CN114163552B - Modified silica gel, preparation method and application thereof, supported catalyst, preparation method and application thereof - Google Patents
Modified silica gel, preparation method and application thereof, supported catalyst, preparation method and application thereof Download PDFInfo
- Publication number
- CN114163552B CN114163552B CN202210003779.7A CN202210003779A CN114163552B CN 114163552 B CN114163552 B CN 114163552B CN 202210003779 A CN202210003779 A CN 202210003779A CN 114163552 B CN114163552 B CN 114163552B
- Authority
- CN
- China
- Prior art keywords
- silica gel
- aluminum chloride
- trifluoromethanesulfonic acid
- modified silica
- aluminum
- 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.)
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 101
- 239000003054 catalyst Substances 0.000 title claims abstract description 76
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims abstract description 286
- -1 trifluoromethyl sulfonic acid modified silica gel Chemical class 0.000 claims abstract description 93
- 239000000741 silica gel Substances 0.000 claims abstract description 83
- 229910002027 silica gel Inorganic materials 0.000 claims abstract description 83
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims abstract description 75
- 239000003960 organic solvent Substances 0.000 claims abstract description 65
- 239000012298 atmosphere Substances 0.000 claims abstract description 57
- 238000002156 mixing Methods 0.000 claims abstract description 46
- 230000004048 modification Effects 0.000 claims abstract description 40
- 238000012986 modification Methods 0.000 claims abstract description 40
- 230000001681 protective effect Effects 0.000 claims abstract description 40
- 230000018044 dehydration Effects 0.000 claims abstract description 17
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 17
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- 229910052723 transition metal Inorganic materials 0.000 claims description 48
- 150000003624 transition metals Chemical class 0.000 claims description 48
- 239000012190 activator Substances 0.000 claims description 46
- 229910052782 aluminium Inorganic materials 0.000 claims description 29
- 238000006116 polymerization reaction Methods 0.000 claims description 27
- 239000011148 porous material Substances 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 22
- 125000000217 alkyl group Chemical group 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 17
- 125000005234 alkyl aluminium group Chemical group 0.000 claims description 16
- 239000007795 chemical reaction product Substances 0.000 claims description 14
- 238000004321 preservation Methods 0.000 claims description 14
- 150000001336 alkenes Chemical class 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- 230000003213 activating effect Effects 0.000 claims description 8
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims description 8
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 4
- 229920000098 polyolefin Polymers 0.000 abstract description 16
- 239000002841 Lewis acid Substances 0.000 abstract description 8
- 150000007517 lewis acids Chemical class 0.000 abstract description 8
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 69
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 59
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 54
- 239000000243 solution Substances 0.000 description 54
- 229910052757 nitrogen Inorganic materials 0.000 description 32
- 238000005406 washing Methods 0.000 description 27
- 239000007788 liquid Substances 0.000 description 25
- 239000006185 dispersion Substances 0.000 description 24
- 238000003756 stirring Methods 0.000 description 22
- 239000011261 inert gas Substances 0.000 description 17
- 208000005156 Dehydration Diseases 0.000 description 15
- 238000000926 separation method Methods 0.000 description 13
- 239000012265 solid product Substances 0.000 description 13
- 238000001291 vacuum drying Methods 0.000 description 13
- 239000012299 nitrogen atmosphere Substances 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 11
- 239000011521 glass Substances 0.000 description 10
- 230000037048 polymerization activity Effects 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 8
- 239000005977 Ethylene Substances 0.000 description 8
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 8
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 8
- 239000012300 argon atmosphere Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 7
- 229910002808 Si–O–Si Inorganic materials 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 6
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- NDJMNNSJDIFFTH-UHFFFAOYSA-L [Cl-].[Cl-].CC1=CC(C(=CC=C2)C=3C=CC=CC=3)=C2C1[Zr+2]([SiH](C)C)C1C(C)=CC2=C1C=CC=C2C1=CC=CC=C1 Chemical compound [Cl-].[Cl-].CC1=CC(C(=CC=C2)C=3C=CC=CC=3)=C2C1[Zr+2]([SiH](C)C)C1C(C)=CC2=C1C=CC=C2C1=CC=CC=C1 NDJMNNSJDIFFTH-UHFFFAOYSA-L 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 description 4
- 101150116295 CAT2 gene Proteins 0.000 description 3
- 101100392078 Caenorhabditis elegans cat-4 gene Proteins 0.000 description 3
- 101100326920 Caenorhabditis elegans ctl-1 gene Proteins 0.000 description 3
- 101100494773 Caenorhabditis elegans ctl-2 gene Proteins 0.000 description 3
- 101100112369 Fasciola hepatica Cat-1 gene Proteins 0.000 description 3
- 241000282326 Felis catus Species 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 101100005271 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-1 gene Proteins 0.000 description 3
- 101100126846 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) katG gene Proteins 0.000 description 3
- KZUKCLOWAMFDDB-UHFFFAOYSA-L butylcyclopentane;dichlorozirconium Chemical compound Cl[Zr]Cl.CCCC[C]1[CH][CH][CH][CH]1.CCCC[C]1[CH][CH][CH][CH]1 KZUKCLOWAMFDDB-UHFFFAOYSA-L 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 125000003944 tolyl group Chemical group 0.000 description 3
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 3
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- VPGLGRNSAYHXPY-UHFFFAOYSA-L zirconium(2+);dichloride Chemical compound Cl[Zr]Cl VPGLGRNSAYHXPY-UHFFFAOYSA-L 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- XWJBRBSPAODJER-UHFFFAOYSA-N 1,7-octadiene Chemical compound C=CCCCCC=C XWJBRBSPAODJER-UHFFFAOYSA-N 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 2
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 101100342039 Halobacterium salinarum (strain ATCC 29341 / DSM 671 / R1) kdpQ gene Proteins 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- RLFRULMEJWRTQH-UHFFFAOYSA-L [Cl-].[Cl-].C1=CC=CC=2C3=CC=CC=C3C(C12)[Zr+2].C1(=CC=CC=C1)C(C1=CC=CC=C1)=C1C=CC=C1 Chemical compound [Cl-].[Cl-].C1=CC=CC=2C3=CC=CC=C3C(C12)[Zr+2].C1(=CC=CC=C1)C(C1=CC=CC=C1)=C1C=CC=C1 RLFRULMEJWRTQH-UHFFFAOYSA-L 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- SIPUZPBQZHNSDW-UHFFFAOYSA-N bis(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]CC(C)C SIPUZPBQZHNSDW-UHFFFAOYSA-N 0.000 description 2
- 238000012662 bulk polymerization Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000012685 gas phase polymerization Methods 0.000 description 2
- 229910052735 hafnium Inorganic materials 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000011534 incubation Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012968 metallocene catalyst Substances 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000003828 vacuum filtration Methods 0.000 description 2
- WCFQIFDACWBNJT-UHFFFAOYSA-N $l^{1}-alumanyloxy(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]O[Al] WCFQIFDACWBNJT-UHFFFAOYSA-N 0.000 description 1
- QCEOZLISXJGWSW-UHFFFAOYSA-K 1,2,3,4,5-pentamethylcyclopentane;trichlorotitanium Chemical compound [Cl-].[Cl-].[Cl-].CC1=C(C)C(C)([Ti+3])C(C)=C1C QCEOZLISXJGWSW-UHFFFAOYSA-K 0.000 description 1
- FOKGVHRHBBEPPI-UHFFFAOYSA-K 1,2,3,4,5-pentamethylcyclopentane;trichlorozirconium Chemical compound Cl[Zr](Cl)Cl.C[C]1[C](C)[C](C)[C](C)[C]1C FOKGVHRHBBEPPI-UHFFFAOYSA-K 0.000 description 1
- PRBHEGAFLDMLAL-UHFFFAOYSA-N 1,5-Hexadiene Natural products CC=CCC=C PRBHEGAFLDMLAL-UHFFFAOYSA-N 0.000 description 1
- YVSMQHYREUQGRX-UHFFFAOYSA-N 2-ethyloxaluminane Chemical compound CC[Al]1CCCCO1 YVSMQHYREUQGRX-UHFFFAOYSA-N 0.000 description 1
- BGGKSZPSSRGVTP-UHFFFAOYSA-L 2-methyl-1h-inden-1-ide;zirconium(4+);dichloride Chemical compound [Cl-].[Cl-].[Zr+4].C1=CC=C2[CH-]C(C)=CC2=C1.C1=CC=C2[CH-]C(C)=CC2=C1 BGGKSZPSSRGVTP-UHFFFAOYSA-L 0.000 description 1
- RDWHKWXYJQUZNS-UHFFFAOYSA-N 4-propan-2-yl-1,3-thiazole-2-carboxylic acid Chemical compound CC(C)C1=CSC(C(O)=O)=N1 RDWHKWXYJQUZNS-UHFFFAOYSA-N 0.000 description 1
- RSPAIISXQHXRKX-UHFFFAOYSA-L 5-butylcyclopenta-1,3-diene;zirconium(4+);dichloride Chemical compound Cl[Zr+2]Cl.CCCCC1=CC=C[CH-]1.CCCCC1=CC=C[CH-]1 RSPAIISXQHXRKX-UHFFFAOYSA-L 0.000 description 1
- KUVYGWRNMAIXHX-UHFFFAOYSA-L CC(C)C1=CC(C(C)C)=CC1[Zr+2]C1(C([SiH](C)C)=CC=C1)[SiH](C)C.[Cl-].[Cl-] Chemical compound CC(C)C1=CC(C(C)C)=CC1[Zr+2]C1(C([SiH](C)C)=CC=C1)[SiH](C)C.[Cl-].[Cl-] KUVYGWRNMAIXHX-UHFFFAOYSA-L 0.000 description 1
- CKNXPIUXGGVRME-UHFFFAOYSA-L CCCCC1(C=CC(C)=C1)[Zr](Cl)(Cl)C1(CCCC)C=CC(C)=C1 Chemical compound CCCCC1(C=CC(C)=C1)[Zr](Cl)(Cl)C1(CCCC)C=CC(C)=C1 CKNXPIUXGGVRME-UHFFFAOYSA-L 0.000 description 1
- AOAGKXYMQXKVSN-UHFFFAOYSA-L C[SiH](C)[Zr+2](C1C2=CC=CC=C2C=C1C1=CC=CC=C1)C1=CC2=CC=CC=C2C1.[Cl-].[Cl-] Chemical compound C[SiH](C)[Zr+2](C1C2=CC=CC=C2C=C1C1=CC=CC=C1)C1=CC2=CC=CC=C2C1.[Cl-].[Cl-] AOAGKXYMQXKVSN-UHFFFAOYSA-L 0.000 description 1
- MPJLHVOQWLKMRN-UHFFFAOYSA-L C[SiH](C)[Zr](Cl)(Cl)(C1C=CC=C1)C1c2ccccc2-c2ccccc12 Chemical compound C[SiH](C)[Zr](Cl)(Cl)(C1C=CC=C1)C1c2ccccc2-c2ccccc12 MPJLHVOQWLKMRN-UHFFFAOYSA-L 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- JDCCJVBIWXMMCE-UHFFFAOYSA-L Cl[Zr](Cl)(C=C)(C1C=CC2=CC=CC=C12)C1C=CC2=CC=CC=C12 Chemical compound Cl[Zr](Cl)(C=C)(C1C=CC2=CC=CC=C12)C1C=CC2=CC=CC=C12 JDCCJVBIWXMMCE-UHFFFAOYSA-L 0.000 description 1
- 101100005280 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-3 gene Proteins 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- BURUBEGPJDKBJV-UHFFFAOYSA-L [Cl-].[Cl-].C(C)(C)(C)C1(C=CC=C1)[Zr+2]C1(C=CC=C1)C(C)(C)C Chemical compound [Cl-].[Cl-].C(C)(C)(C)C1(C=CC=C1)[Zr+2]C1(C=CC=C1)C(C)(C)C BURUBEGPJDKBJV-UHFFFAOYSA-L 0.000 description 1
- JEKOISATHYKFFC-UHFFFAOYSA-L [Cl-].[Cl-].C=1C=CC=CC=1C1=CC2=CC=CC=C2C1[Zr+2]C(C1=CC=CC=C1C=1)C=1C1=CC=CC=C1 Chemical compound [Cl-].[Cl-].C=1C=CC=CC=1C1=CC2=CC=CC=C2C1[Zr+2]C(C1=CC=CC=C1C=1)C=1C1=CC=CC=C1 JEKOISATHYKFFC-UHFFFAOYSA-L 0.000 description 1
- SNRFMCZAAQYJPL-UHFFFAOYSA-L [Cl-].[Cl-].C[Si](C)(C)C=C1C=C(C2=CC=CC=C12)[Zr+2] Chemical compound [Cl-].[Cl-].C[Si](C)(C)C=C1C=C(C2=CC=CC=C12)[Zr+2] SNRFMCZAAQYJPL-UHFFFAOYSA-L 0.000 description 1
- KUNZSLJMPCDOGI-UHFFFAOYSA-L [Cl-].[Cl-].[Hf+2] Chemical compound [Cl-].[Cl-].[Hf+2] KUNZSLJMPCDOGI-UHFFFAOYSA-L 0.000 description 1
- OKPFRHMGNFRBIW-UHFFFAOYSA-L [SiH](c1ccccc1)c1ccccc1.Cl[Zr](Cl)(C1C=CC=C1)C1c2ccccc2-c2ccccc12 Chemical compound [SiH](c1ccccc1)c1ccccc1.Cl[Zr](Cl)(C1C=CC=C1)C1c2ccccc2-c2ccccc12 OKPFRHMGNFRBIW-UHFFFAOYSA-L 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- MKNXBRLZBFVUPV-UHFFFAOYSA-L cyclopenta-1,3-diene;dichlorotitanium Chemical compound Cl[Ti]Cl.C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 MKNXBRLZBFVUPV-UHFFFAOYSA-L 0.000 description 1
- QOXHZZQZTIGPEV-UHFFFAOYSA-K cyclopenta-1,3-diene;titanium(4+);trichloride Chemical group Cl[Ti+](Cl)Cl.C=1C=C[CH-]C=1 QOXHZZQZTIGPEV-UHFFFAOYSA-K 0.000 description 1
- JJQHEAPVGPSOKX-UHFFFAOYSA-L cyclopentyl(trimethyl)silane;dichlorozirconium Chemical compound Cl[Zr]Cl.C[Si](C)(C)[C]1[CH][CH][CH][CH]1.C[Si](C)(C)[C]1[CH][CH][CH][CH]1 JJQHEAPVGPSOKX-UHFFFAOYSA-L 0.000 description 1
- NLDGJRWPPOSWLC-UHFFFAOYSA-N deca-1,9-diene Chemical compound C=CCCCCCCC=C NLDGJRWPPOSWLC-UHFFFAOYSA-N 0.000 description 1
- HJXBDPDUCXORKZ-UHFFFAOYSA-N diethylalumane Chemical compound CC[AlH]CC HJXBDPDUCXORKZ-UHFFFAOYSA-N 0.000 description 1
- CPDVHGLWIFENDJ-UHFFFAOYSA-N dihexylalumane Chemical compound C(CCCCC)[AlH]CCCCCC CPDVHGLWIFENDJ-UHFFFAOYSA-N 0.000 description 1
- TUTOKIOKAWTABR-UHFFFAOYSA-N dimethylalumane Chemical compound C[AlH]C TUTOKIOKAWTABR-UHFFFAOYSA-N 0.000 description 1
- GNPSMYTXIPVJDU-UHFFFAOYSA-N dioctylalumane Chemical compound C(CCCCCCC)[AlH]CCCCCCCC GNPSMYTXIPVJDU-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 229940069096 dodecene Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- MSBGLMWCKRSNHW-UHFFFAOYSA-N ethyl 2-chloro-2,2-diphenylacetate Chemical compound C=1C=CC=CC=1C(Cl)(C(=O)OCC)C1=CC=CC=C1 MSBGLMWCKRSNHW-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical compound C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- QYZLKGVUSQXAMU-UHFFFAOYSA-N penta-1,4-diene Chemical compound C=CCC=C QYZLKGVUSQXAMU-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
- QMBQEXOLIRBNPN-UHFFFAOYSA-L zirconocene dichloride Chemical compound [Cl-].[Cl-].[Zr+4].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 QMBQEXOLIRBNPN-UHFFFAOYSA-L 0.000 description 1
Classifications
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- 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
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
-
- 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
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F10/02—Ethene
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- 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)
Abstract
The invention relates to the technical field of polyolefin catalysis, in particular to aluminum chloride/trifluoromethyl sulfonic acid modified silica gel, a preparation method and application thereof, a supported catalyst, a preparation method and application thereof. According to the preparation method provided by the invention, the silica gel is subjected to heat treatment dehydration in a protective atmosphere or vacuum environment to obtain pretreated silica gel; mixing the pretreated silica gel, aluminum chloride and an organic solvent in a protective atmosphere to carry out aluminum chloride modification to obtain aluminum chloride modified silica gel, wherein the mass ratio of the aluminum chloride to the pretreated silica gel is (0.1-0.5): 1; and in a protective atmosphere, mixing the aluminum chloride modified silica gel, the trifluoromethanesulfonic acid and an organic solvent for trifluoromethanesulfonic acid modification to obtain the aluminum chloride/trifluoromethanesulfonic acid modified silica gel, wherein the mass ratio of the trifluoromethanesulfonic acid to the aluminum chloride modified silica gel is (0.1-0.5): 1. The preparation method provided by the invention can enable silica gel to have proper Lewis acid content.
Description
Technical Field
The invention relates to the technical field of polyolefin catalysis, in particular to modified silica gel, a preparation method and application thereof, a supported catalyst, and a preparation method and application thereof.
Background
Compared with the traditional Z-N catalyst, the metallocene polyolefin catalyst generally has only one active center structure, so that the obtained polymer has high uniformity, narrow molecular weight distribution and uniform distribution of comonomer on a molecular chain. Moreover, the metallocene polyolefin catalyst has very wide adaptability to various types of monomers and good copolymerization performance, so that the metallocene polyolefin catalyst is particularly suitable for developing novel polyolefin products.
Since metallocenes are generally soluble in polymerization media such as hexane, toluene, liquid olefins, etc., the morphology of the resulting polymers is difficult to control if unsupported metallocene polyolefin catalysts are used directly, and there is a severe sticking phenomenon which makes them unsuitable for use in polyolefin production units for gas phase, bulk and slurry polymerization processes. The metallocene is loaded on a proper carrier to obtain the supported metallocene polyolefin catalyst, so that the morphology of the polymer can be effectively improved, the apparent density of the polymer can be improved, and the particle size distribution of the polymer can be easily controlled. The supported metallocene catalyst can be used in the existing polyolefin production devices for gas phase polymerization, bulk polymerization and slurry polymerization processes, and the devices do not need to be changed greatly.
Silica gel (SiO) 2 ) Is a common catalyst carrier and has been industrially applied to a supported Z-N catalyst, a chromium-based catalyst and a metallocene catalyst in the field of polyolefin catalysts. The silica gel carrier has the advantages of large specific surface area and specific pore volume, controllable pore diameter and pore diameter distribution, and is beneficial to improving the catalyst loading capacity. The silica gel carrier supported catalyst has moderate mechanical strength, when the catalyst particles are gradually broken along with the growth of the polymer particles in the process of catalyzing olefin polymerization to form polymers, the internal catalyst active ingredients can be continuously exposed to improve the polymerization activity and prolong the activity life of the catalyst, a large amount of polymer fine powder (the particle size is smaller than 120 microns) is not formed by excessive breaking, and the problem of blocking and caking in polymerization equipment and pipelines is easily caused by excessive polymer fine powder.
However, the supported metallocene polyolefin catalyst obtained by loading the metallocene with the silica gel disclosed in the prior art has lower polymerization activity.
Disclosure of Invention
In view of the above, the invention provides a modified silica gel, a preparation method and application thereof, a supported catalyst and a preparation method and application thereof, and the aluminum chloride/trifluoromethyl sulfonic acid modified silica gel obtained by the preparation method provided by the invention has proper Lewis acid content, and can effectively improve the polymerization activity of the supported catalyst for catalyzing olefin polymerization reaction as a supported catalyst carrier.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of aluminum chloride/trifluoromethanesulfonic acid modified silica gel, which comprises the following steps:
carrying out heat treatment dehydration on silica gel in a protective atmosphere or a vacuum environment to obtain pretreated silica gel;
mixing the pretreated silica gel, aluminum chloride and a first organic solvent in a protective atmosphere to carry out aluminum chloride modification to obtain aluminum chloride modified silica gel, wherein the mass ratio of the aluminum chloride to the pretreated silica gel is (0.1-0.5): 1;
and in a protective atmosphere, mixing the aluminum chloride modified silica gel, the trifluoromethanesulfonic acid and a second organic solvent for trifluoromethanesulfonic acid modification to obtain the aluminum chloride/trifluoromethanesulfonic acid modified silica gel, wherein the mass ratio of the trifluoromethanesulfonic acid to the aluminum chloride modified silica gel is (0.1-0.5): 1.
Preferably, the heat preservation temperature of the aluminum chloride modification is 20-80 ℃, and the heat preservation time of the aluminum chloride modification is 0.5-6 h;
the temperature of the trifluoro-methanesulfonic acid modification is 0-100 ℃, and the temperature of the trifluoro-methanesulfonic acid modification is 0.5-6 h.
Preferably, the average particle diameter of the silica gel is 10-100 μm, and the specific surface area of the silica gel is 100-1000 m 2 Per gram, the specific pore volume of the silica gel is 0.5-3 cm 3 /g。
The invention provides the aluminum chloride/trifluoromethanesulfonic acid modified silica gel prepared by the preparation method in the technical scheme, which comprises silica gel, aluminum chloride, trifluoromethanesulfonic acid and reaction products of the aluminum chloride and the trifluoromethanesulfonic acid adsorbed on the surface and in holes of the silica gel, wherein the chemical composition of the reaction products of the aluminum chloride and the trifluoromethanesulfonic acid is (F) 3 CSO 3 ) x AlCl 3-x ，0＜x＜3。
The invention provides application of the aluminum chloride/trifluoromethanesulfonic acid modified silica gel in a supported catalyst.
The invention provides a supported catalyst, which comprises a carrier and an active component supported on the surface and in holes of the carrier, wherein the active component comprises an organic transition metal complex and an activator, the carrier is the aluminum chloride/trifluoromethane sulfonic acid modified silica gel according to the technical scheme, the organic transition metal complex is a complex formed by unsubstituted or substituted cyclopentadienyl and transition metal, and the activator comprises alkyl aluminum and/or alkyl aluminoxane.
Preferably, the mass ratio of the organic transition metal complex to the aluminum chloride/trifluoromethanesulfonic acid-modified silica gel is (0.01-0.1): 1.
The invention provides a preparation method of the supported catalyst, which comprises the following steps:
mixing a carrier, an organic transition metal complex, an activating agent and a third organic solvent in a protective atmosphere to obtain the supported catalyst, wherein the carrier is the aluminum chloride/trifluoromethane sulfonic acid modified silica gel according to claim 4, the organic transition metal complex is a complex formed by unsubstituted or substituted cyclopentadienyl and transition metal, and the activating agent comprises aluminum alkyl and/or aluminum alkyl aluminoxane.
Preferably, the activator comprises an alkyl aluminum and an alkyl aluminoxane, and the carrier, the organic transition metal complex, the activator and the third organic solvent are mixed together, and the method further comprises a pretreatment of the alkyl aluminum and the alkyl aluminoxane, wherein the pretreatment comprises the following steps:
in a protective atmosphere, mixing the aluminum alkyl, the alkyl aluminoxane and a fourth organic solvent, and removing the solvent; the heat preservation temperature of the mixture of the aluminum alkyl, the alkyl aluminoxane and the fourth organic solvent is 0-80 ℃; the heat preservation time of the mixture of the alkyl aluminum, the alkyl aluminoxane and the fourth organic solvent is 1 to 6 hours.
The invention provides the application of the supported catalyst according to the technical scheme or the supported catalyst prepared by the preparation method according to the technical scheme in olefin polymerization reaction.
The invention provides a preparation method of aluminum chloride/trifluoromethanesulfonic acid modified silica gel, which comprises the following steps: carrying out heat treatment dehydration on silica gel in a protective atmosphere or a vacuum environment to obtain pretreated silica gel; mixing the pretreated silica gel, aluminum chloride and a first organic solvent in a protective atmosphere to carry out aluminum chloride modification to obtain aluminum chloride modified silica gel, wherein the mass ratio of the aluminum chloride to the pretreated silica gel is (0.1-0.5): 1; and in a protective atmosphere, mixing the aluminum chloride modified silica gel, the trifluoromethanesulfonic acid and a second organic solvent for trifluoromethanesulfonic acid modification to obtain the aluminum chloride/trifluoromethanesulfonic acid modified silica gel, wherein the mass ratio of the trifluoromethanesulfonic acid to the aluminum chloride modified silica gel is (0.1-0.5): 1. According to the preparation method provided by the invention, firstly, the silica gel is subjected to heat treatment dehydration in a protective atmosphere or vacuum environment, hydroxyl groups (Si-OH) in the surface and the pore diameter of the silica gel can be dehydrated and condensed to form Si-O-Si groups, then, aluminum chloride is adopted to modify the pretreated silica gel, aluminum atoms in the aluminum chloride have electron withdrawing property, and covalent bonds are formed with oxygen atoms with electron donating property in the Si-O-Si groups on the surface and the pore of the silica gel, so that the covalent bonds are chemically adsorbed on the surface and the pore of the silica gel; after aluminum chloride is modified, the trifluoromethanesulfonic acid is adopted to carry out modification, and the trifluoromethanesulfonic acid is a strong Lewis acid, and can react with aluminum chloride chemically adsorbed on the surface and in the holes of the silica gel to generate (F) 3 CSO 3 ) x AlCl 3-x X is more than 0 and less than 3, and can form covalent bonds with Si-O-Si groups on the surface and in holes of the silica gel to be chemically adsorbed on the surface and in the holes of the silica gel; meanwhile, the mass ratio of the aluminum chloride to the pretreated silica gel is limited to be (0.1-0.5): 1, and the mass ratio of the trifluoromethyl sulfonic acid to the aluminum chloride modified silica gel is limited to be (0.1-0.5): 1; the surface and the holes of the obtained modified silica gel are simultaneously distributed with the chemisorbed reaction products of aluminum chloride, trifluoromethanesulfonic acid, aluminum chloride and trifluoromethanesulfonic acid, and the silica gel can have proper Lewis acid content through the synergistic effect of the three reaction products of aluminum chloride, trifluoromethanesulfonic acid, aluminum chloride and trifluoromethanesulfonic acid, thereby effectively enhancing the catalytic activity when the modified silica gel is used as a polyolefin catalyst carrierCentral polymerization activity and stability.
The invention provides a supported catalyst, which comprises a carrier and an active component supported on the surface and in holes of the carrier, wherein the active component comprises an organic transition metal complex and an activator, the carrier is the aluminum chloride/trifluoromethane sulfonic acid modified silica gel according to the technical scheme, the organic transition metal complex is a complex formed by unsubstituted or substituted cyclopentadienyl and transition metal, and the activator comprises alkyl aluminum and/or alkyl aluminoxane. The carrier of the supported catalyst provided by the invention is modified silica gel which is prepared by simultaneously chemisorbing aluminum chloride, trifluoromethanesulfonic acid, and a reaction product of aluminum chloride and trifluoromethanesulfonic acid in the technical scheme, and three specific Lewis acids of the reaction product of aluminum chloride, trifluoromethanesulfonic acid, aluminum chloride and trifluoromethanesulfonic acid are matched in the same way, so that the polymerization activity of the supported catalyst for catalyzing olefin polymerization can be obviously improved.
Detailed Description
The invention provides a preparation method of aluminum chloride/trifluoromethanesulfonic acid modified silica gel, which comprises the following steps:
carrying out heat treatment dehydration on silica gel in a protective atmosphere or a vacuum environment to obtain pretreated silica gel;
mixing the pretreated silica gel, aluminum chloride and a first organic solvent in a protective atmosphere to carry out aluminum chloride modification to obtain aluminum chloride modified silica gel, wherein the mass ratio of the aluminum chloride to the pretreated silica gel is (0.1-0.5): 1;
and in a protective atmosphere, mixing the aluminum chloride modified silica gel, the trifluoromethanesulfonic acid and a second organic solvent for trifluoromethanesulfonic acid modification to obtain the aluminum chloride/trifluoromethanesulfonic acid modified silica gel, wherein the mass ratio of the trifluoromethanesulfonic acid to the aluminum chloride modified silica gel is (0.1-0.5): 1.
In the present invention, the raw materials used are commercially available products well known to those skilled in the art unless otherwise specified.
In the present invention, the organic solvents used are all subjected to a pre-dehydration treatment. In the present invention, the mode of the pre-dehydration treatment is preferably as follows: and (5) molecular sieve dehydration. In the present invention, the organic solvent used has a water content of < 10ppm.
According to the invention, the silica gel is subjected to heat treatment dehydration in a protective atmosphere or vacuum environment to obtain the pretreated silica gel.
In the present invention, the average particle diameter of the silica gel is preferably 10 to 100. Mu.m, more preferably 30 to 50. Mu.m.
In the present invention, the specific surface area of the silica gel is preferably 100 to 1000m 2 Preferably 250 to 800m 2 /g。
In the invention, the specific pore volume of the silica gel is preferably 0.5-3 cm 3 Preferably 1 to 2.5cm 3 /g。
In the present invention, the heat treatment dehydration is performed in a protective atmosphere or a vacuum environment, and in a specific embodiment of the present invention, the heat treatment dehydration is preferably performed in a vacuum environment, and the vacuum degree of the vacuum environment is preferably-0.08 to-0.1 MPa.
In the present invention, the heat-treatment dehydration is preferably carried out at a holding temperature of 100 to 800 ℃, more preferably 200 to 600 ℃.
In the present invention, the heat-treatment dehydration is preferably carried out for a holding time of 3 to 5 hours, more preferably 4 hours.
In the invention, after the heat treatment and dehydration, the silica gel after the heat treatment and dehydration is naturally cooled to room temperature in a protective atmosphere to obtain the pretreated silica gel, wherein the protective atmosphere is preferably an inert gas atmosphere or a nitrogen atmosphere.
According to the invention, the water in the silica gel raw material surface and the pores is dehydrated and condensed through heat treatment dehydration treatment, and simultaneously, the hydroxyl (Si-OH) on the silica gel surface and in the pores is dehydrated and condensed to form Si-O-Si groups, so that the subsequent modification is facilitated.
After the pretreated silica gel is obtained, the pretreated silica gel, aluminum chloride and a first organic solvent are mixed (hereinafter referred to as first mixing) in a protective atmosphere to carry out aluminum chloride modification, so that the aluminum chloride modified silica gel is obtained, and the mass ratio of the aluminum chloride to the pretreated silica gel is (0.1-0.5): 1.
In the present invention, the first organic solvent is preferably an organic solvent capable of dissolving the aluminum chloride.
In a specific embodiment of the present invention, the first organic solvent is specifically preferably carbon tetrachloride.
In the present invention, the mass ratio of the aluminum chloride to the pretreated silica gel is (0.1 to 0.5): 1, preferably (0.15 to 0.4): 1, and more preferably (0.2 to 0.35): 1.
In the present invention, the ratio of the mass of the aluminum chloride to the volume of the first organic solvent is preferably 1 g/25 mL.
In the present invention, the order of the first mixing is preferably: mixing the pretreated silica gel with the first organic solvent to obtain a pretreated silica gel dispersion; mixing the pretreated silica gel dispersion with the aluminum chloride.
In the present invention, the first mixing is preferably performed under stirring, and the present invention does not require any special requirement for the specific implementation of the stirring.
In the present invention, the first mixing is performed in a protective atmosphere, preferably an inert gas atmosphere or a nitrogen atmosphere, and in a specific embodiment of the present invention, the inert gas atmosphere is particularly preferably an argon atmosphere.
In the present invention, the heat-retaining temperature of the aluminum chloride modification is preferably 20 to 80 ℃, more preferably 25 to 60 ℃, and most preferably 45 to 55 ℃.
In the present invention, the warm-keeping time for the aluminum chloride modification is preferably 0.5 to 6 hours, more preferably 2 to 4.5 hours.
In the present invention, the aluminum chloride modification is preferably performed under reflux conditions.
In the present invention, the aluminum chloride modification is performed in a protective atmosphere, preferably an inert gas atmosphere or a nitrogen atmosphere, and in a specific embodiment of the present invention, the inert gas atmosphere is particularly preferably an argon atmosphere.
In the invention, when the aluminum chloride is modified, chlorine atoms in the aluminum chloride are taken as electron-withdrawing bodies to form covalent bonds with oxygen atoms in Si-O-Si groups on the surface and in the holes of the pretreated silica gel, so that the chlorine atoms are chemically adsorbed on the surface and in the holes of the pretreated silica gel.
In the present invention, when the first organic solvent is preferably an organic solvent capable of dissolving the aluminum chloride, the aluminum chloride modification is preferably: aluminum chloride and the first organic solvent form an aluminum chloride solution, the aluminum chloride solution aluminum chloride modifying the pretreated silica gel. In the present invention, the aluminum chloride solution can sufficiently contact the surface and pore structure of the pretreated silica gel, thereby enabling the modification of the pretreated silica gel by the aluminum chloride to be more sufficient and uniform.
In the invention, the aluminum chloride modification is carried out in a liquid environment, the heat preservation temperature for the aluminum chloride modification is 20-80 ℃, the modification heat preservation temperature is lower, and the energy consumption is less.
In the invention, the aluminum chloride is modified to obtain aluminum chloride modified liquid, and the invention preferably carries out post-treatment on the aluminum chloride modified liquid to obtain the aluminum chloride modified silica gel.
In the present invention, the post-treatment preferably includes: and (5) sequentially performing solid-liquid separation, washing and drying. The method is not particularly limited in the specific embodiment of the solid-liquid separation, the method preferably washes the solid product obtained by the solid-liquid separation, the washing frequency is preferably 3 times, the washing solvent is preferably an organic solvent capable of dissolving the aluminum chloride, the washing solvent is preferably carbon tetrachloride in the specific embodiment of the invention, and the method is not particularly limited in the use amount of the washing solvent in each washing. The solid product after washing is preferably dried, and in the present invention, the drying is preferably vacuum drying, the vacuum degree of the vacuum drying is preferably-0.08 to-0.1 MPa, and the temperature of the vacuum drying is preferably 100 to 800 ℃, and more preferably 200 to 600 ℃. The invention has no special requirement on the time of vacuum drying, and the vacuum drying is carried out until the weight is constant. After vacuum drying, the solid product is naturally cooled to room temperature in a protective atmosphere, preferably an inert gas atmosphere or a nitrogen atmosphere.
According to the invention, unadsorbed aluminum chloride on the surface and in the holes of the pretreated silica gel is removed through aftertreatment, so that the unadsorbed aluminum chloride is free from the pore diameter of the silica gel during modification of the trifluoromethanesulfonic acid, and directly reacts with free trifluoromethanesulfonic acid to influence the modification degree of the trifluoromethanesulfonic acid on the silica gel.
After obtaining aluminum chloride modified silica gel, the invention mixes the aluminum chloride modified silica gel, the trifluoromethanesulfonic acid and a second organic solvent (hereinafter referred to as a second mixture) in a protective atmosphere to carry out trifluoromethanesulfonic acid modification, and obtains the aluminum chloride/trifluoromethanesulfonic acid modified silica gel, wherein the mass ratio of the trifluoromethanesulfonic acid to the aluminum chloride modified silica gel is (0.1-0.5): 1.
In the present invention, the second organic solvent is preferably an organic solvent capable of dissolving the trifluoromethanesulfonic acid.
In a specific embodiment of the present invention, the second organic solvent is specifically preferably toluene.
In the present invention, the mass ratio of the trifluoromethanesulfonic acid to the aluminum chloride-modified silica gel is (0.1 to 0.5): 1, preferably (0.15 to 0.4): 1, and more preferably (0.2 to 0.35): 1.
In the present invention, the ratio of the mass of the trifluoromethanesulfonic acid to the volume of the second organic solvent is preferably 1g:50mL.
In the present invention, the order of the second mixing is preferably: mixing the aluminum chloride modified silica gel with the second organic solvent to obtain an aluminum chloride modified silica gel dispersion; mixing the aluminum chloride modified silica gel dispersion with the trifluoromethanesulfonic acid.
In the present invention, the second mixing is preferably performed under stirring, and the present invention does not require any special requirement for the specific implementation of the stirring.
In the present invention, the second mixing is performed in a protective atmosphere, preferably an inert gas atmosphere or a nitrogen atmosphere, and in a specific embodiment of the present invention, the inert gas atmosphere is particularly preferably an argon atmosphere.
In the present invention, the holding temperature of the trifluoromethanesulfonic acid modification is preferably 0 to 100 ℃, more preferably 5 to 80 ℃, and most preferably 10 to 50 ℃.
In the present invention, the incubation time for the modification with trifluoromethanesulfonic acid is preferably 0.5 to 6 hours, more preferably 2 to 4.5 hours.
In the present invention, the modification of the trifluoromethanesulfonic acid is performed in a protective atmosphere, preferably an inert gas atmosphere or a nitrogen atmosphere, and in a specific embodiment of the present invention, the inert gas atmosphere is particularly preferably an argon atmosphere.
In the invention, when the trifluoromethanesulfonic acid is modified, the trifluoromethanesulfonic acid is a strong Lewis acid and can react with aluminum chloride chemically adsorbed on the surface and in the pores of the silica gel to generate (F) 3 CSO 3 ) x AlCl 3-x 0 < x < 3, and can form covalent bonds with Si-O-Si groups on the surface and in the pores of the silica gel to be chemically adsorbed on the surface and in the pores of the silica gel.
In the present invention, when the second organic solvent is preferably an organic solvent capable of dissolving the trifluoromethanesulfonic acid, the modification of the trifluoromethanesulfonic acid is preferably: the trifluoromethanesulfonic acid and the second organic solvent form a solution of trifluoromethanesulfonic acid, which solution of trifluoromethanesulfonic acid modifies the aluminum chloride modified silica gel. In the invention, the trifluoromethyl sulfonic acid solution can be fully contacted with the surface and the pore structure of the aluminum chloride modified silica gel, so that the aluminum chloride can be more fully and uniformly modified on the aluminum chloride modified silica gel.
In the invention, the heat preservation temperature of the trifluoromethanesulfonic acid modification is 0-100 ℃ in a liquid environment, the modification heat preservation temperature is lower, and the energy consumption is low.
In the invention, the trifluoromethyl sulfonic acid is modified to obtain a trifluoromethyl sulfonic acid modified liquid, and the invention preferably carries out aftertreatment on the trifluoromethyl sulfonic acid modified liquid to obtain the aluminum chloride/trifluoromethyl sulfonic acid modified silica gel.
In the present invention, the post-treatment preferably includes: and (5) sequentially performing solid-liquid separation, washing and drying. The solid-liquid separation is preferably performed by washing the solid product obtained by the solid-liquid separation, the number of times of washing is preferably 3, the washing solvent is preferably an organic solvent capable of dissolving the trifluoromethanesulfonic acid, the washing solvent is preferably toluene in the specific example of the invention, and the amount of the washing solvent used in each washing is not particularly limited. The solid product after washing is preferably dried, and in the present invention, the drying is preferably vacuum drying, the vacuum degree of the vacuum drying is preferably-0.08 to-0.1 MPa, and the temperature of the vacuum drying is preferably 100 to 800 ℃, and more preferably 200 to 600 ℃. The invention has no special requirement on the time of vacuum drying, and the vacuum drying is carried out until the weight is constant. After vacuum drying, the solid product is naturally cooled to room temperature in a protective atmosphere, preferably an inert gas atmosphere or a nitrogen atmosphere.
According to the invention, the non-adsorbed and reacted trifluoromethane sulfonic acid on the surface and in the pores of the aluminum chloride modified silica gel is removed through post-treatment, so that when the modified silica gel is used as a polyolefin catalyst carrier to load the organic transition metal complex, the non-adsorbed trifluoromethane sulfonic acid can swim out from the pore diameter of the silica gel, and the load capacity and the load firmness degree of the organic transition metal complex on the surface and in the pore diameter of the modified silica gel are reduced.
The invention provides the aluminum chloride/trifluoromethanesulfonic acid modified silica gel prepared by the preparation method in the technical scheme, which comprises silica gel, aluminum chloride, trifluoromethanesulfonic acid and reaction products of the aluminum chloride and the trifluoromethanesulfonic acid adsorbed on the surface and in holes of the silica gel, wherein the chemical composition of the reaction products of the aluminum chloride and the trifluoromethanesulfonic acid is (F) 3 CSO 3 ) x AlCl 3-x ，0＜x＜3。
According to the aluminum chloride/trifluoromethanesulfonic acid modified silica gel provided by the invention, through the synergistic effect of the aluminum chloride, the trifluoromethanesulfonic acid, the reaction product of the aluminum chloride and the trifluoromethanesulfonic acid, the silica gel can have proper Lewis acid content, and the polymerization activity and stability of a catalytic active center can be effectively enhanced when the silica gel is used as a polyolefin catalyst carrier.
The invention provides application of the aluminum chloride/trifluoromethanesulfonic acid modified silica gel in preparation of a supported catalyst.
In the present invention, the aluminum chloride/trifluoromethanesulfonic acid-modified silica gel is preferably used as a carrier for the supported catalyst.
The invention provides a supported catalyst, which comprises a carrier and an active component supported on the surface and in holes of the carrier, wherein the active component comprises an organic transition metal complex and an activator, the carrier is the aluminum chloride/trifluoromethane sulfonic acid modified silica gel according to the technical scheme, the organic transition metal complex is a complex formed by unsubstituted or substituted cyclopentadienyl and transition metal, and the activator comprises alkyl aluminum and/or alkyl aluminoxane.
In the present invention, the organic transition metal is a complex formed by unsubstituted or substituted cyclopentadienyl and a transition metal. The transition metal is preferably titanium, zirconium or hafnium.
In the present invention, the organic transition metal complex is preferably cyclopentadienyl titanium trichloride, pentamethyl cyclopentadienyl titanium trichloride, tris (indenyl) titanium dichloride, titanocene dichloride, pentamethyl cyclopentadienyl zirconium trichloride, zirconocene dichloride, bis (n-butylcyclopentadienyl) zirconium dichloride, bis (t-butylcyclopentadienyl) zirconium dichloride, bis (1-butyl-3-methylcyclopentadienyl) zirconium dichloride, bisindenyl zirconium dichloride, bis (2-methylindenyl) zirconium dichloride, bis (2-phenylindenyl) zirconium dichloride, bis (trimethylsilyl cyclopentadienyl) zirconium dichloride, bis [1, 3-bis (trimethylsilyl) cyclopentadienyl ] zirconium dichloride dimethylsilyl bis (cyclopentenyl) zirconium dichloride, rac-vinylbisindenyl zirconium dichloride, rac-dimethylsilyl bis (2-methyl-4-phenylindenyl) zirconium dichloride, rac-dimethylsilyl bis (2-methyl-4, 5-benzindenyl) zirconium chloride, dimethylsilyl (cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylsilyl (cyclopentadienyl) (9-fluorenyl) zirconium dichloride, isopropylidene (3-methylcyclopentadienyl) (9-fluorenyl) zirconium dichloride, dibenzoylmethylene (cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene cyclopentadiene (2, 7-di-tert-butyl-fluorenyl) zirconium dichloride, di-p-tolylene cyclopentadiene (2, 7-di-tert-butyl-fluorenyl) zirconium dichloride, dimethylsilyl bis (9-fluorenyl) zirconium dichloride, disilyl tert-butylamine tetramethylcyclopentadiene titanium dichloride, 1, 2-bis (dimethylsilyl) cyclopentadienyl (3, 5-diisopropylcyclopentadienyl) zirconium dichloride, (1, 1' -dimethylsilyl) (2 ',2' -dimethylsilyl) -bisindenyl zirconium dichloride, (1, 2' -dimethylsilyl) (2, 1' -dimethylsilyl) -bis (3-trimethylsilylmethyleneindenyl) zirconium dichloride, rac-dimethylsilyl bis (2, 5-dimethyl-3-phenyl-6-cyclopenta [2,3-b ] thiophene) zirconium dichloride, dimethylsilyl (2-indenyl) (2-phenylindenyl) zirconium dichloride, hafnium bis (n-propyl) cyclopentadienyl) hafnium dichloride, bis (n-propyl) cyclopentadienyl, bis (tert-butyl) cyclopentadienyl dichloride.
In the present invention, the activator comprises an aluminum alkyl and/or an aluminum alkyl oxygen alkane.
In the present invention, the alkyl aluminum preferably includes one or more of trimethylaluminum, triethylaluminum, triisobutylaluminum, dimethylaluminum hydride, diethylaluminum hydride, diisobutylaluminum hydride, trihexylaluminum, dihexylaluminum hydride, trioctylaluminum and dioctylaluminum hydride.
In the present invention, the alkylaluminoxane preferably includes one or more of methylaluminoxane, ethylaluminoxane, n-propylaluminoxane, n-butylaluminoxane and isobutylaluminoxane.
In the present invention, when the activator preferably includes an aluminum alkyl and an aluminum alkyl, the molar ratio of the aluminum alkyl to the aluminum alkyl in the activator is preferably (0.01 to 1): 1.
In the present invention, the mass ratio of the organic transition metal complex to the aluminum chloride/trifluoromethanesulfonic acid-modified silica gel is preferably (0.01 to 0.1): 1, more preferably (0.02 to 0.08): 1.
In the present invention, the mass ratio of the activator to the aluminum chloride/trifluoromethanesulfonic acid-modified silica gel is preferably (0.105 to 1.1): 1.
The invention provides a preparation method of the supported catalyst, which comprises the following steps:
And mixing a carrier, an organic transition metal complex, an activator and a third organic solvent (hereinafter referred to as third mixing) in a protective atmosphere to obtain the supported catalyst, wherein the carrier is the aluminum chloride/trifluoromethanesulfonic acid modified silica gel according to the technical scheme, the organic transition metal complex is a complex formed by unsubstituted or substituted cyclopentadienyl and transition metal, and the activator comprises aluminum alkyl and/or aluminum alkyl oxygen alkane.
In a specific embodiment of the present invention, the third organic solvent is preferably toluene or hexane.
In the present invention, the activator preferably comprises an aluminum alkyl and an aluminum alkyl, and the carrier, the organic transition metal complex, the activator, and the third organic solvent are mixed, and further comprises a pretreatment of the aluminum alkyl and the aluminum alkyl, the pretreatment comprising the steps of:
mixing the aluminum alkyl, the alkyl aluminoxane and a fourth organic solvent (hereinafter referred to as a fourth mixture) in a protective atmosphere, and then removing the solvent; the heat preservation temperature of the mixture of the aluminum alkyl, the alkyl aluminoxane and the fourth organic solvent is 0-80 ℃; the heat preservation time of the mixture of the alkyl aluminum, the alkyl aluminoxane and the fourth organic solvent is 1 to 6 hours.
In the present invention, the fourth organic solvent preferably includes one or more of toluene, hexane, heptane, methylcyclohexane, and the amount of the fourth organic solvent is not particularly limited, and the alkylaluminum and alkylaluminoxane may be completely dissolved.
In the present invention, the order of the four mixing is preferably: mixing the alkyl aluminum and part of the fourth organic solvent to obtain an alkyl aluminum solution, mixing the alkyl aluminoxane and the rest of the fourth organic solvent to obtain an alkyl aluminoxane solution, and mixing the alkyl aluminum solution and the alkyl aluminoxane solution.
In the present invention, the holding temperature of the fourth mixture is preferably 0 to 80 ℃, more preferably 15 to 65 ℃.
In the present invention, the holding time of the fourth mixing is preferably 1 to 6 hours, more preferably 2 to 5 hours.
In the present invention, the fourth mixing is preferably performed under stirring, and the present invention does not require any special requirement for the specific implementation of the stirring.
In the present invention, the fourth mixing is performed in a protective atmosphere, preferably an inert gas atmosphere or a nitrogen atmosphere, and in a specific embodiment of the present invention, the inert gas atmosphere is particularly preferably an argon atmosphere.
In the invention, the specific implementation mode of the solvent removal is preferably vacuum filtration, and the specific implementation process of the vacuum filtration is not particularly required.
The activator obtained by the pretreatment can be dissolved in aromatic hydrocarbon solvent or aliphatic hydrocarbon solvent to prepare solution, and can be stored for a long time at room temperature in protective atmosphere for standby without gel or precipitation of solid precipitate to affect use.
The activator obtained by the pretreatment can be suitable for activating other polyolefin catalysts, and is especially used for olefin polymerization systems with requirements on aromatic hydrocarbon-free solvents.
In the present invention, the third mixing preferably includes the steps of:
mixing the carrier, part of the activating agent and part of the third organic solvent to obtain an activated aluminum chloride/trifluoromethanesulfonic acid modified silica gel dispersion;
mixing the organic transition metal complex, the residual activator and the residual third organic solvent to obtain an activated organic transition metal complex solution;
mixing the activated aluminum chloride/trifluoromethanesulfonic acid modified silica gel dispersion with the activated organic transition metal complex solution.
The aluminum chloride/trifluoromethanesulfonic acid modified silica gel, a part of activating agent and a part of fourth organic solvent are mixed to obtain an activated aluminum chloride/trifluoromethanesulfonic acid modified silica gel dispersion liquid.
In the present invention, the partial activator is preferably the above-mentioned pretreated aluminum alkyl and aluminum alkyl oxyalkyl activator.
In the present invention, the mass ratio of the partial activator to the carrier is preferably (0.1 to 0.6): 1, more preferably (0.2 to 0.5): 1.
In the present invention, the order in which the support, part of the activator and the first part of the third organic solvent are mixed is preferably: dispersing the carrier in a third organic solvent to obtain a carrier dispersion; dissolving a part of the activator in a second part of the third organic solvent to obtain a part of activator solution; the carrier dispersion and a portion of the activator solution are mixed. In the present invention, the ratio of the mass of the carrier to the volume of the first portion of the fourth organic solvent is preferably 1g to 5ml; the mass percentage of the partial activator solution is 10wt%.
After mixing the carrier dispersion and a portion of the activator solution, the invention preferably continues to stir for 1 hour.
The organic transition metal complex, the rest of the activating agent and the rest of the third organic solvent are mixed to obtain an activated organic transition metal complex solution.
In the present invention, the remaining activator is preferably an aluminum alkyl or an aluminum alkyl oxygen alkane.
In the present invention, the mass ratio of the residual activator to the organic transition metal complex is preferably (0.5 to 5): 1, more preferably (1.5 to 4): 1.
In the present invention, the order in which the organic transition metal complex, the remaining activator and the remaining third organic solvent are mixed is preferably: dissolving the organic transition metal complex in the first part of the rest of the third organic solvent to obtain an organic transition metal complex solution; mixing the remaining activator and the second portion of the remaining third organic solvent to obtain a remaining activator solution, and mixing the organic transition metal complex solution and the remaining activator solution. In the present invention, the volume ratio of the mass of the organic transition metal complex to the first portion of the remaining third organic solvent is preferably 1g (150 to 300 mL). In the present invention, the mass percentage of the remaining activator solution is preferably 10wt% or the molar concentration of the remaining activator solution is preferably 1mol/L.
After the organic transition metal complex solution and the rest activator solution are mixed, the invention preferably continues to stir and mix for 0.5 to 1 hour.
After the activated aluminum chloride/trifluoromethanesulfonic acid modified silica gel dispersion and the activated organic transition metal complex solution are obtained, the activated aluminum chloride/trifluoromethanesulfonic acid modified silica gel dispersion and the activated organic transition metal complex solution are mixed.
In the present invention, the holding temperature of the third mixture is preferably 25 to 100 ℃, more preferably 45 to 80 ℃.
In the present invention, the incubation time after mixing the activated aluminum chloride/trifluoromethanesulfonic acid modified silica gel dispersion and the activated organic transition metal complex solution is preferably 2 hours.
In the present invention, the third mixing is performed in a protective atmosphere, preferably an inert gas atmosphere or a nitrogen atmosphere, and in a specific embodiment of the present invention, the inert gas atmosphere is particularly preferably an argon atmosphere.
In the present invention, the third mixed solution is obtained after the third mixing, and the present invention preferably performs a post-treatment on the third mixed solution to obtain the supported catalyst. In the present invention, the post-treatment preferably includes: sequentially performing solid-liquid separation, washing and drying. The specific implementation mode of the solid-liquid separation is not particularly required, the solid product obtained by the solid-liquid separation is preferably washed, and in the invention, the washing preferably comprises a first washing and a second washing in sequence; in the present invention, the number of times of the first washing is preferably 3, and the first washing solvent is preferably toluene; in the present invention, the number of times of the second washing is preferably 3, the second washing solvent is preferably hexane, and the amount of the washing solvent to be used in each washing is not particularly limited. The invention preferably provides for drying the washed solid product, and the invention is not particularly limited to the particular implementation of said drying. In the present invention, the solid-liquid separation, washing and drying are all performed in a protective atmosphere, which is preferably an inert gas atmosphere or a nitrogen atmosphere.
The supported catalyst is preferably stored in a protective atmosphere, preferably an inert gas atmosphere or a nitrogen atmosphere.
The invention provides the application of the supported catalyst according to the technical scheme or the supported catalyst prepared by the preparation method according to the technical scheme in olefin polymerization reaction.
In the present invention, the olefin preferably includes one or more of ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, norbornene, styrene, divinylbenzene, 1, 3-butadiene, 2-methyl-1, 3-butadiene, 1, 4-pentadiene, 1, 5-hexadiene, 1, 7-octadiene, 1, 9-decadiene.
In the present invention, the polymerization reaction preferably includes a homo-polymerization reaction or a copolymerization reaction.
In the present invention, the specific embodiment of the polymerization reaction is preferably one or a combination of several of bulk polymerization, gas phase polymerization and slurry polymerization.
In the present invention, the polymerization reaction is preferably a continuous process and/or a batch process.
In the present invention, the polymerization reaction temperature is preferably 50 to 120 ℃.
In the present invention, the pressure of the polymerization reaction is preferably 0.1 to 10MPa.
In the present invention, the raw material for the polymerization reaction preferably includes hydrogen.
In the present invention, the supported catalyst is preferably used in the form of a solid dry powder or in the form of a supported catalyst dispersion,
in the present invention, when the supported catalyst is used in the form of a supported catalyst dispersion, the dispersion medium in the supported catalyst dispersion is preferably one or more of pentane, hexane, heptane, octane, toluene and white oil.
The technical solutions of the present invention will be clearly and completely described in the following in connection with the embodiments of the present invention.
In the examples below, the preparation is carried out, unless otherwise specified, in an anhydrous and oxygen-free protective atmosphere, in particular in a nitrogen atmosphere or in an argon atmosphere. The organic solvents used, unless otherwise specified, were treated with dry molecular sieves to a water content of < 10ppm before use.
Example 1
The silica gel material has average particle diameter of 70 μm, particle morphology of spheroid, and 1.5cm 3 Specific pore volume per gram and 200m 2 Specific surface area/g;
heating 50g of silica gel to 100 ℃ and vacuum (the vacuum degree is minus 0.08 to minus 0.1 MPa), drying and dehydrating for 4 hours, and naturally cooling to room temperature under the protection of nitrogen to obtain pretreated silica gel;
Under the protection of nitrogen or argon, 10g of pretreated silica gel is weighed and transferred into a glass reactor fully replaced by nitrogen, and 50mL of carbon tetrachloride is added. After stirring to disperse the mixture uniformly, 2g of aluminum chloride was added, and the mixture was heated to 80℃and reacted for 0.5 hour (the reaction system was in a reflux state). After the reaction is finished, washing the solid product for 2 times by using 50mL of carbon tetrachloride, heating the product to 800 ℃ for vacuum drying, and naturally cooling to room temperature under the protection of nitrogen to obtain an aluminum chloride modified silica gel carrier;
under the protection of nitrogen or argon, 5g of aluminum chloride modified silica gel is weighed and transferred into a glass reactor which is fully replaced by nitrogen, 25mL of toluene is added, the mixture is stirred to be uniformly dispersed, 0.5g of trifluoromethanesulfonic acid is added, and the mixture is heated to 100 ℃ for reaction for 0.5 hour. After the reaction is finished, the solid product is washed by 25mL of toluene for 2 times, the product is heated to 400 ℃ and dried in vacuum, and then the temperature is naturally reduced to room temperature under the protection of nitrogen, thus obtaining the aluminum chloride/trifluoromethanesulfonic acid modified silica gel carrier.
Example 2
7.1g of the dry methylaluminoxane powder was weighed under nitrogen protection, transferred to a glass reactor which was fully replaced by nitrogen, and 20mL of hexane was added. Stirring to uniformly disperse the mixture to obtain methylaluminoxane dispersion;
Under the protection of nitrogen, trioctylaluminum is dissolved in hexane to obtain trioctylaluminum solution with the concentration of 1 mol/L;
10mL of trioctylaluminum solution was added to the methylaluminoxane dispersion and stirred at 40℃for 1 hour to give a clear colorless liquid. And removing hexane by vacuum pumping, and preserving the product under nitrogen for later use, and recording as an activator A.
5g of the aluminum chloride/trifluoromethanesulfonic acid-modified silica gel prepared in example 1 was accurately weighed under nitrogen protection, transferred to a glass reactor fully replaced with nitrogen, and 25mL of toluene was added. After stirring to disperse uniformly, 20g of an activator A solution (10 wt% toluene solution) is added, and stirring is carried out at 50 ℃ for 1 hour to obtain an activated aluminum chloride/trifluoromethanesulfonic acid modified silica gel dispersion;
50mg of bis (butylcyclopentadienyl) zirconium dichloride was accurately weighed under nitrogen protection, transferred to a glass reactor fully replaced with nitrogen, and 15mL of toluene was added. Stirring at 50deg.C to dissolve, adding 1g methylaluminoxane solution (10 wt% toluene solution), and stirring for 0.5 hr to obtain activated bis (butylcyclopentadienyl) zirconium dichloride solution;
the activated aluminum chloride/trifluoromethanesulfonic acid modified silica gel dispersion and the activated bis (butylcyclopentadienyl) zirconium dichloride solution were mixed under nitrogen protection, stirred at 50 ℃ for 2 hours to obtain a mixed solution, and after solid-liquid separation, the solid product was washed with 30mL of toluene for 2 times and then with 30mL of hexane for 2 times. The product was dried in vacuo to give the supported catalyst (designated cat 1).
Example 3
5g of aluminum chloride/trifluoromethanesulfonic acid modified silica gel is accurately weighed under the protection of nitrogen, transferred to a glass reactor fully replaced by nitrogen, and 25mL of toluene is added. After stirring to disperse uniformly, 10g of the activator A (10 wt% toluene solution) prepared in example 2 was added, and stirred at 30℃for 1 hour to obtain an activated aluminum chloride/trifluoromethanesulfonic acid modified silica gel dispersion;
100mg of rac-dimethylsilyl bis (2-methyl-4-phenylindenyl) zirconium dichloride was accurately weighed under nitrogen protection, transferred to a glass reactor fully replaced with nitrogen, and 15mL of toluene was added. It was dissolved by stirring at 30 ℃. 1mL of triisobutylaluminum solution (1 mol/L toluene solution) was added thereto, and stirring was continued for 1 hour to obtain an activated rac-dimethylsilyl bis (2-methyl-4-phenylindenyl) zirconium dichloride solution;
the activated aluminum chloride/trifluoromethanesulfonic acid modified silica gel dispersion and the activated rac-dimethylsilyl bis (2-methyl-4-phenylindenyl) zirconium dichloride solution are mixed under the protection of nitrogen, heated to 80 ℃ and stirred for 1 hour to obtain a mixed solution, and the solid product after solid-liquid separation is washed 2 times with 30mL of toluene and 2 times with 30mL of hexane. The product was dried in vacuo to give the supported catalyst (designated cat 2).
Example 4
65mL of methylaluminoxane solution (10 wt% in toluene) was transferred under nitrogen protection to a glass reactor which was fully replaced with nitrogen. 13mL of triisobutylaluminum solution (1 mol/L hexane solution) was added dropwise to the methylaluminoxane solution at room temperature, and after stirring at 40℃for 1 hour, a clear colorless liquid was obtained. And (5) removing the solvent by vacuum pumping, and preserving the product under nitrogen for standby, and recording as an activator B.
5g of aluminum chloride/trifluoromethanesulfonic acid modified silica gel is accurately weighed under the protection of nitrogen, transferred to a glass reactor fully replaced by nitrogen, and 25mL of toluene is added. After stirring to disperse uniformly, 5g of an activator B (10 wt% toluene solution) is added, and the mixture is stirred at 30 ℃ for 1 hour to obtain an activated aluminum chloride/trifluoromethanesulfonic acid modified silica gel dispersion;
100mg of diphenylmethylene (cyclopentadiene) (9-fluorenyl) zirconium dichloride was accurately weighed under nitrogen protection, transferred to a glass reactor fully replaced with nitrogen, and 15mL of toluene was added. It was dissolved by stirring at 30 ℃. 0.5mL of diisobutylaluminum hydride solution (1 mol/L hexane solution) was added thereto, and stirred for 0.5 hour to obtain an activated diphenylmethylene (cyclopentadiene) (9-fluorenyl) zirconium dichloride solution;
the activated aluminum chloride/trifluoromethanesulfonic acid modified silica gel dispersion and the activated benzhydryl (cyclopentadiene) (9-fluorenyl) zirconium dichloride solution are mixed under the protection of nitrogen, heated to 80 ℃ and stirred for 1 hour to obtain a mixed solution, the mixed solution is subjected to solid-liquid separation, and after the solid product is washed with 30mL of toluene for 2 times and then with 30mL of hexane for 2 times. The product was dried in vacuo to give the supported catalyst (designated cat 3).
Comparative example 1
The preparation process was essentially the same as in example 2, except that: the pretreated silica gel of example 1 was used in place of the aluminum chloride/trifluoromethanesulfonic acid modified silica gel to give a supported catalyst (designated cat 4).
Comparative example 2
The preparation process was essentially the same as in example 3, except that: the aluminum chloride-modified silica gel of example 1 was used in place of the aluminum chloride/trifluoromethanesulfonic acid-modified silica gel to give a supported catalyst (designated cat 5).
Comparative example 3
The preparation process was essentially the same as in example 4, except that: the aluminum chloride-modified silica gel of example 1 was used in place of the aluminum chloride/trifluoromethanesulfonic acid-modified silica gel to give a supported catalyst (designated cat 6).
Application example 1
The cat1 prepared in example 2 and the cat4 prepared in comparative example 1 were used for ethylene homo-or copolymerization;
the ethylene homopolymerization reaction is as follows: in a 5L stainless steel autoclave, after sufficient displacement with ethylene, 2L of hexane was added, 5mL of triethylaluminum (1 mol/L hexane solution) was added, stirring was turned on, then 100mg of catalyst (cat 1 or cat 4) was added, ethylene was introduced, the pressure was increased and maintained at 1.0MPa, and the mixture was heated to 60℃for reaction for 1 hour. After the polymerization is finished, stopping ethylene feeding, cooling to room temperature, opening a vent valve to enable the pressure in the kettle to be reduced to normal pressure, replacing 2 times by nitrogen, and discharging. After filtration to remove hexane, the polymer product was dried at 40 ℃.
The ethylene copolymerization is essentially the same as the ethylene homopolymerization, except that: 1L of hexane was added, and a certain mass of comonomer was added, the monomer types and masses being shown in Table 1. The polymerization activities of the catalysts are shown in Table 1.
Table 1 application example 1 ethylene polymerization conditions and results
Application example 2
The catalyst prepared in example 3, catalyst prepared in example 4, catalyst prepared in comparative example 2, catalyst prepared in comparative example 3 and catalyst prepared in comparative example 6 were used for propylene homopolymerization and hydrogenation polymerization;
the propylene homopolymerization reaction is as follows: in a 5L stainless steel autoclave, after sufficient displacement with nitrogen, 1.5kg of liquid propylene was added, 5mL of triethylaluminum (1 mol/L in hexane) was added, stirring was turned on, followed by addition of 100mg of catalyst (cat 2, cat3, cat5 or cat 6), and the temperature was raised to 60℃for reaction for 1 hour. After the homopolymerization reaction is finished, the temperature is reduced to room temperature, a vent valve is opened to enable the pressure in the kettle to be reduced to normal pressure, nitrogen is used for replacing for 2 times, then the material is discharged, and the polymer is dried at 40 ℃.
The propylene hydro-polymerization is substantially the same as the propylene homo-polymerization except that: before 1.5kg of liquid propylene was added, a quantity of hydrogen was added to the polymerizer, the quantity of hydrogen added being shown in Table 2, and the polymerization activity of the catalyst cat2, cat3, cat5 or cat6 being shown in Table 2.
TABLE 2 application example 1 propylene polymerization conditions and results
From the results shown in tables 1 and 2, the catalyst prepared by the invention adopts aluminum chloride/trifluoromethanesulfonic acid modified silica gel as a catalyst carrier, and three specific Lewis acids of aluminum chloride, trifluoromethanesulfonic acid, and reaction products of aluminum chloride and trifluoromethanesulfonic acid are matched identically, so that the polymerization activity of the supported catalyst in the process of catalyzing olefin polymerization can be obviously improved.
The catalyst prepared by the invention runs for 400min on a polymerization device, and the polymerization activity is kept stable.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. The preparation method of the aluminum chloride/trifluoromethyl sulfonic acid modified silica gel comprises the following steps:
carrying out heat treatment dehydration on silica gel in a protective atmosphere or a vacuum environment to obtain pretreated silica gel;
mixing the pretreated silica gel, aluminum chloride and a first organic solvent in a protective atmosphere to carry out aluminum chloride modification to obtain aluminum chloride modified silica gel, wherein the mass ratio of the aluminum chloride to the pretreated silica gel is (0.1-0.5): 1;
Mixing the aluminum chloride modified silica gel, the trifluoromethanesulfonic acid and a second organic solvent in a protective atmosphere to perform trifluoromethanesulfonic acid modification to obtain aluminum chloride/trifluoromethanesulfonic acid modified silica gel, wherein the mass ratio of the trifluoromethanesulfonic acid to the aluminum chloride modified silica gel is (0.1-0.5): 1;
aluminum chloride/trifluoromethanesulfonic acid modified silica gel including silica gel, aluminum chloride, trifluoromethanesulfonic acid and reaction products of aluminum chloride and trifluoromethanesulfonic acid adsorbed on the surface and in the pores of the silica gel, the chemical composition of the reaction products of aluminum chloride and trifluoromethanesulfonic acid being (F) 3 CSO 3 ) x AlCl 3-x ，0＜x＜3。
2. The preparation method according to claim 1, wherein the heat preservation temperature of the aluminum chloride modification is 20-80 ℃, and the heat preservation time of the aluminum chloride modification is 0.5-6 h;
the temperature of the trifluoro-methanesulfonic acid modification is 0-100 ℃, and the temperature of the trifluoro-methanesulfonic acid modification is 0.5-6 h.
3. The method according to claim 1, wherein the silica gel has an average particle diameter of 10 to 100. Mu.m, and a specific surface area of 100 to 1000m 2 Per gram, the specific pore volume of the silica gel is 0.5-3 cm 3 /g。
4. An aluminum chloride/trifluoromethanesulfonic acid-modified silica gel as defined in any one of claims 1 to 3, comprising a silica gel, aluminum chloride, trifluoromethanesulfonic acid and a reaction product of aluminum chloride and trifluoromethanesulfonic acid adsorbed on the surface and in the pores of said silica gel, said reaction product of aluminum chloride and trifluoromethanesulfonic acid having a chemical composition of (F 3 CSO 3 ) x AlCl 3-x ，0＜x＜3。
5. The use of the aluminum chloride/trifluoromethanesulfonic acid modified silica gel according to claim 4 in supported catalysts.
6. A supported catalyst comprising a support, an active component supported on the surface and in the pores of the support, the active component comprising an organic transition metal complex and an activator, the support being the aluminum chloride/trifluoromethanesulfonic acid modified silica gel of claim 4, the organic transition metal complex being a complex of an unsubstituted or substituted cyclopentadienyl and a transition metal, the activator comprising an alkyl aluminum and/or an alkyl aluminoxane.
7. The supported catalyst according to claim 6, wherein the mass ratio of the organic transition metal complex to the aluminum chloride/trifluoromethanesulfonic acid-modified silica gel is (0.01 to 0.1): 1.
8. The method for preparing the supported catalyst according to claim 6 or 7, comprising the steps of:
mixing a carrier, an organic transition metal complex, an activating agent and a third organic solvent in a protective atmosphere to obtain the supported catalyst, wherein the carrier is the aluminum chloride/trifluoromethane sulfonic acid modified silica gel according to claim 4, the organic transition metal complex is a complex formed by unsubstituted or substituted cyclopentadienyl and transition metal, and the activating agent comprises aluminum alkyl and/or aluminum alkyl aluminoxane.
9. The method of preparing according to claim 8, wherein the activator comprises an alkyl aluminum and an alkyl aluminoxane, and the pre-treating the alkyl aluminum and the alkyl aluminoxane before the mixing of the support, the organic transition metal complex, the activator, and the third organic solvent, the pre-treating comprising the steps of:
in a protective atmosphere, mixing the aluminum alkyl, the alkyl aluminoxane and a fourth organic solvent, and removing the solvent; the heat preservation temperature of the mixture of the aluminum alkyl, the alkyl aluminoxane and the fourth organic solvent is 0-80 ℃; the heat preservation time of the mixture of the alkyl aluminum, the alkyl aluminoxane and the fourth organic solvent is 1 to 6 hours.
10. Use of the supported catalyst according to claim 6 or 7 or the supported catalyst according to claim 8 or 9 in olefin polymerization.
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| CN102171253A (en) * | 2008-10-02 | 2011-08-31 | 道达尔石油化学产品研究弗吕公司 | Activating supports based on perfluorinated boronic acids |
| CN103370344A (en) * | 2011-01-20 | 2013-10-23 | 英尼奥斯商业服务英国有限公司 | Activating supports |
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| CN102171253A (en) * | 2008-10-02 | 2011-08-31 | 道达尔石油化学产品研究弗吕公司 | Activating supports based on perfluorinated boronic acids |
| CN103370344A (en) * | 2011-01-20 | 2013-10-23 | 英尼奥斯商业服务英国有限公司 | Activating supports |
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