.
Detailed Description
The present invention is illustrated by the following specific examples, but the scope of the present invention is not limited to the following examples.
The feed molar concentration to be used in the present invention means the initial concentration of the propylene monomer when entering the reaction vessel in terms of the volume of the organic solvent, and the feed molar ratio means the initial molar concentration ratio of the propylene monomer to the ethylene monomer when entering the reaction vessel.
Examples 1 to 15 were high-temperature high-pressure two-pot series continuous solution polymerizations carried out in two 300ml polymerization reactors.
Example 1
In the experiment, the main catalyst homopolymerization catalyst adopts rac-dimethylsilicon bridged-bis (2-methyl-4-phenyl-indenyl) zirconium dichloride, the copolymerization catalyst adopts dimethylsilyl bridged-tetramethylcyclopentadienyl-tert-butylamino-dimethyl titanium, the cocatalyst adopts methylaluminoxane, the solvent is Isopar E, the monomers are ethylene and propylene, and the polymerization experiment is carried out in a double-kettle series high-temperature high-pressure continuous solution system. Prior to the experiment, the autoclave and tubing were purged with a solution of triisobutylaluminum and Isopar E to remove water oxygen. Weighing a certain amount of homopolymerization catalyst, copolymerization catalyst and cocatalyst, transferring under the protection of nitrogen atmosphere, preparing solutions with Isopar E respectively, and storing the solutions in respective storage tanks, wherein the solvent Isopar E is also stored in a solvent storage tank.
The experimental steps comprise opening a reaction kettle and a pipeline oil bath, raising the temperature of a kettle 1 to 120 ℃, raising the temperature of a kettle 2 to 140 ℃, setting the stirring speed to 1000rpm, opening a feeding valve and a discharging valve of the two kettles, opening No. 1-5 high-pressure chemical metering pumps, continuously inputting propylene, a propylene homopolymerization catalyst, an auxiliary catalyst and a solvent into the reaction kettle according to a set flow rate, continuously inputting the propylene, the propylene homopolymerization catalyst, the auxiliary catalyst and the solvent into the kettle 1, continuously inputting the kettle 1, the copolymerization catalyst, the auxiliary catalyst, ethylene and the solvent into the kettle 2, decompressing and discharging the kettle 2 to obtain a final product, controlling the pressure in the reaction kettle through a proportional valve, opening a propylene air inlet valve when the pressure of the kettle 1 is stabilized at 22bar and the pressure of the kettle 2 is stabilized at 20bar, opening an ethylene air inlet valve, enabling ethylene to enter the reaction kettle 2 through a flow meter at a constant speed, controlling the concentration of the homopolymerization catalyst in the kettle 1 to be 4 mu mol/L, the concentration of the auxiliary catalyst to be 10 mmol/L, controlling the molar ratio of the auxiliary catalyst to be 5000, controlling the concentration of the propylene in the reaction kettle 1, controlling the feeding concentration of the auxiliary catalyst to be 70.92 mol/L, controlling the concentration of the ethylene in the reaction kettle 1, controlling the feeding kettle to be 70 mu mol/368, controlling the concentration of the dry material in the reaction kettle at about 20 min, controlling the concentration of the dry material in the reaction kettle, controlling the reaction kettle after the dry concentration of the dry acidification kettle, controlling the concentration of the dry material in the acidification kettle at about 20 min, the acidification kettle at 70.20 mu mol/368, controlling the concentration of the acidification kettle, controlling the concentration.
The molecular weight (Mw and Mn) and the distribution index (PDI) of the polymer are measured by high-temperature gel permeation chromatography (P L-GPC 220), 1,2, 4-trichlorobenzene is used as a solvent to prepare a 0.1-0.3 wt% polymer solution at 150 ℃, polystyrene with narrow molecular weight distribution is used as a standard sample to measure at 150 ℃, the flow rate of the solvent is 1.0ml/min, the parameter k is 5.91 × 10-4, the parameter α is 0.69, the parameter k is 15.6 × 10-4, and the parameter α is 0.76 for all PS standard samples.
The melting point (Tm) of the copolymer was determined by TA Instruments Q200. And (3) taking a 5.0-7.0 mg polymer sample, heating to 190 ℃ at a speed of 30 ℃/min, keeping the temperature for 5min to eliminate thermal history, then cooling to-90 ℃ at a speed of 10 ℃/min, keeping the temperature for 3min, heating to 190 ℃ at a speed of 10 ℃/min, and obtaining the melting point of the polymer from the second heating curve.
Average composition of comonomer in copolymer Using carbon Spectroscopy Nuclear magnetism: (13C NMR) was measured at 125 ℃ and the instrument model was Bruker AC 400. The polymer is prepared into a deuterated o-dichlorobenzene solution with the mass fraction of 10% at 150 ℃, and the deuterated o-dichlorobenzene solution is dissolved in advance for 3 to 4 hours, so 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.
Uniaxial tensile testing of the polymers was carried out in a universal materials tester (INSTRON 2710-100, Germany) at room temperature at a tensile rate of 50mm/min, with 5 replicates per sample. The polymer specimens were produced by compression molding at 170 ℃ and quenching at room temperature, the shape and size of which were determined by cutting with a cutter according to model 5 (GBT 1040.3-2006), and the thickness was about 0.3 mm.
Example 2
The experimental conditions were that after the system reached steady state, the concentration of the homopolymerization catalyst in the reactor 1 was 2. mu. mol/L, the concentration of the cocatalyst was 10 mmol/L, the molar ratio of cocatalyst to homopolymerization catalyst was 10000, and the other experimental conditions were the same as in example 1.
Example 3
The experimental conditions were that after the system reached steady state, the concentration of the homopolymerization catalyst in the reactor 1 was 6. mu. mol/L, the concentration of the cocatalyst was 10 mmol/L, the molar ratio of the cocatalyst to the homopolymerization catalyst was 2500, and the other experimental conditions were the same as in example 1.
Example 4
The experimental conditions were that after the system reached steady state, the concentration of the homopolymerization catalyst in the reactor 1 was 8. mu. mol/L, the concentration of the cocatalyst was 10 mmol/L, and the molar ratio of the cocatalyst to the homopolymerization catalyst was 1250, and the other experimental conditions were the same as in example 1.
Example 5
The experimental conditions were that the concentration of the copolymerization catalyst in the reactor 2 was 40. mu. mol/L, the concentration of the cocatalyst was 20 mmol/L, the molar ratio of the cocatalyst to the main catalyst was 500 after the system reached steady state, and the other experimental conditions were the same as in example 1.
Example 6
The experimental conditions were that after the system reached steady state, the concentration of the copolymerization catalyst in the reactor 2 was 10. mu. mol/L, the concentration of the cocatalyst was 20 mmol/L, the molar ratio of cocatalyst to the main catalyst was 2000, and the other experimental conditions were the same as in example 1.
Example 7
The experimental conditions were that after the system reached steady state, the pressure in tank 1 was stabilized at 12bar, the pressure in tank 2 was stabilized at 10bar, the feed concentration of propylene in tank 1 was 0.46 mol/L, the feed concentration of propylene in tank 2 was 0.40 mol/L, the feed concentration of ethylene was 0.195 mol/L, and the molar ratio of propylene feed to ethylene feed was 2.05, otherwise the experimental conditions were the same as in example 1.
Example 8
The experimental conditions were that after the system reached steady state, the pressure in tank 1 was stabilized at 6bar, the pressure in tank 2 was stabilized at 5bar, the feed concentration of propylene in tank 1 was 0.23 mol/L, the feed concentration of propylene in tank 2 was 0.20 mol/L, the feed concentration of ethylene was 0.096 mol/L, and the molar ratio of propylene feed to ethylene feed was 2.08, and the other experimental conditions were the same as in example 1.
Example 9
The experimental conditions were the same as in example 1 except that after the system reached steady state, the propylene feed concentration in tank 1 was 0.92 mol/L, the propylene feed concentration in tank 2 was 0.80 mol/L, the ethylene feed concentration was 0.53 mol/L, and the molar ratio of propylene feed to ethylene feed was 1.50.
Example 10
The experimental conditions were the same as in example 1 except that after the system reached steady state, the propylene feed concentration in tank 1 was 0.92 mol/L, the propylene feed concentration in tank 2 was 0.80 mol/L, the ethylene feed concentration was 0.64 mol/L, and the molar ratio of propylene feed to ethylene feed was 1.25.
Example 11
The experimental conditions were the same as in example 1 except that the propylene feed concentration was 0.92 mol/L, the propylene feed concentration in tank 2 was 0.80 mol/L, the ethylene feed concentration was 0.08 mol/L, and the molar ratio of propylene feed to ethylene feed was 10.0 after the system reached steady state.
Example 12
The experimental conditions were: after the system reached a steady state, the residence time of tank 1 was 6min, the residence time of tank 2 was 5min, and the other experimental conditions were the same as in example 1.
Example 13
The experimental conditions were: after the system reaches a steady state, the residence time of the kettle 1 is 10min, the residence time of the kettle 2 is 8min, and other experimental conditions are the same as those in example 1.
Example 14
The experimental conditions were the same as in example 1 except that after the system reached steady state, the polymerization temperature in tank 2 was maintained at 160 ℃, the propylene feed concentration in tank 1 was 0.92 mol/L, the propylene feed concentration in tank 2 was 0.80 mol/L, the ethylene feed concentration was 0.39 mol/L, and the molar ratio of propylene feed to ethylene feed was 2.05.
Example 15
The experimental conditions were: the copolymerization catalyst was changed to diphenylcarba-bridged-cyclopentadienyl-fluorenyl zirconium dichloride, and the other experimental conditions were the same as in example 1.
Example 16 is a high temperature, high pressure batch copolymerization conducted in a 500ml olefin batch polymerization reactor.
Example 16
In the experiment, the main catalyst homopolymerization catalyst adopts rac-dimethylsilicon bridged-bis (2-methyl-4-phenyl-indenyl) zirconium dichloride, the copolymerization catalyst adopts dimethylsilyl-tetramethylcyclopentadienyl-tert-butylamino-dimethyl titanium, the cocatalyst adopts methylaluminoxane, the solvent is Isopar E, the monomers are ethylene and propylene, and the polymerization experiment is carried out in a high-temperature high-pressure batch solution system. Before the experiment, the reaction kettle is repeatedly vacuumized and replaced by nitrogen for 6 hours at the temperature of 100 ℃, and then vacuumized and replaced by propylene for three times, so that the whole pipeline and the inside of the reaction kettle meet the requirements of sealing, no water and no oxygen.
The experimental steps are as follows: firstly heating a reaction kettle to 120 ℃, then opening a liquid feed valve, adding 220ml of solvent Isopar E and 10mmol of cocatalyst into the reaction kettle, then immediately closing the liquid feed valve, opening and stirring to 1000 r/min, adding a homopolymerization catalyst into the reaction kettle through pressure difference after the temperature in the kettle is raised to the reaction temperature, rapidly increasing the pressure in the kettle to 1.0MPa, and then continuously supplying the propylene 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 10min, adding a copolymerization catalyst into the reaction kettle by pressure difference, opening an ethylene air inlet valve, continuing to react for 30min, closing a gas inlet valve, opening a gas vent valve to release pressure, then opening a liquid discharge valve, and pouring the material 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 homopolymerization catalyst in the kettle is 2 mu mol/L, the concentration of the copolymerization catalyst is 10 mu mol/L, the feeding molar ratio of propylene to ethylene is 2.05, and all materials used in the experiment are subjected to water removal and oxygen removal treatment.
Example 17 is a high temperature, high pressure, serial continuous solution polymerization in two reactors, 300ml loop reactor and 300ml polymerization reactor.
Example 17
In the experiment, the main catalyst homopolymerization catalyst adopts rac-dimethylsilicon bridged-bis (2-methyl-4-phenyl-indenyl) zirconium dichloride, the copolymerization catalyst adopts dimethylsilyl bridged-tetramethylcyclopentadienyl-tert-butylamino-dimethyl titanium, the cocatalyst adopts methylaluminoxane, the solvent is Isopar E, the monomers are ethylene and propylene, and the polymerization experiment is carried out in a series high-temperature high-pressure continuous solution system. Prior to the experiment, the autoclave and tubing were purged with a solution of triisobutylaluminum and Isopar E to remove water oxygen. Weighing a certain amount of homopolymerization catalyst, copolymerization catalyst and cocatalyst, transferring under the protection of nitrogen atmosphere, preparing solutions with Isopar E respectively, and storing the solutions in respective storage tanks, wherein the solvent Isopar E is also stored in a solvent storage tank.
The experimental steps comprise opening a reaction kettle and a pipeline oil bath, raising the temperature of a loop reactor to 120 ℃, raising the temperature of the reaction kettle to 140 ℃, setting the stirring speed to 1000rpm, opening a feeding valve and a discharging valve of the two reactors, opening No. 1-5 high-pressure chemical metering pumps, continuously inputting propylene, a propylene homopolymerization catalyst, an auxiliary catalyst and a solvent into the reaction kettle according to a set flow rate, continuously inputting the propylene, the propylene homopolymerization catalyst, the auxiliary catalyst and the solvent into the loop reactor, continuously inputting the propylene, the copolymerization catalyst, the auxiliary catalyst, ethylene and the solvent into the reaction kettle, decompressing and discharging the reaction kettle to obtain a final product, controlling the pressure in the reaction kettle through a proportional valve, opening a propylene air inlet valve when the pressure of the loop reactor is stabilized at 22bar and the pressure in the reaction kettle is stabilized at 20bar, opening an ethylene air inlet valve, enabling ethylene to enter the reaction kettle through a flow meter at a constant speed, controlling the concentration of the homopolymerization catalyst in the loop reactor to be 4 mu mol/L, the concentration of the auxiliary catalyst to be 10 mmol/L, controlling the molar ratio of the main catalyst to be 5000, the feeding concentration of the ethylene and the auxiliary catalyst to be 2 mol/L, controlling the concentration of the ethylene in the loop reactor when the feeding material is stabilized, controlling the feeding temperature of the loop reactor to be 70.8 min, controlling the concentration of the ethylene, controlling the ethylene, the concentration of the ethylene, controlling the concentration of the ethylene and the ethylene in the loop reactor to be 70.20 mol/368, controlling the concentration of the pressure of the loop reactor, controlling the concentration of the ethylene, controlling the concentration of the ethylene in the loop reactor, controlling the concentration of the pressure of the ethylene, controlling the concentration of the pressure of the ethylene.
TABLE 1 Experimental results of the tandem catalytic continuous solution copolymerization
Note: ENGAGE 8150 represents a POE industrial sample from DOW
As shown in the above Table 1, a series of comb-shaped propylene-based polyolefin thermoplastic elastomers are prepared under the conditions of high temperature and high pressure, and the mechanical properties show that the polymers all show the properties of typical thermoplastic elastomers. Compared with industrial samples, the elastomer has a higher melting point (>140 ℃) and shows a wider use temperature than POE.
Claims (7)
1. The preparation method of the comb-shaped propenyl polyolefin thermoplastic elastomer is characterized by comprising the following steps:
(1) adding propylene, a propylene homopolymerization catalyst, a cocatalyst and an organic solvent into a first reactor under the anhydrous and anaerobic conditions, and carrying out polymerization reaction to obtain a polypropylene macromonomer, wherein the polymerization temperature is 60-300 ℃, the polymerization pressure is 0.1-10MPa, the concentration of the propylene homopolymerization catalyst is 0.1-100 mu mol/L, the molar ratio of the cocatalyst to the propylene homopolymerization catalyst is 50-10000: 1, the feeding concentration of the propylene is 0.1-20 mol/L, the residence time of all materials in the first reactor is controlled to be 2-240 min, the weight average molecular weight of the prepared polypropylene macromonomer is 1000-50000 g/mol, the molecular weight distribution index is 1.0-5.0, the proportion of double bonds at the tail end of the polypropylene macromonomer is more than 80%, and the isotacticity or the syndiotactic degree of the polypropylene is more than 80%;
(2) the method comprises the steps of enabling a polymer solution obtained through polymerization reaction in a first reactor to enter a second reactor, adding propylene, ethylene, a copolymerization catalyst, a cocatalyst and an organic solvent into the second reactor under the anhydrous and oxygen-free conditions, carrying out ternary copolymerization on ethylene/propylene/polypropylene macromonomer, enabling the polymerization temperature to be 60-300 ℃, the polymerization pressure to be 0.1-10MPa, enabling the concentration of the copolymerization catalyst to be 0.1-100 mu mol/L based on the volume of the organic solvent in a reaction kettle, enabling the molar ratio of the copolymerization catalyst to a propylene homopolymerization catalyst to be 20: 1-1: 10, enabling the molar ratio of the cocatalyst to the copolymerization catalyst to be 50-10000: 1, enabling the ethylene feeding concentration to be 0.1-20 mol/L, enabling the feeding molar ratio of the propylene to the ethylene to be 0.1-25: 1, controlling the residence time of all materials in the second reactor to be 2-240 min, and enabling the weight average molecular weight of the prepared copolymer to be 500000g/mol, the molecular weight distribution index to be 1.0.1-10, and the propylene content to be 0.1-10 mol/95-95% of the main chain.
2. The process according to claim 1, wherein the propylene homopolymerization catalyst is a single-site metallocene catalyst or a post-metallocene catalyst selected from rac-ethylenebridged bis-indenyl zirconium dichloride, rac-dimethylsilicon-bridged-bis (2-methylindenyl) zirconium dichloride, rac-dimethylsilicon-bridged-bis (2-methyl-4-phenyl-indenyl) zirconium dichloride, rac-dimethylsilicon-bridged-bis-indenyl hafnium dimethyl, meso-diphenylmethyl-bridged-cyclopentadienyl-fluorenyl-zirconium dichloride, bis (dimethylsilyl) - (3, 5-diisopropylcyclopentadienyl) - (4-isopropylcyclopentadienyl) zirconium dichloride, dimethylsilicon-fluorenyl-tert-butylamino-titanium dimethyl, and mixtures thereof, Bis (3-trimethylsilylsalicyl-3, 5-difluorophenyl) titanium dichloride.
3. The process according to claim 1, wherein the copolymerization catalyst is a single-site metallocene catalyst or post-metallocene catalyst selected from 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 (2-methyl-4, 5-phenyl-indenyl) zirconium dichloride, bis (cyclopentadienyl-bisphenoxy) zirconium dichloride, and post-metallocene catalysts, 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.
4. The method of claim 1, wherein the cocatalyst is selected from the group consisting of methylalumoxane, modified methylalumoxane, tris (pentafluorophenyl) boron compound, triisobutylaluminum, triethylaluminum, and trimethylaluminum.
5. The method according to claim 1, wherein the organic solvent is a linear alkane, an isoparaffin, a cycloalkane, or an arylalkane having 4 to 10 carbon atoms.
6. The method according to claim 5, wherein the organic solvent is selected from the group consisting of n-pentane, isopentane, n-hexane, cyclohexane, n-heptane, isoheptane, n-octane, isooctane, n-decane, toluene, and xylene.
7. The method of claim 1, wherein the polymer obtained in step (2) has an elongation at break of more than 100% and a strength at break of more than 1 MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811148679.3A CN109456445B (en) | 2018-09-29 | 2018-09-29 | Preparation method of comb-shaped propenyl polyolefin thermoplastic elastomer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811148679.3A CN109456445B (en) | 2018-09-29 | 2018-09-29 | Preparation method of comb-shaped propenyl polyolefin thermoplastic elastomer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109456445A CN109456445A (en) | 2019-03-12 |
| CN109456445B true CN109456445B (en) | 2020-08-04 |
Family
ID=65607155
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811148679.3A Active CN109456445B (en) | 2018-09-29 | 2018-09-29 | Preparation method of comb-shaped propenyl polyolefin thermoplastic elastomer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109456445B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN114539477A (en) * | 2022-01-05 | 2022-05-27 | 浙江大学衢州研究院 | Preparation method of ethylene propylene diene monomer |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1994021692A1 (en) * | 1993-03-18 | 1994-09-29 | Neste Oy | Ethylene-propylene copolymer and method for manufacturing the same |
| CN101331163A (en) * | 2005-09-15 | 2008-12-24 | 陶氏环球技术公司 | Catalytic olefin block copolymers via polymerizable shuttling agent |
| CN107949589A (en) * | 2015-09-14 | 2018-04-20 | 埃克森美孚化学专利公司 | It can be used as the atactic polypropylene comb block polyolefin of the modifying agent in polyolefin and hydrocarbon |
-
2018
- 2018-09-29 CN CN201811148679.3A patent/CN109456445B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1994021692A1 (en) * | 1993-03-18 | 1994-09-29 | Neste Oy | Ethylene-propylene copolymer and method for manufacturing the same |
| CN101331163A (en) * | 2005-09-15 | 2008-12-24 | 陶氏环球技术公司 | Catalytic olefin block copolymers via polymerizable shuttling agent |
| CN107949589A (en) * | 2015-09-14 | 2018-04-20 | 埃克森美孚化学专利公司 | It can be used as the atactic polypropylene comb block polyolefin of the modifying agent in polyolefin and hydrocarbon |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109456445A (en) | 2019-03-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109535323B (en) | Preparation method of comb-shaped propenyl polyolefin thermoplastic elastomer | |
| CN109384885B (en) | Preparation method of comb-shaped vinyl polyolefin thermoplastic elastomer | |
| US4916099A (en) | Solid catalyst component for olefin copolymerization and process for olefin copolymerization using said solid catalyst component | |
| CA1118945A (en) | Process for the polymerization ethylene | |
| CN111732682B (en) | Preparation method of cross-linked polyolefin for packaging high-light-transmittance solar cell | |
| CN114539478A (en) | Preparation method of comb-shaped polyolefin thermoplastic elastomer based on feeding strategy regulation and control | |
| CN109456445B (en) | Preparation method of comb-shaped propenyl polyolefin thermoplastic elastomer | |
| CA1150883A (en) | Process for producing propylene-ethylene block copolymers | |
| CN111635494A (en) | Preparation method of comb-shaped propenyl olefin polymer | |
| JPS62121711A (en) | Lowly crystalline ethylene random copolymer and its production | |
| WO1998030614A1 (en) | Propylene/ethylene copolymer, process for the production thereof, and molded articles thereof | |
| JP2021091896A (en) | Polyethylene resin composition | |
| EP1448633A1 (en) | Two-step polymerization process | |
| CN111662417A (en) | Preparation method of novel crosslinkable comb-shaped propenyl olefin polymer | |
| CN115232239B (en) | Ethylene-butene-octene terpolymer and preparation method and system thereof | |
| CN111704703A (en) | Preparation method of crosslinkable comb-shaped vinyl olefin polymer | |
| JP4538768B2 (en) | Polyolefin composition and method for producing the same. | |
| JP4783964B2 (en) | Polypropylene composition and method for producing the same | |
| KR100472771B1 (en) | high stereospecific polybutene-1 polymer and the highly active preparation method thereof | |
| CN110092856B (en) | Liquid copolymerized olefin, preparation method and application | |
| JPS6150087B2 (en) | ||
| JPH09110934A (en) | Propylene-ethylene copolymer, its production, and its molded item | |
| JP3984290B2 (en) | Polypropylene polymer resins made from highly active catalysts having a wide heat-processed window and articles made therefrom | |
| CN114539477A (en) | Preparation method of ethylene propylene diene monomer | |
| CN115850586A (en) | Comb-shaped ethylene-propylene copolymer, cross-linked comb-shaped ethylene-propylene copolymer and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |