CN116023532A - Preparation method of saturated metallocene poly alpha-olefin - Google Patents
Preparation method of saturated metallocene poly alpha-olefin Download PDFInfo
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- CN116023532A CN116023532A CN202111241242.6A CN202111241242A CN116023532A CN 116023532 A CN116023532 A CN 116023532A CN 202111241242 A CN202111241242 A CN 202111241242A CN 116023532 A CN116023532 A CN 116023532A
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- Prior art keywords
- dimethylindenyl
- zirconium dichloride
- dichloride
- borate
- hafnium
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- 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.)
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- 229920013639 polyalphaolefin Polymers 0.000 title claims abstract description 51
- 229920006395 saturated elastomer Polymers 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 30
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000001257 hydrogen Substances 0.000 claims abstract description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 20
- 239000012968 metallocene catalyst Substances 0.000 claims abstract description 18
- 239000000178 monomer Substances 0.000 claims abstract description 12
- 239000004711 α-olefin Substances 0.000 claims abstract description 12
- 239000012190 activator Substances 0.000 claims abstract description 7
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 3
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 46
- -1 ethylenebisindenyl zirconium dichloride Chemical compound 0.000 claims description 42
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 36
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 25
- 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 23
- 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 23
- 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 claims description 15
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 13
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 claims description 12
- 238000004821 distillation Methods 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 10
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 claims description 8
- VQOXUMQBYILCKR-UHFFFAOYSA-N 1-Tridecene Chemical compound CCCCCCCCCCCC=C VQOXUMQBYILCKR-UHFFFAOYSA-N 0.000 claims description 8
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 claims description 8
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 claims description 8
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 8
- JRZJOMJEPLMPRA-UHFFFAOYSA-N 1-nonene Chemical compound CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 8
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 claims description 8
- DCTOHCCUXLBQMS-UHFFFAOYSA-N 1-undecene Chemical compound CCCCCCCCCC=C DCTOHCCUXLBQMS-UHFFFAOYSA-N 0.000 claims description 8
- 238000005984 hydrogenation reaction Methods 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 claims description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 4
- ADOBXTDBFNCOBN-UHFFFAOYSA-N 1-heptadecene Chemical compound CCCCCCCCCCCCCCCC=C ADOBXTDBFNCOBN-UHFFFAOYSA-N 0.000 claims description 4
- PJLHTVIBELQURV-UHFFFAOYSA-N 1-pentadecene Chemical compound CCCCCCCCCCCCCC=C PJLHTVIBELQURV-UHFFFAOYSA-N 0.000 claims description 4
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 4
- KUNZSLJMPCDOGI-UHFFFAOYSA-L [Cl-].[Cl-].[Hf+2] Chemical compound [Cl-].[Cl-].[Hf+2] KUNZSLJMPCDOGI-UHFFFAOYSA-L 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 229940069096 dodecene Drugs 0.000 claims description 4
- VAMFXQBUQXONLZ-UHFFFAOYSA-N n-alpha-eicosene Natural products CCCCCCCCCCCCCCCCCCC=C VAMFXQBUQXONLZ-UHFFFAOYSA-N 0.000 claims description 4
- NHLUYCJZUXOUBX-UHFFFAOYSA-N nonadec-1-ene Chemical compound CCCCCCCCCCCCCCCCCC=C NHLUYCJZUXOUBX-UHFFFAOYSA-N 0.000 claims description 4
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 claims description 4
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadec-1-ene Chemical compound CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 claims description 4
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 claims description 3
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 3
- 229940106006 1-eicosene Drugs 0.000 claims description 2
- FIKTURVKRGQNQD-UHFFFAOYSA-N 1-eicosene Natural products CCCCCCCCCCCCCCCCCC=CC(O)=O FIKTURVKRGQNQD-UHFFFAOYSA-N 0.000 claims description 2
- JBCJDHGAPWGIPC-UHFFFAOYSA-L CC(C)=[Hf+2](C1C=CC=C1)C1C2=C(C)C=CC(C)=C2C=C1.[Cl-].[Cl-] Chemical compound CC(C)=[Hf+2](C1C=CC=C1)C1C2=C(C)C=CC(C)=C2C=C1.[Cl-].[Cl-] JBCJDHGAPWGIPC-UHFFFAOYSA-L 0.000 claims description 2
- SBYQAHFMFSZPSO-UHFFFAOYSA-L CC(C)=[Zr+2](C1C=CC=C1)C1C2=C(C)C=CC(C)=C2C=C1.[Cl-].[Cl-] Chemical compound CC(C)=[Zr+2](C1C=CC=C1)C1C2=C(C)C=CC(C)=C2C=C1.[Cl-].[Cl-] SBYQAHFMFSZPSO-UHFFFAOYSA-L 0.000 claims description 2
- XCGSOQOXFGEESW-UHFFFAOYSA-L CCC(CC)=[Hf+2](C1C=CC=C1)C1C2=C(C)C=CC(C)=C2C=C1.[Cl-].[Cl-] Chemical compound CCC(CC)=[Hf+2](C1C=CC=C1)C1C2=C(C)C=CC(C)=C2C=C1.[Cl-].[Cl-] XCGSOQOXFGEESW-UHFFFAOYSA-L 0.000 claims description 2
- CYFYPJZUIBRYBU-UHFFFAOYSA-L CCCCC(C=C1)=C(C)C1[Hf+2](C1C(C)=C(CCCC)C=C1)[SiH](C)C.[Cl-].[Cl-] Chemical compound CCCCC(C=C1)=C(C)C1[Hf+2](C1C(C)=C(CCCC)C=C1)[SiH](C)C.[Cl-].[Cl-] CYFYPJZUIBRYBU-UHFFFAOYSA-L 0.000 claims description 2
- LQRJZRRAAVEUDP-UHFFFAOYSA-N CCC[Zr](CCC)(C1C=CC=C1)[SiH](C)C.Cl.Cl Chemical compound CCC[Zr](CCC)(C1C=CC=C1)[SiH](C)C.Cl.Cl LQRJZRRAAVEUDP-UHFFFAOYSA-N 0.000 claims description 2
- SLKHLFAQQPIJCS-UHFFFAOYSA-L CC[SiH]CC.Cl[Hf](Cl)(C1C=Cc2ccccc12)C1C=Cc2ccccc12 Chemical compound CC[SiH]CC.Cl[Hf](Cl)(C1C=Cc2ccccc12)C1C=Cc2ccccc12 SLKHLFAQQPIJCS-UHFFFAOYSA-L 0.000 claims description 2
- HKQMTZGUFSJHMQ-UHFFFAOYSA-L C[SiH]C.Cl[Hf](Cl)(C1C=CC=C1)C1C=CC=C1 Chemical compound C[SiH]C.Cl[Hf](Cl)(C1C=CC=C1)C1C=CC=C1 HKQMTZGUFSJHMQ-UHFFFAOYSA-L 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-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
- JCSRQZYANBDTOZ-UHFFFAOYSA-L [Cl-].[Cl-].C[SiH](C)[Zr+2](C1(C(=CC=C1)C)CCCC)C1(C(=CC=C1)C)CCCC Chemical compound [Cl-].[Cl-].C[SiH](C)[Zr+2](C1(C(=CC=C1)C)CCCC)C1(C(=CC=C1)C)CCCC JCSRQZYANBDTOZ-UHFFFAOYSA-L 0.000 claims description 2
- TYGPYZGVLXKYCG-UHFFFAOYSA-L [Cl-].[Cl-].Cc1ccc(C)c2C(C=Cc12)[Hf++](C1C=Cc2c1c(C)ccc2C)[SiH](c1ccccc1)c1ccccc1 Chemical compound [Cl-].[Cl-].Cc1ccc(C)c2C(C=Cc12)[Hf++](C1C=Cc2c1c(C)ccc2C)[SiH](c1ccccc1)c1ccccc1 TYGPYZGVLXKYCG-UHFFFAOYSA-L 0.000 claims description 2
- NKBOZRQSWJWPAO-UHFFFAOYSA-L [SiH](c1ccccc1)c1ccccc1.CC1=CC(C=C1)[Hf](Cl)(Cl)C1C=CC(C)=C1 Chemical compound [SiH](c1ccccc1)c1ccccc1.CC1=CC(C=C1)[Hf](Cl)(Cl)C1C=CC(C)=C1 NKBOZRQSWJWPAO-UHFFFAOYSA-L 0.000 claims description 2
- BWERVJKOOGHCEW-UHFFFAOYSA-L [SiH](c1ccccc1)c1ccccc1.CC1=CC(C=C1)[Zr](Cl)(Cl)C1C=CC(C)=C1 Chemical compound [SiH](c1ccccc1)c1ccccc1.CC1=CC(C=C1)[Zr](Cl)(Cl)C1C=CC(C)=C1 BWERVJKOOGHCEW-UHFFFAOYSA-L 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical group 0.000 claims description 2
- 125000005234 alkyl aluminium group Chemical group 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- DIOQZVSQGTUSAI-NJFSPNSNSA-N decane Chemical compound CCCCCCCCC[14CH3] DIOQZVSQGTUSAI-NJFSPNSNSA-N 0.000 claims description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-O diethylammonium Chemical compound CC[NH2+]CC HPNMFZURTQLUMO-UHFFFAOYSA-O 0.000 claims description 2
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 claims description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N n-butylhexane Natural products CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 2
- ZCIPNVZMTFGXOD-UHFFFAOYSA-N tri(nonyl)alumane Chemical compound CCCCCCCCC[Al](CCCCCCCCC)CCCCCCCCC ZCIPNVZMTFGXOD-UHFFFAOYSA-N 0.000 claims description 2
- IMFACGCPASFAPR-UHFFFAOYSA-O tributylazanium Chemical compound CCCC[NH+](CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-O 0.000 claims description 2
- FQMMZTDQJFUYSA-UHFFFAOYSA-N triheptylalumane Chemical compound CCCCCCC[Al](CCCCCCC)CCCCCCC FQMMZTDQJFUYSA-UHFFFAOYSA-N 0.000 claims description 2
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 claims description 2
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-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
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 claims description 2
- JOJQVUCWSDRWJE-UHFFFAOYSA-N tripentylalumane Chemical compound CCCCC[Al](CCCCC)CCCCC JOJQVUCWSDRWJE-UHFFFAOYSA-N 0.000 claims description 2
- CNWZYDSEVLFSMS-UHFFFAOYSA-N tripropylalumane Chemical compound CCC[Al](CCC)CCC CNWZYDSEVLFSMS-UHFFFAOYSA-N 0.000 claims description 2
- USJZIJNMRRNDPO-UHFFFAOYSA-N tris-decylalumane Chemical compound CCCCCCCCCC[Al](CCCCCCCCCC)CCCCCCCCCC USJZIJNMRRNDPO-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- VPGLGRNSAYHXPY-UHFFFAOYSA-L zirconium(2+);dichloride Chemical compound Cl[Zr]Cl VPGLGRNSAYHXPY-UHFFFAOYSA-L 0.000 claims 2
- JAISZFQFJAQAQT-UHFFFAOYSA-L CC[SiH]CC.Cl[Zr](Cl)(C1C=Cc2ccccc12)C1C=Cc2ccccc12 Chemical compound CC[SiH]CC.Cl[Zr](Cl)(C1C=Cc2ccccc12)C1C=Cc2ccccc12 JAISZFQFJAQAQT-UHFFFAOYSA-L 0.000 claims 1
- VWOTWOPAYZNLIU-UHFFFAOYSA-L C[SiH]C.Cl[Zr](Cl)(C1C=CC=C1)C1C=CC=C1 Chemical compound C[SiH]C.Cl[Zr](Cl)(C1C=CC=C1)C1C=CC=C1 VWOTWOPAYZNLIU-UHFFFAOYSA-L 0.000 claims 1
- NZDLIIBVQQCHBI-UHFFFAOYSA-L Cl[Zr]Cl.CC1=C[CH]C=C1 Chemical compound Cl[Zr]Cl.CC1=C[CH]C=C1 NZDLIIBVQQCHBI-UHFFFAOYSA-L 0.000 claims 1
- ONIXKSAHVIIWFQ-UHFFFAOYSA-L [Cl-].[Cl-].C[SiH](C)[Zr++](C1C=Cc2c1c(C)ccc2C)C1C=Cc2c1c(C)ccc2C Chemical compound [Cl-].[Cl-].C[SiH](C)[Zr++](C1C=Cc2c1c(C)ccc2C)C1C=Cc2c1c(C)ccc2C ONIXKSAHVIIWFQ-UHFFFAOYSA-L 0.000 claims 1
- PCRVPTVYRLHWKZ-UHFFFAOYSA-L [Cl-].[Cl-].Cc1ccc(C)c2C(C=Cc12)[Zr++](C1C=Cc2c1c(C)ccc2C)[SiH](c1ccccc1)c1ccccc1 Chemical compound [Cl-].[Cl-].Cc1ccc(C)c2C(C=Cc12)[Zr++](C1C=Cc2c1c(C)ccc2C)[SiH](c1ccccc1)c1ccccc1 PCRVPTVYRLHWKZ-UHFFFAOYSA-L 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 10
- 239000002994 raw material Substances 0.000 abstract description 10
- 238000006243 chemical reaction Methods 0.000 description 21
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 15
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 15
- 229910052794 bromium Inorganic materials 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 11
- 239000000203 mixture Substances 0.000 description 10
- 229910001873 dinitrogen Inorganic materials 0.000 description 9
- 238000011056 performance test Methods 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000002199 base oil Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000010687 lubricating oil Substances 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002685 polymerization catalyst Substances 0.000 description 2
- OPQDIKQGTDOHCY-UHFFFAOYSA-L CCC(CC)=[Zr+2](C1C=CC=C1)C1C2=C(C)C=CC(C)=C2C=C1.[Cl-].[Cl-] Chemical compound CCC(CC)=[Zr+2](C1C=CC=C1)C1C2=C(C)C=CC(C)=C2C=C1.[Cl-].[Cl-] OPQDIKQGTDOHCY-UHFFFAOYSA-L 0.000 description 1
- VUPIVVISEUYJQH-UHFFFAOYSA-L CCCC1=CC(C=C1)[Zr](Cl)(Cl)(C1C=CC(CCC)=C1)[SiH](C)C Chemical group CCCC1=CC(C=C1)[Zr](Cl)(Cl)(C1C=CC(CCC)=C1)[SiH](C)C VUPIVVISEUYJQH-UHFFFAOYSA-L 0.000 description 1
- KOELNXRXBKYALK-UHFFFAOYSA-N CCC[Hf](CCC)(C1C=CC=C1)[SiH](C)C.Cl.Cl Chemical group CCC[Hf](CCC)(C1C=CC=C1)[SiH](C)C.Cl.Cl KOELNXRXBKYALK-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 1
- VCOKPLHNHKEXIO-UHFFFAOYSA-L [Cl-].[Cl-].CC1=CC=C(C)C2=C1C=CC2[Zr+2] Chemical compound [Cl-].[Cl-].CC1=CC=C(C)C2=C1C=CC2[Zr+2] VCOKPLHNHKEXIO-UHFFFAOYSA-L 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 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
- JZZIHCLFHIXETF-UHFFFAOYSA-N dimethylsilicon Chemical compound C[Si]C JZZIHCLFHIXETF-UHFFFAOYSA-N 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000012208 gear oil Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Images
Classifications
-
- 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
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- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention discloses a preparation method of saturated metallocene poly alpha-olefin. The preparation method comprises the following steps: polymerizing alpha-olefin monomer in the presence of metallocene catalyst and activator, removing unreacted monomer, and adding hydrogen to hydrogenate. The method of the invention does not need to add extra catalyst, saves equipment investment and raw material cost, does not cause saturation and loss to raw materials, and the prepared saturated metallocene poly alpha-olefin has excellent performance.
Description
Technical Field
The invention relates to a preparation method of saturated metallocene poly alpha-olefin.
Background
Poly-Alpha-Olefins (PAO) is a fully synthetic hydrocarbon lubricant base oil prepared by a chemical synthesis method, has the advantages of high viscosity index, excellent low-temperature performance, good thermal oxidation stability, low volatility, good shear stability and the like, and is currently considered to be the most potential fully synthetic lubricant base oil. PAO is usually polymerized by conventional catalysts such as Lewis acid or Ziegler-Natta catalysts, e.g. using BF 3 Catalytic preparation of low viscosity PAO using AlCl 3 Catalytic preparation of medium viscosity PAO high viscosity PAO was prepared using Ziegler-Natta catalyst catalysis. And the metallocene poly alpha-olefin (mPAO) is a product which is obtained by catalyzing alpha-olefin polymerization by a metallocene catalyst and has a comb structure and no upright side chain. Such structures affect PAO product performance and mPAO generally possesses improved rheological and flow characteristics, providing better shear than conventional PAOsShear stability, lower pour point and higher viscosity index, has good viscosity-temperature characteristics. These characteristics determine that the mPAO can be used in high severity environments, including power transmission and gear oils, compressor lubricating oils, transmission fluids, and industrial lubricating oils. Along with the increasing requirements of society on energy utilization rate and ecological environment protection, the demand of people on high-performance mPAO lubricating oil base oil is increased.
The mPAO prepared by catalyzing alpha-olefin with metallocene compound has double bond in the structure. In order to improve the oxidation resistance of the mPAO, the mPAO must be hydrogenated to saturation.
CN105008409B discloses a process for producing an alpha-olefin polymer and a hydrogenated alpha-olefin polymer. The addition of hydrogen during polymerization is disclosed therein. The addition of hydrogen during the polymerization process tends to cause problems with the saturation of the feed. Although it discloses the hydrogenation of the prepared alpha-olefin polymer, no specific hydrogenation scheme is disclosed.
CN104370675B discloses a process for preparing polyalphaolefins in a continuous manner, but it requires the addition of an additional catalyst, for example 17 thereof, to which 0.5 wt% (based on the total weight of polyalphaolefin to be hydrotreated) of basf Ni-5249 catalyst is added, hydrogen is introduced thereto until the hydrogen pressure is 4.0MPa, the reaction vessel is heated to 200 ℃ and reacted at this temperature for 3 hours. By means of hydrogenation catalysts, such as nickel, equipment investment and raw material costs are increased.
To sum up, at present, there are two main methods for hydrogenating saturated mPAO, namely, hydrogenation catalyst such as nickel or other noble metal inorganic substances is used for carrying out fixed bed or kettle hydrogenation; in the other, hydrogen is added to regulate the molecular weight during the polymerization process, and saturated mPAO is prepared. The former hydrogenation process increases equipment investment and raw material costs, and the latter tends to cause raw materials to be saturated. For this reason, it is necessary to find an economical way to hydrogenate saturated mPAO.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention provides a novel preparation method of saturated metallocene poly alpha-olefin, which uses the self catalytic hydrogenation saturation characteristic of a polymerization catalyst metallocene compound to saturate double bonds in a mPAO structure by adding hydrogen. Therefore, the method of the invention does not need to add extra catalyst, saves equipment investment and raw material cost, does not cause saturation loss to raw materials, and the prepared saturated metallocene poly alpha-olefin has excellent performance.
The first aspect of the invention provides a method for preparing saturated metallocene poly alpha-olefin, comprising the following steps: polymerizing alpha-olefin monomer in the presence of metallocene catalyst and activator, removing unreacted monomer, and adding hydrogen to hydrogenate.
According to some embodiments of the preparation process of the present invention, preferably, the hydrogenation reaction conditions include: the temperature is 50-150 ℃, the time is 0.5-12 h, and the hydrogen pressure is 0.1-2 MPa.
According to some embodiments of the preparation process of the present invention, preferably, the process for removing unreacted monomers is distillation under reduced pressure.
According to some embodiments of the preparation process of the present invention, preferably, the α -olefin is selected from one or more of 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene and 1-eicosene, preferably one or more of 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene and 1-tetradecene.
According to some embodiments of the preparation method of the present invention, preferably, the metallocene catalyst is selected from dimethylsilylbis (n-propylcyclopentadienyl) zirconium dichloride, dimethylsilylbis (indenyl) zirconium dichloride, diethylsilylbis (4, 7-dimethylindenyl) zirconium dichloride, dimethylsilylbis (indenyl) zirconium dichloride, diphenylsilylbis (2-methylcyclopentadienyl) zirconium dichloride, ethylenebisindenyl zirconium dichloride, ethylenebis (2-methylindenyl) zirconium dichloride, dimethylsilylbis (2-methyl-3-butylcyclopentadienyl) zirconium dichloride, dimethylsilylbis (3, 5-dimethylindenyl) zirconium dichloride, diethylmethylenecyclopentadienyl (4, 7-dimethylindenyl) zirconium dichloride, dimethylmethylenecyclopentadienyl (4, 7-dimethylindenyl) zirconium dichloride, dimethylsilyclopentadienyl (4, 7-dimethylindenyl) zirconium dichloride, dimethylsilenyl (2-dimethylindenyl) zirconium dichloride Dimethylsilylbis-indenyl hafnium dichloride, diethylsilylbis-indenyl hafnium dichloride, diphenylsilylbis (4, 7-dimethylindenyl) hafnium dichloride, dimethylsilylenebis (4, 7-dimethylindenyl) hafnium dichloride, diphenylsilylbis (2-methylcyclopentadienyl) hafnium dichloride, ethylenebisindenyl hafnium dichloride, ethylenebis (2-methylindenyl) hafnium dichloride, dimethylsilylbis (2-methyl-3-butylcyclopentadienyl) hafnium dichloride, dimethylsilylbiscyclopentadienyl hafnium dichloride, diethylmethylenecyclopentadienyl (3, 5-dimethylindenyl) hafnium dichloride, diethylmethylenecyclopentadienyl (4, 7-dimethylindenyl) hafnium dichloride, dimethylmethylenecyclopentadienyl (4, 7-dimethylindenyl) hafnium dichloride, dimethylcyclopentadienyl (4, 7-dimethylindenyl) hafnium dichloride, hafnium dimethylcyclopentadienyl (3, 5-dimethylindenyl) hafnium dichloride, dimethylcyclopentadienyl (2-dimethylindenyl) hafnium dichloride, and at least one of dimethylsilacyclopentadienyl (2-dimethylindenyl) hafnium dichloride.
According to some embodiments of the preparation method of the present invention, preferably, the activator is an aluminum alkyl and/or a borate.
According to some embodiments of the preparation method of the present invention, preferably, the aluminum alkyl has a chemical formula of AlR 3 Wherein R is C 1 -C 10 Preferably, the alkyl aluminum is at least one selected from trimethylaluminum, triethylaluminum, triisopropylaluminum, tri-n-propylaluminum, triisobutylaluminum, tri-n-butylaluminum, triisopentylaluminum, tri-n-pentylaluminum, triisohexylaluminum, tri-n-hexylaluminum, triisoheptylaluminum, tri-n-heptylaluminum, triisooctylaluminum, tri-n-octylaluminum, triisononylaluminum, tri-n-nonylaluminum, triisodecylaluminum and tri-n-decylaluminum.
According to some embodiments of the preparation method of the present invention, preferably, the borate is at least one selected from the group consisting of dimethylanilinium tetrakis (pentafluorophenyl) borate, diethylanilinium tetrakis (pentafluorophenyl) borate, dibutylanilinium tetrakis (pentafluorophenyl) borate, trimethylammonium tetrakis (pentafluorophenyl) borate, diethylammonium tetrakis (pentafluorophenyl) borate, and tributylammonium tetrakis (pentafluorophenyl) borate.
In the present invention, the ratio of the amount of the metallocene catalyst, the activator, and the α -olefin monomer may have a wide range, for example, but not limited to, the weight ratio of the metallocene catalyst, the activator, and the α -olefin monomer may be 1: (10-1000): (100-1X 10) 5 )。
According to some embodiments of the preparation process of the present invention, preferably, the polymerization reaction further comprises using a solvent, preferably, the solvent is an alkane solvent and/or an arene solvent, more preferably at least one selected from hexane, heptane, octane, nonane, decane, cyclohexane, benzene, toluene and xylene. In the present invention, the amount of the solvent may have a wide selection range, for example, the volume ratio of the solvent to the monomer is (1 to 1000): 1.
according to some embodiments of the preparation method of the present invention, preferably, the polymerization reaction conditions include: the temperature is 20-200 ℃, the pressure is 0.1-2 MPa, and the time is 0.5-5 h.
The invention has the beneficial effects that:
by adopting the method, no additional catalyst is needed, no saturation is caused to the raw materials, and the polymerization catalyst metallocene compound is used for carrying out the saturation of the product by the self catalytic hydrogenation. The economic benefit is high, and the method is suitable for industrial production.
Drawings
FIG. 1 is a process flow diagram of a method of preparing a saturated metallocene polyalphaolefin of example 1 of the present invention.
Detailed Description
In order that the invention may be more readily understood, the invention will be described in detail below with reference to the following examples, which are given by way of illustration only and are not limiting of the scope of application of the invention.
[ example 1 ]
The process flow diagram is shown in figure 1. Into a 500mL flask filled with nitrogen gas were charged 100g of 1-octene and 200mL of toluene, and the mixture was heated at a constant temperature of 100℃for 30 minutes, and 50mL of a metallocene catalyst solution (dimethylsilylbis-indenyl zirconium dichloride 3. Mu. Mol, dimethylanilinium tetrakis (pentafluorophenyl) borate 50mg, triethylaluminum 35 mg) was added. After 1 hour of reaction, unreacted 1-octene was removed by distillation under reduced pressure. Hydrogen of 0.1MPa was added at 100 c and the reaction was continued for 2 hours to finally obtain 92g of a saturated metallocene polyalphaolefin product, calculated to yield 92%.
The performance of the saturated metallocene polyalphaolefin product was tested with a kinematic viscosity at 100℃of 20cSt, a viscosity index of 191, a weight average molecular weight of 2843 and a bromine index of 80mg/100g.
[ example 2 ]
Into a 500mL flask filled with nitrogen gas were charged 100g of 1-octene and 200mL of toluene, and the mixture was heated at a constant temperature of 100℃for 30 minutes, and 50mL of a metallocene catalyst solution (dimethylsilylbis-indenyl zirconium dichloride 3. Mu. Mol, dimethylanilinium tetrakis (pentafluorophenyl) borate 50mg, triethylaluminum 35 mg) was added. After 1 hour of reaction, unreacted 1-octene was removed by distillation under reduced pressure. Hydrogen of 0.5MPa is added at 100 ℃ and the reaction is continued for 2 hours, finally 90g of saturated metallocene poly alpha-olefin product is obtained, and the yield is calculated to be 90%.
The performance of the saturated metallocene polyalphaolefin product was tested with a kinematic viscosity at 100℃of 19cSt, a viscosity index of 191, a weight average molecular weight of 2780 and a bromine index of 50mg/100g.
[ example 3 ]
Into a 500mL flask filled with nitrogen gas were charged 100g of 1-octene and 200mL of toluene, and the mixture was heated at a constant temperature of 100℃for 30 minutes, and 50mL of a metallocene catalyst solution (dimethylsilylbis-indenyl zirconium dichloride 3. Mu. Mol, dimethylanilinium tetrakis (pentafluorophenyl) borate 50mg, triethylaluminum 35 mg) was added. After 1 hour of reaction, unreacted 1-octene was removed by distillation under reduced pressure. Hydrogen gas of 1MPa is added at 100 ℃ to continue the reaction for 2 hours, and finally 92g of saturated metallocene poly alpha-olefin product is obtained, and the yield is calculated to be 92%.
The performance of the saturated metallocene polyalphaolefin product was tested with a kinematic viscosity at 100℃of 22cSt, a viscosity index of 191, a weight average molecular weight of 2875 and a bromine index of 20mg/100g.
[ example 4 ]
Into a 500mL flask filled with nitrogen gas were charged 100g of 1-octene and 200mL of toluene, and the mixture was heated at a constant temperature of 100℃for 30 minutes, and 50mL of a metallocene catalyst solution (dimethylsilylbis-indenyl zirconium dichloride 3. Mu. Mol, dimethylanilinium tetrakis (pentafluorophenyl) borate 50mg, triethylaluminum 35 mg) was added. After 1 hour of reaction, unreacted 1-octene was removed by distillation under reduced pressure. Hydrogen gas of 1MPa is added at 100 ℃ to continue the reaction for 3 hours, and finally 93g of saturated metallocene poly alpha-olefin product is obtained, and the yield is calculated to be 93%.
The performance of the saturated metallocene polyalphaolefin product was tested with a kinematic viscosity of 20cSt at 100℃and a viscosity index of 191, a weight average molecular weight 2818 and a bromine index of 9mg/100g.
[ example 5 ]
Into a 500mL flask filled with nitrogen gas were charged 100g of 1-octene and 200mL of toluene, and the mixture was heated at a constant temperature of 100℃for 30 minutes, and 50mL of a metallocene catalyst solution (dimethylsilylbis-indenyl zirconium dichloride 3. Mu. Mol, dimethylanilinium tetrakis (pentafluorophenyl) borate 50mg, triethylaluminum 35 mg) was added. After 1 hour of reaction, unreacted 1-octene was removed by distillation under reduced pressure. Hydrogen of 2MPa was added at 100 c and the reaction was continued for 2 hours to finally obtain 91g of a saturated metallocene polyalphaolefin product, calculated to yield 91%.
The performance test was carried out on a saturated metallocene polyalphaolefin product with a kinematic viscosity at 100℃of 20cSt, a viscosity index of 190, a weight average molecular weight of 2802 and a bromine index of 5mg/100g.
[ example 6 ]
Into a 500mL flask filled with nitrogen gas were charged 100g of 1-octene and 200mL of toluene, and the mixture was heated at a constant temperature of 100℃for 30 minutes, and 50mL of a metallocene catalyst solution (dimethylsilylbis-indenyl zirconium dichloride 3. Mu. Mol, dimethylanilinium tetrakis (pentafluorophenyl) borate 50mg, triethylaluminum 35 mg) was added. After 1 hour of reaction, unreacted 1-octene was removed by distillation under reduced pressure. Hydrogen of 0.1MPa was added at 100 c and the reaction was continued for 6 hours to finally obtain 92g of a saturated metallocene polyalphaolefin product, calculated to yield 92%.
The performance of the saturated metallocene polyalphaolefin product was tested with a kinematic viscosity at 100℃of 21cSt, a viscosity index of 190, a weight average molecular weight of 2836 and a bromine index of 18mg/100g.
[ example 7 ]
Into a 500mL flask filled with nitrogen gas were charged 100g of 1-octene and 200mL of toluene, and the mixture was heated at a constant temperature of 50℃for 30 minutes, and 50mL of a metallocene catalyst solution (dimethylsilylbis-indenyl zirconium dichloride 3. Mu. Mol, dimethylanilinium tetrakis (pentafluorophenyl) borate, 50mg, triethylaluminum, 35 mg) was added. After 1 hour of reaction, unreacted 1-octene was removed by distillation under reduced pressure. Hydrogen of 0.1MPa is added at 50 ℃ and the reaction is continued for 2 hours, and finally, 95g of saturated metallocene poly alpha-olefin product is obtained, and the yield is calculated to be 95%.
The performance test was carried out on a saturated metallocene polyalphaolefin product having a kinematic viscosity at 100℃of 160cSt, a viscosity index of 218, a weight average molecular weight of 7407 and a bromine index of 107mg/100g.
[ example 8 ]
Into a 500mL flask filled with nitrogen gas were charged 100g of 1-octene and 200mL of toluene, and the mixture was heated at a constant temperature of 150℃for 30 minutes, and 50mL of a metallocene catalyst solution (dimethylsilylbis-indenyl zirconium dichloride 3. Mu. Mol, dimethylanilinium tetrakis (pentafluorophenyl) borate, 50mg, triethylaluminum, 35 mg) was added. After 1 hour of reaction, unreacted 1-octene was removed by distillation under reduced pressure. Hydrogen of 0.1MPa is added at 150 ℃ and the reaction is continued for 2 hours, and finally 86g of saturated metallocene poly alpha-olefin product is obtained, and the yield is calculated to be 86%.
The performance test was carried out on a saturated metallocene polyalphaolefin product having a kinematic viscosity at 100℃of 11cSt, a viscosity index of 156, a weight average molecular weight of 1855 and a bromine index of 3mg/100g.
[ example 9 ]
The procedure of example 1 was followed except that 1-octene was replaced with 1-hexadecene. 93g of a saturated metallocene polyalphaolefin product were obtained, calculated to give a yield of 93%.
The performance test was carried out on a saturated metallocene polyalphaolefin product having a kinematic viscosity at 100℃of 104cSt, a viscosity index of 200, a weight average molecular weight of 5658 and a bromine index of 87mg/100g.
[ example 10 ]
The procedure of example 1 was followed except that dimethylsilylbis indenyl zirconium dichloride was replaced with dimethylsilylbis-n-propylcyclopentadienyl zirconium dichloride. 85g of a saturated metallocene polyalphaolefin product was obtained, calculated to yield 85%.
The performance of the saturated metallocene polyalphaolefin product was tested with a kinematic viscosity at 100℃of 17cSt, a viscosity index of 160, a weight average molecular weight of 2537 and a bromine index of 60mg/100g.
[ example 11 ]
The procedure of example 1 was followed except that dimethylsilylbis indenyl zirconium dichloride was replaced with dimethylsilylbis-n-propylcyclopentadienyl hafnium dichloride. Finally, 80g of saturated metallocene poly-alpha-olefin product was obtained, the yield was calculated to be 80%.
The performance of the saturated metallocene polyalphaolefin product was tested with a kinematic viscosity at 100℃of 15cSt, a viscosity index of 170, a weight average molecular weight of 2410 and a bromine index of 62mg/100g.
[ example 12 ]
The procedure of example 1 was followed except that dimethylanilinium tetrakis (pentafluorophenyl) borate was replaced with trimethylammonium tetrakis (pentafluorophenyl) borate. 93g of a saturated metallocene polyalphaolefin product were obtained, calculated to give a yield of 93%.
The performance of the saturated metallocene polyalphaolefin product was tested with a kinematic viscosity at 100℃of 20cSt, a viscosity index of 190, a weight average molecular weight of 2752 and a bromine index of 76mg/100g.
[ example 13 ]
The procedure of example 1 was followed except that triethylaluminum was replaced with tri-n-butylaluminum. Finally, 95g of saturated metallocene poly-alpha-olefin product was obtained, and the yield was calculated to be 95%.
The performance of the saturated metallocene polyalphaolefin product was tested with a kinematic viscosity of 20cSt at 100℃and a viscosity index of 190 and a weight average molecular weight of 2689 and a bromine index of 81mg/100g.
Comparative example 1
The procedure of example 1 was followed except that no distillation under reduced pressure was carried out, i.e., no removal of unreacted monomers was carried out. The method comprises the following steps:
into a 500mL flask filled with nitrogen gas were charged 100g of 1-octene and 200mL of toluene, and the mixture was heated at a constant temperature of 100℃for 30 minutes, and 50mL of a metallocene catalyst solution (dimethylsilylbis-indenyl zirconium dichloride 3. Mu. Mol, dimethylanilinium tetrakis (pentafluorophenyl) borate 50mg, triethylaluminum 35 mg) was added. After 1 hour of reaction, hydrogen of 0.1MPa is added, and the reaction is continued for 2 hours, finally 90g of saturated metallocene poly alpha-olefin product is obtained, and the yield is calculated to be 90%.
The performance of the saturated metallocene polyalphaolefin product was tested with a kinematic viscosity of 20cSt at 100℃and a viscosity index of 191, a weight average molecular weight of 2905 and a bromine index of 120mg/100g.
Comparative example 2
The procedure of example 1 was followed except that hydrogen was added during the reaction as follows:
100g of 1-octene and 200mL of toluene are added into a 500mL flask filled with nitrogen, the mixture is heated for 30 minutes at the constant temperature of 100 ℃,50 mL of metallocene catalyst solution (dimethyl silicon-based bis-indenyl zirconium dichloride, 50mg of dimethyl phenyl ammonium tetrakis (pentafluorophenyl) borate and 35mg of triethylaluminum) are added, 0.1MPa of hydrogen is added, the reaction is continued for 3 hours, and finally 60g of saturated metallocene poly alpha-olefin product is obtained, and the yield is calculated to be 60%.
The performance test was carried out on a saturated metallocene polyalphaolefin product with a kinematic viscosity of 9cSt at 100℃and a viscosity index of 150, a weight average molecular weight of 1692 and a bromine index of 50mg/100g.
As can be seen from examples 1-13 and comparative examples 1-2, the method of the present invention does not require the addition of an additional catalyst, saves equipment investment and raw material cost, does not cause the loss of raw materials due to the saturation, and the prepared saturated metallocene poly-alpha-olefin has excellent performance.
What has been described above is merely a preferred example of the present invention. It should be noted that other equivalent modifications and improvements will occur to those skilled in the art, and are intended to be within the scope of the present invention, as a matter of common general knowledge in the art, in light of the technical teaching provided by the present invention.
Claims (10)
1. A method for preparing a saturated metallocene polyalphaolefin comprising: polymerizing alpha-olefin monomer in the presence of metallocene catalyst and activator, removing unreacted monomer, and adding hydrogen to hydrogenate.
2. The method of claim 1, wherein the hydrogenation conditions comprise: the temperature is 50-150 ℃, the time is 0.5-12 h, and the hydrogen pressure is 0.1-2 MPa.
3. The process according to claim 1 or 2, wherein the process for removing unreacted monomers is distillation under reduced pressure.
4. A process according to any one of claims 1 to 3, wherein the α -olefin is selected from one or more of 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene and 1-eicosene, preferably one or more of 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene and 1-tetradecene.
5. The process according to any one of claims 1 to 4, wherein the metallocene catalyst is selected from the group consisting of dimethylsilylbis-n-propylcyclopentadienyl zirconium dichloride, dimethylsilylbis-indenyl zirconium dichloride, diethylsilyldiindenyl zirconium dichloride, diphenylsilyldi (4, 7-dimethylindenyl) zirconium dichloride, dimethylsilylbis (4, 7-dimethylindenyl) zirconium dichloride, dimethylsilylbisindenyl zirconium dichloride, diphenylsilyldi (2-methylcyclopentadienyl) zirconium dichloride, ethylenebisindenyl zirconium dichloride, ethylenebis (2-methylindenyl) zirconium dichloride, dimethylsilylbis (2-methyl-3-butylcyclopentadienyl) zirconium dichloride, dimethylsilyldicyclopentadienyl zirconium dichloride, diethylcyclopentadienyl (3, 5-dimethylbenzylindenyl) zirconium dichloride, diethylcyclopentadienyl (4, 7-dimethylindenyl) zirconium dichloride, dimethylmethylenecyclopentadienyl (4, 7-dimethylindenyl) zirconium dichloride, diphenyldicyclopentadiene (2-methylcyclopentadienyl) zirconium dichloride, dimethylsilacyclopentadienyl (2-dimethylindenyl) zirconium dichloride, dimethylsilenyl (2-dimethylindenyl) zirconium dichloride, dimethylsilacyclopentadienyl (3, 5-dimethylindenyl) zirconium dichloride, dimethylsilenyl (2-dimethylindenyl) zirconium dichloride Dimethylsilylbis-indenyl hafnium dichloride, diethylsilylbis-indenyl hafnium dichloride, diphenylsilylbis (4, 7-dimethylindenyl) hafnium dichloride, dimethylsilylenebis (4, 7-dimethylindenyl) hafnium dichloride, diphenylsilylbis (2-methylcyclopentadienyl) hafnium dichloride, ethylenebisindenyl hafnium dichloride, ethylenebis (2-methylindenyl) hafnium dichloride, dimethylsilylbis (2-methyl-3-butylcyclopentadienyl) hafnium dichloride, dimethylsilylbiscyclopentadienyl hafnium dichloride, diethylmethylenecyclopentadienyl (3, 5-dimethylindenyl) hafnium dichloride, diethylmethylenecyclopentadienyl (4, 7-dimethylindenyl) hafnium dichloride, dimethylmethylenecyclopentadienyl (4, 7-dimethylindenyl) hafnium dichloride, dimethylcyclopentadienyl (4, 7-dimethylindenyl) hafnium dichloride, hafnium dimethylcyclopentadienyl (3, 5-dimethylindenyl) hafnium dichloride, dimethylcyclopentadienyl (2-dimethylindenyl) hafnium dichloride, and at least one of dimethylsilacyclopentadienyl (2-dimethylindenyl) hafnium dichloride.
6. The process according to any one of claims 1 to 5, wherein the activator is an aluminum alkyl and/or a borate.
7. The method of claim 6, wherein the aluminum alkyl has the chemical formula AlR 3 Wherein R is C 1 -C 10 Preferably, the alkyl aluminum is at least one selected from trimethylaluminum, triethylaluminum, triisopropylaluminum, tri-n-propylaluminum, triisobutylaluminum, tri-n-butylaluminum, triisopentylaluminum, tri-n-pentylaluminum, triisohexylaluminum, tri-n-hexylaluminum, triisoheptylaluminum, tri-n-heptylaluminum, triisooctylaluminum, tri-n-octylaluminum, triisononylaluminum, tri-n-nonylaluminum, triisodecylaluminum and tri-n-decylaluminum.
8. The production method according to claim 6, wherein the borate is at least one selected from the group consisting of dimethylanilinium tetrakis (pentafluorophenyl) borate, diethylanilinium tetrakis (pentafluorophenyl) borate, dibutylanilinium tetrakis (pentafluorophenyl) borate, trimethylammonium tetrakis (pentafluorophenyl) borate, diethylammonium tetrakis (pentafluorophenyl) borate, and tributylammonium tetrakis (pentafluorophenyl) borate.
9. The method according to any one of claims 1 to 8, wherein the polymerization further comprises using a solvent, preferably the solvent is an alkane solvent and/or an aromatic hydrocarbon solvent, more preferably at least one selected from hexane, heptane, octane, nonane, decane, cyclohexane, benzene, toluene and xylene.
10. The production method according to any one of claims 1 to 9, wherein the conditions of the polymerization reaction include: the temperature is 0-200 ℃, the pressure is 0.1-2 MPa, and the time is 0.5-5 h.
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