CN111285903A - 一种铬系催化剂、催化剂的制备方法及其应用 - Google Patents
一种铬系催化剂、催化剂的制备方法及其应用 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 100
- 239000011651 chromium Substances 0.000 title claims abstract description 39
- 229910052804 chromium Inorganic materials 0.000 title claims abstract description 22
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims description 7
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims abstract description 29
- AFFLGGQVNFXPEV-UHFFFAOYSA-N n-decene Natural products CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 claims abstract description 23
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims abstract description 17
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 claims abstract description 17
- 229910021556 Chromium(III) chloride Inorganic materials 0.000 claims abstract description 16
- 239000004711 α-olefin Substances 0.000 claims abstract description 16
- 238000006384 oligomerization reaction Methods 0.000 claims abstract description 11
- -1 ethylene, propylene, butene Chemical class 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 229960000359 chromic chloride Drugs 0.000 claims abstract description 3
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 claims abstract 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 87
- 239000003446 ligand Substances 0.000 claims description 52
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 32
- 238000006116 polymerization reaction Methods 0.000 claims description 28
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 16
- 239000011636 chromium(III) chloride Substances 0.000 claims description 13
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 7
- 229920002866 paraformaldehyde Polymers 0.000 claims description 7
- 125000001424 substituent group Chemical group 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 5
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 2
- 125000004663 dialkyl amino group Chemical group 0.000 claims description 2
- 239000008098 formaldehyde solution Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 125000002924 primary amino group Chemical class [H]N([H])* 0.000 claims 3
- 230000000536 complexating effect Effects 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 17
- 230000015572 biosynthetic process Effects 0.000 abstract description 15
- 238000003786 synthesis reaction Methods 0.000 abstract description 15
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 37
- 239000005977 Ethylene Substances 0.000 description 37
- 238000006243 chemical reaction Methods 0.000 description 23
- 239000007789 gas Substances 0.000 description 19
- 238000003756 stirring Methods 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 230000003197 catalytic effect Effects 0.000 description 12
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- 238000009826 distribution Methods 0.000 description 9
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- 229910052757 nitrogen Inorganic materials 0.000 description 9
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- 238000005303 weighing Methods 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 239000012074 organic phase Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 6
- 230000001276 controlling effect Effects 0.000 description 6
- DZGCGKFAPXFTNM-UHFFFAOYSA-N ethanol;hydron;chloride Chemical compound Cl.CCO DZGCGKFAPXFTNM-UHFFFAOYSA-N 0.000 description 6
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- 238000004458 analytical method Methods 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- 239000002199 base oil Substances 0.000 description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 125000002524 organometallic group Chemical group 0.000 description 4
- 230000037048 polymerization activity Effects 0.000 description 4
- 150000003141 primary amines Chemical class 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 150000001844 chromium Chemical class 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 125000005842 heteroatom Chemical group 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000004445 quantitative analysis Methods 0.000 description 3
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 3
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- PAPNRQCYSFBWDI-UHFFFAOYSA-N 2,5-Dimethyl-1H-pyrrole Chemical compound CC1=CC=C(C)N1 PAPNRQCYSFBWDI-UHFFFAOYSA-N 0.000 description 2
- 229940105325 3-dimethylaminopropylamine Drugs 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 125000005234 alkyl aluminium group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000004104 aryloxy group Chemical group 0.000 description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- BFGKITSFLPAWGI-UHFFFAOYSA-N chromium(3+) Chemical compound [Cr+3] BFGKITSFLPAWGI-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- IUNMPGNGSSIWFP-UHFFFAOYSA-N dimethylaminopropylamine Chemical compound CN(C)CCCN IUNMPGNGSSIWFP-UHFFFAOYSA-N 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000012263 liquid product Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 150000003335 secondary amines Chemical group 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- LKLLNYWECKEQIB-UHFFFAOYSA-N 1,3,5-triazinane Chemical compound C1NCNCN1 LKLLNYWECKEQIB-UHFFFAOYSA-N 0.000 description 1
- UPLWZGWRVORKQS-UHFFFAOYSA-N 2,3,4,5-tetraethyl-1H-phosphole Chemical compound C(C)C1=C(C(=C(P1)CC)CC)CC UPLWZGWRVORKQS-UHFFFAOYSA-N 0.000 description 1
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexanol Substances CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 1
- XZKIHKMTEMTJQX-UHFFFAOYSA-N 4-Nitrophenyl Phosphate Chemical compound OP(O)(=O)OC1=CC=C([N+]([O-])=O)C=C1 XZKIHKMTEMTJQX-UHFFFAOYSA-N 0.000 description 1
- ALLHOOZJEFGTPW-UHFFFAOYSA-N 7-methylidenepentadecane Chemical compound CCCCCCCCC(=C)CCCCCC ALLHOOZJEFGTPW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910021555 Chromium Chloride Inorganic materials 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- NEDVJZNVOSNSHF-ZNHDNBJUSA-N [(1r,5s)-8,8-dimethyl-8-azoniabicyclo[3.2.1]octan-3-yl] 3-hydroxy-2-phenylpropanoate;nitrate Chemical compound [O-][N+]([O-])=O.C([C@H]1CC[C@@H](C2)[N+]1(C)C)C2OC(=O)C(CO)C1=CC=CC=C1 NEDVJZNVOSNSHF-ZNHDNBJUSA-N 0.000 description 1
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 1
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical group [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 description 1
- QQHSIRTYSFLSRM-UHFFFAOYSA-N alumanylidynechromium Chemical compound [Al].[Cr] QQHSIRTYSFLSRM-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- TYYBBNOTQFVVKN-UHFFFAOYSA-N chromium(2+);cyclopenta-1,3-diene Chemical class [Cr+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 TYYBBNOTQFVVKN-UHFFFAOYSA-N 0.000 description 1
- FRBFQWMZETVGKX-UHFFFAOYSA-K chromium(3+);6-methylheptanoate Chemical compound [Cr+3].CC(C)CCCCC([O-])=O.CC(C)CCCCC([O-])=O.CC(C)CCCCC([O-])=O FRBFQWMZETVGKX-UHFFFAOYSA-K 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 239000012230 colorless oil Substances 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- 229940069096 dodecene Drugs 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QOHMWDJIBGVPIF-UHFFFAOYSA-N n',n'-diethylpropane-1,3-diamine Chemical compound CCN(CC)CCCN QOHMWDJIBGVPIF-UHFFFAOYSA-N 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229940109850 royal jelly Drugs 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F11/00—Compounds containing elements of Groups 6 or 16 of the Periodic Table
- C07F11/005—Compounds containing elements of Groups 6 or 16 of the Periodic Table compounds without a metal-carbon linkage
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
- B01J31/182—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine comprising aliphatic or saturated rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
- C07C2/08—Catalytic processes
- C07C2/26—Catalytic processes with hydrides or organic compounds
- C07C2/32—Catalytic processes with hydrides or organic compounds as complexes, e.g. acetyl-acetonates
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
- C10M107/02—Hydrocarbon polymers; Hydrocarbon polymers modified by oxidation
- C10M107/10—Hydrocarbon polymers; Hydrocarbon polymers modified by oxidation containing aliphatic monomer having more than 4 carbon atoms
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/20—Olefin oligomerisation or telomerisation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
- B01J2531/0244—Pincer-type complexes, i.e. consisting of a tridentate skeleton bound to a metal, e.g. by one to three metal-carbon sigma-bonds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
- B01J2531/62—Chromium
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
- C10M2205/028—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
- C10M2205/0285—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms used as base material
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- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
Description
技术领域
本发明涉及一种铬系催化剂,具体涉及用于α-烯烃聚合的铬系配合物催化剂,催化剂的制备方法及其应用。
背景技术
铬系催化剂按配体的结构和性质分为:阴离子性、具有芳香结构的催化体系和中性、带有多齿杂原子结构的催化体系两类。阴离子性芳香族催化体系采用具有平面结构的芳香化合物为三聚配体,一般以烷基铝为助催化剂。中性的多齿杂原子催化体系的配体,一般带有可与铬(III)形成配位键的杂原子供体(电子对供体),具有双齿或三齿结构,通常与烷基铝氧烷一起使用。多齿杂原子配体特别是磷氮和硫氮杂原子配体具有较高的催化活性和选择性,其应用前景十分广阔。
Phillps公司最先发现吡咯基配体可被用于乙烯三聚合成1-己烯。20世纪80年代后期,茂铬络合物作为聚乙烯催化剂被广泛地应用,而与茂化合物电子结构和化学空间结构都非常相似的杂环化合物,如吡啶、吡咯等的研究却很少。Reagan等【Reagen W K,Pettijohn T M,Freeman J W,et al.Process for olefin polymerization[P].US5451645A,1995】将铬(III)和吡咯络合得到化合物Cr(C4H4N)2Cl,并在催化乙烯聚合的过程中发现:产品中PE的产率很低,而所得液态产物中己烯的比重却高达90.5%,且己烯中92%为正构1-己烯。Reagan等【Reagan W K,Freeman J W,Conroyb K,et al.Processforolefin polymerization[P].US,5451645,1995】随后进行了深入研究,优选2,5-二甲基吡咯(DMP)与异辛酸铬[Cr(III)2-EH]、一氯二乙基铝和TEA体系以3.3:1:7.8:10.8(摩尔比)的比例,在无水无氧的条件下制备了乙烯三聚催化剂,并在115℃、乙烯压力10.0MPa的条件下反应36min,催化剂活性为1.57~10g/gCr·h,产品中99.85%为液态产物,l-己烯选择性为93%,副产物主要是混合癸烯。
2000年BASF公司【BASF AKTIENGESELLSCHAFT;MAAS,HEIKO;MIHAN,SHAHRAM;KOEHN,RANDOLF;SEIFERT,GUIDO;TROPSCH,JUERGEN,OLIGOMERISATION CATALYST,WO2000EP02660,2000】申请一种以1,3,5-三氮环己烷为配体的铬系催化剂催化烯烃齐聚制备α-烯烃,在三氮杂环己烷的氮原子上的基团优选是β-烷基取代的烷基,例如2-乙基己基或2-正丙基庚基。优选的用于低聚的烯烃是具有2-10个碳原子的烯烃。该专利实施例描述了乙烯的齐聚反应和1-丁烯的齐聚反应,在所有使用1-丁烯的实施例中,使用其中在三氮杂环己烷的氮原子上的基团具有β-烷基支链的催化剂。根据其公开(WO00/58319)内容可知,硼化合物和烷基铝可以用作活化添加剂。该方法实现高的烯烃低聚物收率,和优选以高选择性获得指定的低聚物,特别是三聚物。该专利中催化剂不能耐高温,而且只有使用昂贵的硼化合物作为助催化剂才能有高活性,不适合工业使用。
IFP与Sasol公司【Morgan D H,Grove J J C,Bezuidenhout B C,Schwikkard SL.Oligo-merisation process and catalystsystem[P].WO,02/083306,2001】对芳氧基配体进行了详尽的研究,芳氧基催化体系活性很低,一般不超过3.0×10 4g/gCr·h,1-己烯选择性最高为83%,其产品中有大量的固态低聚物,因此难以工业应用。
2001年【Wasserscheid P,Grimm S,R D,et al.Synthesis ofSynthetic Lubr-icants by Trimerization of 1-Decene and 1-Dodecene withHomogeneous Chromium Catalysts[J].Advanced Synthesis&Catalysis.2001,343(8):814-818】报道了用三氮杂环己烷同CrCl3(THF)3反应,得到非茂类的铬系催化剂,取代基R分别为甲基、正戊基、正辛基和正十二烷基时的催化活性分别为455,552,490和7.17g·mol-1·h-1·bar1,Mw/Mn=2~4,Mw=40000。
2001年Jolly等【Jensen V R,Jolly P W,et al.Donor-Ligand-Substituted Cycl-opentadienylchromium(III)Complexes:A New Class of AlkenePolymerization Catalyst.2.Phosphinoalkyl-Substituted Systems[J].Organometallics.2001,20(11):2234-2245】报道了一系列含P,As取代的茂环、茚环和CrCl3(THF)3反应,得到一系列含P,As的铬络合物。在Cr:MAO=1:100,压力为203kPa,t=4min,T=21℃的条件下,得到了乙烯的齐聚产物和聚乙烯.活性和齐聚的程度主要取决于P原子上的取代基R的大小,取代基越大,活性越低,齐聚的程度越高.如R=iPr时,活性为3590g·mol-1·h-1,其中C6-C10的产物占3.1%,PE占96.9%。
2005年,McGuinness等【McGuinness D S,Wassetscheid P,Kelm W,et a1.NovelCr-PNP comple-xesascatalysts for the trimerisation of ethylene[J].ChemicalCommunications.2003,34(3):334-335;McGuinnessD S,Wassetscheid P,MorganDH,etal.EthyleneTrimerization with M-ixed-Donor Ligand(N,P,S)Chromium Complexes:Effect of Ligand Structure on Activity and Selectivity[J].Organometallics.2005,24(4):552-556】进行了PNP配体与低价态铬(+2价或+1价)在低铝铬比(摩尔比约30:1)情况下催化乙烯三聚的试验研究,发现在低TEA用量的情况下,1-己烯在液相产品中所占比重可达99.6%,催化活性最高可达4.18×l04g/gCr·h。通常二膦胺配体更倾向于在相对较低的温度下催化乙烯三聚,如反应温度由100℃降至80℃,催化剂寿命明显延长。
2009年,McGuinness等人【McGuinnessDS.Oligomerization ofα-Olefins viaChromium Metallacycle-s[J].Organometallics.2009,28:244-248】采用Cr(III)-二(碳烯)吡啶络合物为催化剂,其结构如式b,以MAO为助催化剂催化α-烯烃聚合。以1-辛烯为单体,产物主要为头尾结构亚乙烯基二聚体的2-己基1-癸烯,其含量为91%,无三聚体。
2010年,Peitz等【Peitz S,Peulecke N,Aluri B R,et al.A SelectiveChromium Catalyst System for the Trimerization of Ethene and Its CoordinationChemistry[J].Eur-opean Journal of Inorganic Chemistry.2010,2010(8):1167-1171】成出一种新型配体PNPNH用于均相高选择性乙烯三聚反应制备1-己烯,其结构如式a所示,反应体系:CrCl3(THF)3为催化剂,Ph2PN(iPr)P(Ph)N(iPr)H为配体,Et3Al为助催化剂,甲苯为溶剂。此催化体系对合成1-己烯具有很高的选择性,达到99%以上,延长反应时间,其反应活性恒定,为5200g/(g Cr-1·h-1)。加入少量的Et3Al,有少量的PE生成,对工业生产有重要意义。
2013年,祁彦平等【祁彦平,王霄青.四氢呋喃氯化铬在乙烯三聚反应中的研究[J].广州化工.2013,41(12):117-119】以CrCl3(THF)3作为金属活性中心,烷基铝为助催化剂,研究评价了反应体系中Cr离子的浓度、N/Cr摩尔比以及Al/Cr摩尔比对催化剂性能的影响。研究结果表明:该催化剂具有较高的乙烯三聚催化活性,催化剂活性可达2.48×105g产品/(g Cr-1·h-1),1-己烯正构率大于98.5%。
2013年,Stennett等【Stennett T E,Hey T W,Ball LT,et al.N,N-Diphospholylamines-A New Family of Ligands for Highly Active,Chromium-Based,Selective Ethen-e Oligomerisation Catalysts[J].Chemcatchem,2013,5(10):2946-2954】采用Ph2PCl与伯胺反应,合成一系列含有偶磷氮烷(PNP)类配体,以MAO为助催化剂,Al/Cr=300,催化乙烯低聚,其活性大于2×104g/(g Cr-1·h-1),三聚体含量达到80%以上,取代基比较大时,更容易使得七元金属环断裂,得到三聚体。由2,3,4,5-四乙基磷杂环戊二烯衍生出的配体对乙烯低聚具有比较高的活性,对C6和C8线性α-烯烃具有很好的选择性。因此,PNP配体的空间结构对催化剂的选择性和活性产生很大的影响。
总之,在过去的20年中α-烯烃聚合催化剂飞速发展,经历了由第四副族的茂金属催化剂到后过渡金属催化剂的巨大飞跃,这些新型催化剂在聚合方面的特点有利于生产牌号多样的聚烯烃产品,而均相铬系催化剂将逐渐成为人们寻求新的单“中心活性点催化剂的研究热点”。使用价格低廉的原料,缩短合成路线,简化合成工艺,降低成本,提高催化活性仍然是本领域开发的方向。
发明内容
本发明的目的是提供一种含有仲胺取代基的三氮杂环己烷三氯化铬配合物催化剂,同时,公开上述催化剂的制备方法以及催化剂在α-烯烃聚合中的应用。
本发明所述的铬配合物催化剂结构如式(I)所示:
其中,R1、R2为C1-C10的烷基。
优选地,含有仲胺取代基的三氮杂环己烷三氯化铬配合物中,R1、R2结构分别选自:
当R1为-CH2CH2-时,R2为(CH3)2CH-
当R1为-CH2CH2CH2-时,R2为CH3-或CH3CH2-
当R1为-CH2C(CH3)2CH2-时,R2为CH3-
当R1为-CH2CH2CH2CH2-时,R2为CH3-或CH3CH2-
当R1为-CH2CH2CH2CH(CH3)-时,R2为CH3CH2-
当R1为-CH2CH2CH2CH2CH2-时,R2为(CH3)2CH-
当R1为-CH2CH2CH2CH2CH2CH2-时,R2为CH3-或CH3CH2-
上述式(I)化合物的制备采用含有二烷基氨基的伯胺与多聚甲醛的甲醛溶液,制备N取代基的β或γ位含有N原子的三氮杂环己烷配体,再与金属络合得到铬配合物催化剂。具体包括:
(1)在100~130ml四氢呋喃(THF)中,以10~15g CrCl3·6H2O和50~60ml二氯亚砜(SOCl2)为原料,室温反应1h~2h后,升温至70~80℃回流至无气体生成,制备得到CrCl3(THF)3;
(2)在30~50ml甲苯中,以3.0g~4.0g多聚甲醛和过量伯胺为原料,100~120℃反应18~21h,制备三氮杂环己烷配体,
所述的伯胺为(R2)2NR1NH2通式化合物,式中,R1、R2选自C1-C10的烷基;
所述的多聚甲醛分子式为HO-(CH2O)n-H,其中,n=10-100;
(3)在30~50ml甲苯中,以0~3.0g CrCl3(THF)3和过量三氮杂环己烷配体为原料,在室温下反应18~21h,制备得到铬系催化剂。
本发明得到的一系列铬系催化剂,在结构上由于在N原子上引入带有不同原子、不同链长的烷基链,因此改变了活性中心的空间结构和电子环境,从而有效提高催化活性和选择性;同时也由于不同配体的结构可以控制金属中心的电子环境与空间环境,进而调控制备聚合物的活性以及分子量分布,能够得到分子量比较低的聚烯烃;最后由于烷基上的可配位N原子与活化态的中心金属的弱配位作用因此极大提高了该类催化剂的稳定性以及温度耐受性。本发明的铬系催化剂的制备方法具有合成路线短,工艺简单,工业成本低廉的优点,且催化剂特别适用于乙烯、丙烯、丁烯、己烯和辛烯、癸烯等α-烯烃的齐聚反应,与现有技术相比,具有更高活性和选择性。
本发明催化剂用于α-烯烃聚合是作为主催化剂,甲基铝氧烷(MAO)作为助催化剂,主催化剂与助催化剂用量的摩尔比为1:500-2000。
所述的铬催化剂用于乙烯聚合,以烷基铝为助催化剂,齐聚产物中三聚体和四聚体的选择性达到90%以上,催化活性至少达到3.53×105g/molCr·h。例如,在乙烯压力为0.1MPa下,以甲苯为溶剂,加入本发明所述催化剂的甲苯溶液,反应温度0℃~80℃下反应时间0.5小时。此外,还能够有效催化1-丁烯、1-癸烯等长碳链的α-烯烃聚合,催化活性至少达到1.8×105g/molCr·h,可用于制备高品质的PAO润滑油。
具体实施方式
以下对本发明的实施例作详细说明:本实施例在以本发明技术方案为前提下进行实施,给出了详细的实施方式和过程,但本发明的保护范围不限于下述的实施例,下列实施例中未注明具体条件的实验方法,通常按照常规条件。
实施例1
铬系配体催化剂A:[((CH3)2NCH2CH2CH2)3TAC)CrCl3]的合成
配体A[((CH3)2NCH2CH2CH2)3TAC]的合成:称取多聚甲醛(4g)于Schlenk瓶中,量取甲苯40mL,加入3-二甲氨基丙胺(20mL);升温至110℃,搅拌20h,除溶剂,得到无色油状物,加入无水硫酸镁,搅拌,过滤,加入无水硫酸镁进一步除水,得到配体1。1H NMR(δ,400MHz,CDCl3,25℃):3.24(s,6H,N-CH2-N),2.37(q,6H,N-CH2-),2.22(q,6H,CH2-N-(CH3)2),2.14(s,18H,-CH3),1.56(m,6H,-CH2-)。
配体催化剂A[((CH3)2NCH2CH2CH2)3TACCrCl3]的合成:采用Schlenk技术,于手套箱中称取CrCl3(THF)3(1g)于Schlenk瓶中,加入甲苯(20mL),使其溶解,称取配体(1g)于单口瓶中,加入甲苯(20mL),使其溶解,将配体的甲苯溶液滴加到Schlenk瓶中,滴加完成,室温下搅拌反应20h,压滤,洗涤,除溶剂,得到紫色固体粉末1.27g,收率95%。
络合物1的合成路线如下:
实施例2
催化剂A催化乙烯聚合
将配有磁力搅拌子和导气管的100mL高压釜用乙烯气体置换3次,在氮气保护下,依次加入甲苯、助催化剂MAO 2.5mL(1.60M)[Al/Cr=1000],6mg催化剂A,控制总体积为100mL,通入乙烯气体,在60℃下开始聚合反应,维持乙烯压力0.8MPa,搅拌反应30min,关闭气瓶,泄压,然后用10%的盐酸乙醇终止反应,取聚合物液相进行气相色谱分析,计算α-烯烃分布:丁烯-15.40%,己烯65.62%,辛烯26.35%,己烯和辛烯的总选择性达到92%;对聚合物液相进行定量分析,计算得到催化剂的聚合活性为3.53×105g/molCr·h。
实施例3
催化剂A催化1-癸烯聚合
在手套箱中分别称取12mg催化剂A,分别溶于10mL甲苯中,溶液变为紫色,加入20mL1-癸烯单体,20mL甲苯于已烘干抽换气的三口瓶中,加入5mL MAO,搅拌30min,将催化剂溶液加入到三口烧瓶中,60℃下搅拌6h,加入2mol/L的盐酸,直到无气泡产生,出现分层,分液取上层有机相;对有机相进行减压蒸馏,得到PAO基础油,转化率52%,催化活性为1.8×105g/molCr·h,100℃运动粘度6mm2/s,40℃运动粘度31mm2/s,粘度指数143。
实施例4
铬系配体催化剂B:[((CH3CH2)2NCH2CH2CH2)3TAC)CrCl3]的合成
配体B[((CH3CH2)2NCH2CH2CH2)3TAC]的合成同实施例1中配体A,仅是以3-二乙基丙胺代替3-二甲氨基丙胺。测定1H NMR(δ,400MHz,CDCl3,25℃):3.43(s,6H,N-CH2-N),2.40(m,12H,-N-CH2-CH3),2.36(q,12H,-N-CH2-),1.49(m,6H,-CH2-),2.14(q,18H,-CH3)。
铬系配体催化剂B的合成同实施例1,产物收率91%。
实施例5
催化剂B均相催化乙烯聚合
将配有磁力搅拌子和导气管的100mL高压釜用乙烯气体置换3次,在氮气保护下,依次加入甲苯、助催化剂MAO 2.5mL(1.60M)[Al/Cr=1000],6mg催化剂B,控制总体积为100mL,通入乙烯气体,在60℃下开始聚合反应,维持乙烯压力0.8MPa,搅拌反应30min,关闭气瓶,泄压,然后用10%的盐酸乙醇终止反应,取聚合物液相进行气相色谱分析,计算α-烯烃分布:丁烯12.20%,己烯66.85%,辛烯24.74%,己烯和辛烯的总选择性达到91.6%;对聚合物液相进行定量分析,计算得到催化剂的聚合活性为4.26×105g/molCr·h。
实施例6
催化剂B均相催化1-癸烯聚合
在手套箱中分别称取12mg催化剂B,分别溶于10mL甲苯中,溶液变为紫色,加入20mL1-癸烯单体,20mL甲苯于已烘干抽换气的三口瓶中,加入5mL MAO,搅拌30min,将催化剂溶液加入到三口烧瓶中,60℃下搅拌6h,加入2mol/L的盐酸,直到无气泡产生,出现分层,分液取上层有机相;对有机相进行减压蒸馏,得到PAO基础油,转化率58%,催化活性为2.4×105g/molCr·h100℃运动粘度3.2mm2/s,40℃运动粘度12.0mm2/s,粘度指数137。
实施例7
铬系配体催化剂C:[(((CH3)2CH)2NCH2CH2)3TAC)CrCl3]的合成
配体C[((CH3)2CH)2NCH2CH2TAC]的合成同实施例1中配体A,不同之处在于以((CH3)2CH)2NCH2CH2代替(CH3)2NCH2CH2CH2。
催化剂C[(((CH3)2CH)2NCH2CH2)3TAC)CrCl3]的合成:采用Schlenk技术,于手套箱中称取CrCl3(THF)3(1g)于Schlenk瓶中,加入甲苯(20mL),使其溶解,称取配体3(1g)于单口瓶中,加入甲苯(20mL),使其溶解,将配体的甲苯溶液滴加到Schlenk瓶中,滴加完成,室温下搅拌反应20h,压滤,洗涤,除溶剂,得到紫色固体粉末1.23g,收率92%。
实施例8
催化剂C均相催化乙烯聚合
将配有磁力搅拌子和导气管的100mL高压釜用乙烯气体置换3次,在氮气保护下,依次加入甲苯、助催化剂MAO 2.5mL(1.60M)[Al/Cr=1000],6mg催化剂C,控制总体积为100mL,通入乙烯气体,在60℃下开始聚合反应,维持乙烯压力0.8MPa,搅拌反应30min,关闭气瓶,泄压,然后用10%的盐酸乙醇终止反应,取聚合物液相进行气相色谱分析,计算α-烯烃分布:丁烯-16.04%,己烯61.55%,辛烯28.48%,己烯和辛烯的总选择性达到91%;对聚合物液相进行定量分析,计算得到催化剂的聚合活性为6.12×105g/molCr·h。
实施例9
催化剂C均相催化1-癸烯聚合
在手套箱中分别称取12mg催化剂C,分别溶于10mL甲苯中,溶液变为紫色,加入20mL1-癸烯单体,20mL甲苯于已烘干抽换气的三口瓶中,加入5mL MAO,搅拌30min,将催化剂溶液加入到三口烧瓶中,60℃下搅拌6h,加入2mol/L的盐酸,直到无气泡产生,出现分层,分液取上层有机相;对有机相进行减压蒸馏,得到PAO基础油,转化率62.8%,100℃运动粘度6.42mm2/s,40℃运动粘度33.82mm2/s,粘度指数145。
实施例10
铬系配体催化剂D:[((CH3)2NCH2C(CH3)2CH2)3TAC)CrCl3]的合成
配体D[((CH3)2NCH2C(CH3)2CH2)3TAC]的合成同实施例1中配体1,不同之处在于以(CH3)2NCH2C(CH3)2CH2代替(CH3)2NCH2CH2CH2。
催化剂D[((CH3)2NCH2C(CH3)2CH2)3TAC)CrCl3]的合成:采用Schlenk技术,于手套箱中称取CrCl3(THF)3(1g)于Schlenk瓶中,加入甲苯(20mL),使其溶解,称取配体4(1g)于单口瓶中,加入甲苯(20mL),使其溶解,将配体的甲苯溶液滴加到Schlenk瓶中,滴加完成,室温下搅拌反应20h,压滤,洗涤,除溶剂,得到紫色固体粉末1.19g,收率90%。
实施例11
催化剂D均相催化乙烯聚合
将配有磁力搅拌子和导气管的100mL高压釜用乙烯气体置换3次,在氮气保护下,依次加入甲苯、助催化剂MAO 2.5mL(1.60M)[Al/Cr=1000],6mg络合物4,控制总体积为100mL,通入乙烯气体,在60℃下开始聚合反应,维持乙烯压力0.8MPa,搅拌反应30min,关闭气瓶,泄压,然后用10%的盐酸乙醇终止反应,取聚合物液相进行气相色谱分析,计算α-烯烃分布:丁烯-15.54%,己烯62.86%,辛烯28.67%,己烯和辛烯的总选择性达到91.5%;对聚合物液相进行定量分析,计算得到催化剂的聚合活性为6.56×105g/molCr·h。
实施例12
催化剂D均相催化1-癸烯聚合
在手套箱中分别称取12mg催化剂D,分别溶于10mL甲苯中,溶液变为紫色,加入20mL1-癸烯单体,20mL甲苯于已烘干抽换气的三口瓶中,加入5mL MAO,搅拌30min,将催化剂溶液加入到三口烧瓶中,60℃下搅拌6h,加入2mol/L的盐酸,直到无气泡产生,出现分层,分液取上层有机相;对有机相进行减压蒸馏,得到PAO基础油,转化率65.3%,100℃运动粘度7.32mm2/s,40℃运动粘度39.81mm2/s,粘度指数150。
对比例1
取PNPNH型配体:(苯)2磷氮(异丙基)磷(苯)氮(异丙基)氢(Ph2PN(iPr)P(Ph)N(iPr)H)为配体,结构式如式1所示,CrCl3(THF)3为催化剂,Et3Al为助催化剂,甲苯为溶剂(参照文献Peitz S,Peulecke N,Aluri B R,et al.A Selective Chromium CatalystSystem for the Trimerization of Ethene and Its Coordination Chemistry[J].Eur-opean Journal of Inorganic Chemistry,2010(8):1167-1171制备化合物),将配有磁力搅拌子和导气管的100mL高压釜用乙烯气体置换3次,在氮气保护下,依次加入甲苯、助催化剂MAO 2.5mL(1.60M)[Al/Cr=1000],6mg该催化剂,控制总体积为100mL,通入乙烯气体,在60℃下开始聚合反应,维持乙烯压力0.8MPa,搅拌反应30min。聚合结束后,关闭气瓶,泄压,然后用10%的盐酸乙醇终止反应,过滤收集高聚物,滤液进行气相色谱分析,催化剂活性为3.32×105g/molCr·h,1-己烯选择性为42wt%,1-辛烯选择性为32%。
对比例2
取PNNP型配体:(苯)2磷氮(异丙基)氮(异丙基)磷(苯)2(Ph2PN(iPr)N(iPr)P(Ph)2)为配体,结构式如式2所示,CrCl3(THF)3为催化剂,Et3Al为助催化剂,甲苯为溶剂(参照文献EthyleneTrimerization with M-ixed-Donor Ligand(N,P,S)Chromium Complexes:Effect of Ligand Structure on Activity and Selectivity[J].Organometallics.2005,24(4):552-556制备),将配有磁力搅拌子和导气管的100mL高压釜用乙烯气体置换3次,在氮气保护下,依次加入甲苯、助催化剂MAO 2.5mL(1.60M)[Al/Cr=1000],6mg该催化剂,控制总体积为100mL,通入乙烯气体,在60℃下开始聚合反应,维持乙烯压力0.8MPa,搅拌反应30min。聚合结束后,关闭气瓶,泄压,然后用10%的盐酸乙醇终止反应,过滤收集高聚物,滤液进行气相色谱分析,催化剂活性为1.09×105g/molCr·h,1-己烯选择性为39wt%,1-辛烯选择性为11%。
当然,本发明还可有其它多种实施例,在不背离本发明精神及其实质的情况下,熟悉本领域的技术人员可根据本发明作出各种相应的改变和变形,但这些相应的改变和变形都应属于本发明权利要求的保护范围。
Claims (6)
2.根据权利要求1所述的配合物催化剂,其特征在于,结构式中R1、R2结构分别为:
当R1为-CH2CH2-时,R2为(CH3)2CH-
当R1为-CH2CH2CH2-时,R2为CH3-或CH3CH2-
当R1为-CH2C(CH3)2CH2-时,R2为CH3-
当R1为-CH2CH2CH2CH2-时,R2为CH3-或CH3CH2-
当R1为-CH2CH2CH2CH(CH3)-时,R2为CH3CH2-
当R1为-CH2CH2CH2CH2CH2-时,R2为(CH3)2CH-
当R1为-CH2CH2CH2CH2CH2CH2-时,R2为CH3-或CH3CH2-。
3.一种制备权利要求1或2所述配合物催化剂的方法,其特征在于,配合物的制备采用含有二烷基氨基的伯胺与多聚甲醛(甲醛溶液)制备N取代基的β或γ位含有N原子的三氮杂环己烷配体,再与金属络合,得到配合物催化剂。
4.根据权利要求3所述的配合物催化剂的制备方法,其特征在于,具体包括:
(1)在100~130ml四氢呋喃中,以10~15gCrCl3·6H2O和50~60ml二氯亚砜为原料,室温反应1h~2h后,升温至70~80℃回流至无气体生成,制备得到CrCl3(thf)3;
(2)在30~50ml甲苯中,以3.0g~4.0g多聚甲醛和过量伯胺为原料,100~120℃反应18~21h,制备三氮杂环己烷配体,
所述的伯胺为(R2)2NR1NH2通式化合物,式中,R1、R2选自C1-C10的烷基;
所述的多聚甲醛分子式为HO-(CH2O)n-H,其中,n=10-100;
(3)在30~50ml甲苯中,以0~3.0gCrCl3(THF)3和过量三氮杂环己烷配体为原料,在室温下反应18~21h,制备铬系催化剂。
5.权利要求1所述配合物催化剂在α-烯烃聚合反应中的应用,其特征在于,所述的配合物催化剂用于乙烯、丙烯、丁烯、己烯和辛烯、癸烯等α-烯烃的齐聚反应。
6.根据权利要求5所述的配合物催化剂的应用,其特征在于,所述配合物催化剂作为主催化剂,甲基铝氧烷作为助催化剂,主催化剂与助催化剂用量摩尔比为1:500-2000。
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