CN107149947A - A kind of ethylene oligomerization catalyst and its application - Google Patents
A kind of ethylene oligomerization catalyst and its application Download PDFInfo
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- CN107149947A CN107149947A CN201610124178.6A CN201610124178A CN107149947A CN 107149947 A CN107149947 A CN 107149947A CN 201610124178 A CN201610124178 A CN 201610124178A CN 107149947 A CN107149947 A CN 107149947A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 48
- 238000006384 oligomerization reaction Methods 0.000 title claims abstract description 31
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 239000005977 Ethylene Substances 0.000 title claims abstract description 25
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 20
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 13
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 10
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 9
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 7
- 239000001257 hydrogen Substances 0.000 claims abstract description 7
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract description 7
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 5
- 150000002367 halogens Chemical class 0.000 claims abstract description 5
- 125000003118 aryl group Chemical group 0.000 claims abstract description 4
- 125000003107 substituted aryl group Chemical group 0.000 claims abstract description 4
- 125000004429 atom Chemical group 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 17
- -1 substituted-phenyl Chemical group 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 14
- 239000004411 aluminium Substances 0.000 claims description 12
- 239000011651 chromium Substances 0.000 claims description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 9
- 229910052804 chromium Inorganic materials 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- 239000003426 co-catalyst Substances 0.000 claims description 7
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 230000003197 catalytic effect Effects 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 5
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 3
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 claims description 2
- YVSMQHYREUQGRX-UHFFFAOYSA-N 2-ethyloxaluminane Chemical compound CC[Al]1CCCCO1 YVSMQHYREUQGRX-UHFFFAOYSA-N 0.000 claims description 2
- DCERHCFNWRGHLK-UHFFFAOYSA-N C[Si](C)C Chemical compound C[Si](C)C DCERHCFNWRGHLK-UHFFFAOYSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 239000005864 Sulphur Substances 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 150000001399 aluminium compounds Chemical class 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 150000001924 cycloalkanes Chemical class 0.000 claims description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- 229940117389 dichlorobenzene Drugs 0.000 claims description 2
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical class C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 claims description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000012188 paraffin wax Substances 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 2
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 claims description 2
- CNWZYDSEVLFSMS-UHFFFAOYSA-N tripropylalumane Chemical compound CCC[Al](CCC)CCC CNWZYDSEVLFSMS-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- OQOGEOLRYAOSKO-UHFFFAOYSA-N 1,1-dichloro-1-nitroethane Chemical compound CC(Cl)(Cl)[N+]([O-])=O OQOGEOLRYAOSKO-UHFFFAOYSA-N 0.000 claims 1
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 claims 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims 1
- 125000005418 aryl aryl group Chemical group 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 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 claims 1
- 239000000126 substance Substances 0.000 claims 1
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 7
- 239000004711 α-olefin Substances 0.000 description 9
- 150000001336 alkenes Chemical class 0.000 description 8
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 7
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000013638 trimer Substances 0.000 description 3
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical class CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 238000003556 assay Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- NPDACUSDTOMAMK-UHFFFAOYSA-N 4-Chlorotoluene Chemical compound CC1=CC=C(Cl)C=C1 NPDACUSDTOMAMK-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical group [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 150000001845 chromium compounds Chemical class 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002362 mulch Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
Classifications
-
- 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
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
-
- 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
- C07C2/14—Catalytic processes with inorganic acids; with salts or anhydrides of acids
- C07C2/20—Acids of halogen; Salts thereof ; Complexes thereof with organic compounds
- C07C2/22—Metal halides; Complexes thereof with organic compounds
-
- 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
- B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
- B01J2531/62—Chromium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- C07C2531/24—Phosphines
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention relates to a kind of ethylene oligomerization catalyst, including as lead to formula (I) shown in major catalyst and containing aluminum cocatalyst,In formula, described A, B and D, one of those is S, and other two is independently selected from CR1And CR2；The R1And R2Identical or different, the atom being respectively selected from hydrogen, alkyl, cycloalkyl and halogen, and the alkyl and cycloalkyl is optionally exchanged for heteroatoms or not replaced；Ar is aryl or substituted aryl.The catalyst provided according to the present invention, with good oligomerization activity, and product is distributed the advantage such as excellent.
Description
Technical field
The present invention relates to a kind of catalyst for oligomerization, and in particular to a kind of thiophene-based catalyst for oligomerization is in ethylene oligomerization reaction
Application, the invention further relates to a kind of ethylene oligomerization technique.
Background technology
Olefin(e) oligomerization is carried out using chromium-based catalysts, the oligomerisation of mainly alpha-olefin has obtained extensive research.It is more accurate
Really say, developed many chromium-based catalysts, and alpha-olefin is prepared for olefin(e) oligomerization.Wherein, 1- is made in ethylene trimer
Hexene and ethylene tetramerization have more special meaning in terms of 1- octenes are made.By the LLDPE resins of 1- alkene, 1- octene copolymers
Compared with the copolymer of 1- butylene, tensile strength, impact strength, tear resistance and performance durable in use are all substantially excellent, special
Shi Yu not agricultural mulch films such as packaging film and greenhouse, canopy room etc..In terms of alpha-olefin is as comonomer, 1- hexenes and 1- octenes
1- butylene has progressively been substituted to produce high performance PE products.
The production method of alpha-olefin mainly has wax destructive distillation method, ethylene oligomerization method, extraction separation method, fatty alcohol dehydriding, interior
Olefin isomerization method etc..Wherein, ethylene oligomerization method because its alpha-olefin produced have purity it is high, selectivity good, raw material availability it is high
The features such as one of the important channel that is produced as alpha-olefin.
Reported after John R.Briggs in J.Chem.Soc., Chem.Commun., 1989,674-675 with homogeneous
Ternary chromium-based catalysts are selectively prepared to be catalyzed ethylene trimer after the approach of 1- hexenes, and 1- hexene production technologies have obtained considerable
Development.In order to more rationally utilize petroleum, people are being directed to developing efficient catalyst for oligomerization always, are expecting to obtain height
Purity higher alpha-olefin.In numerous explorations, heteroatom ligand is acted on chromium sub-group compound, and is turned into for its olefin(e) oligomerization
The new study hotspot in the field.A kind of multiple tooth dentate phosphine, arsenic containing aikyiaiurnirsoxan beta and chromic salts are disclosed in CN1606539A
And/or the complex of antimony, and use it in ethylene oligomerization course of reaction；WO2003053890 reports a kind of new sulphur
Nitrogen heteroatom part is used for olefin oligomerization, occurs olefin oligomerization in the presence of chromium compound and alkylaluminoxane, this is urged
Agent composition has the characteristics of catalytic activity is high, product 1- hexene purities are high.Aluminum alkoxide (including MAO, modification
MAO) etc. as co-catalyst, there are problems that cost it is too high, on a large scale be used for ethylene trimer reaction
When, the problem of production cost is high will certainly be caused.
It is undoubted, remain the demand to the new catalyst of excellent combination property in olefin(e) oligomerization field.
Notice is placed on the Novel Ligands compound how obtained for ethylene oligomerisation catalyst, so as to develop with high activity and choosing
The ethylene oligomerisation catalyst of selecting property, is worth paying close attention in the industry.
The content of the invention
Present inventor is neat for ethene by furtheing investigate there is provided a kind of new ethylene oligomerisation catalyst
Poly-, specific catalytic activity is high, product distribution is excellent (C6 and C8 product assays are high), and the few advantage of high molecular polymer.This hair
The bright application for having further related to the poly- catalyst of above-mentioned ethene.
According to an aspect of the invention, there is provided a kind of ethylene oligomerization catalyst, including as led to the master shown in formula (I)
Catalyst and containing aluminum cocatalyst,
In formula, described A, B and D, one of those is S, and other two is independently selected from CR1And CR2；The R1And R2Phase
It is same or different, the atom on hydrogen, alkyl, cycloalkyl and halogen, and the alkyl and cycloalkyl is respectively selected from optionally by miscellaneous original
Son substitution or not；Ar is aryl or substituted aryl.
According to the catalyst that provides of the present invention, structure novel, for ethylene oligomerization, with good activity, and product point
Cloth is excellent, and C6 and C8 product assay are high, with preferable prospects for commercial application and economic value.
According to a preferred embodiment of the present invention, the major catalyst shown in the formula (I) includes formula (II) and/or formula
(III) major catalyst shown in,
According to another preferred embodiment of the present invention, the R1And R2It is identical or different, it is respectively selected from hydrogen, C1-C10Alkane
Base, C3-C10Carbon atom on cycloalkyl and halogen, and the alkyl and cycloalkyl is optionally exchanged for heteroatoms or not replaced.
The hetero atom in the present invention is selected from sulphur, silicon, nitrogen and oxygen.In a specific embodiment, R1And R2Selected from hydrogen, first
Base, ethyl, butyl, hexyl, octyl group, cyclopenta, cyclohexyl and trimethyl silicon substrate.Preferably, Ar is C5-C20Aryl or substitution
Aryl, preferably phenyl or substituted-phenyl.
It is described to be selected from alkyl aluminum compound and alkoxy containing aluminum cocatalyst according to a preferred embodiment of the present invention
Aluminium compound.Preferably, the alkyl aluminum compound is selected from trimethyl aluminium, triethyl aluminum, tri-propyl aluminum, triisobutyl aluminium, three
At least one of n-hexyl aluminium, tri-n-octylaluminium, diethylaluminum chloride and ethylaluminium dichloride.Preferably, the alkoxy
Aluminium is selected from least one of MAO, modified methylaluminoxane, ethylaluminoxane and isobutyl aluminium alkoxide.
According to a preferred embodiment of the present invention, the mol ratio of aluminium and chromium in major catalyst is in the co-catalyst
(20-1500):1, there is preferable catalytic performance in the scope.In a preferred embodiment, the co-catalyst
The mol ratio of middle aluminium and chromium in major catalyst is (50-1000):1, be, for example, (100-500):1.In above range, with more preferable
Catalytic performance.
According to another aspect of the present invention, a kind of ethylene oligomerization method is additionally provided, including：Using above-mentioned catalysis
Agent, carries out ethylene oligomerization reaction in organic solvent.
Organic solvent in the present invention is organic solvent conventional in the art, for example, the organic solvent includes aliphatic series
Hydrocarbon compound and/or arene compounds.For example, aliphatic hydrocarbon compound is selected from least one of following compound：Directly
At least one of alkane, branched paraffin and cycloalkane, more preferably pentane, heptane, hexane, hexamethylene and hexahydrotoluene.
Arene compounds preferably are selected from least one of following compound：Benzene,toluene,xylene, monochlor-benzene, dichlorobenzene, three
Chlorobenzene, monochlorotoluene and its derivative.
In a preferred embodiment of the above method, the consumption of the catalyst is not particularly limited.At one
In instantiation, using the volume of organic solvent as calculating benchmark, the major catalyst concentration is 2-500 μm of ol/L, preferably 5-50 μ
mol/L。
In another preferred embodiment of the above method, the reaction temperature of the reaction is 0-200 DEG C, is preferably
20-150 DEG C, such as 30-100 DEG C, such as 30-90 DEG C.Reaction pressure is 0.1-20MPa, such as 1-10MPa, such as 1-5MPa.
Major catalyst structure that the present invention is provided is novel, prepares simple, and cost is relatively low, is urged by the major catalyst and being helped containing aluminium
The catalyst of agent composition can carry out ethylene oligomerization reaction.The product of acquisition is mainly C6 and C8, and its content is more than 80%, its
It is for a small amount of C4, C10 and with first-class alpha-olefin.Catalyst activity highest can be more than 1000kg oligomerization products g (Cr)-1·h-1, high molecular polymer is few.Excellent feature is distributed with high activity, product, there is preferable prospects for commercial application and economic valency
Value.
Embodiment
The following example is only used for that the present invention is described in detail, it will be appreciated that the scope of the present invention is not limited to
These embodiments.
Wherein, the testing conditions of gas-chromatography are：Chromatographic column SE-54, High Purity Nitrogen carrier gas, fid detector；Column temperature uses two
Rank temperature programming.
Embodiment 1
Using stainless steel polymeric kettle.Autoclave is heated to 80 DEG C, after vacuumizing with nitrogen displacement for several times, second is then charged with
Reaction temperature is down to after alkene displacement.Then heptane is added at 60 DEG C, while adding 10 μm of (structure such as formulas of ol major catalysts 1
II, wherein R1=R2=H, Ar are phenyl) and co-catalyst triethyl aluminum (AlEt3), the cumulative volume of mixed liquor is 100mL, wherein
The mol ratio of aluminium is 1 in chromium and co-catalyst in major catalyst：100, reaction pressure 1MPa is controlled, ethene is passed through, ethene is carried out
Oligomerisation reaction.
After the completion of reaction, system is cooled to room temperature, and gaseous products are collected in aerometer measuring tank, and liquid-phase product is collected
In conical flask, 1mL ethanol is added as terminator, terminates ethylene oligomerization reaction.Gas-chromatography is carried out after liquid phase gauging of products
Analysis.As a result show, the product of acquisition is mainly C6 and C8, its content is more than 80%, it is other for a small amount of C4, C10 and more than
Alpha-olefin.Catalyst activity about 363kg oligomerization products g (Cr)-1·h-1, high molecular polymer is seldom.
Embodiment 2
Be the same as Example 1, difference is that reaction pressure is 5MPa.Data result is shown in Table 1.
Embodiment 3
Be the same as Example 1, difference is that reaction temperature is 30 DEG C.Data result is shown in Table 1.
Embodiment 4
Be the same as Example 1, difference is that reaction temperature is 90 DEG C.Data result is shown in Table 1.
Embodiment 5
Be the same as Example 1, difference is that the mol ratio of aluminium in chromium and co-catalyst in major catalyst is 1：500.Data
It the results are shown in Table 1.
Embodiment 6
Be the same as Example 1, difference is triethyl aluminum being changed to MAO (MAO).Data result is shown in Table 1.
Embodiment 7
Be the same as Example 1, difference is major catalyst 1 being changed to major catalyst 2 (structure such as formula II, wherein R1=
SiMe3, R2=H, Ar are phenyl).Data result is shown in Table 1.
Embodiment 8
Be the same as Example 1, difference is major catalyst 1 being changed to major catalyst 3 (structure such as general formula III, wherein R1=
R2=H, Ar are phenyl).Data result is shown in Table 1.
Table 1
Invention technician can be with it can be seen from the data in Table 1 that the catalysis of the new structure provided according to the present invention
Agent, for ethylene oligomerization, with good oligomerization activity, and product distribution is excellent, and the content of C6 and C8 products is high, and C4 and
More than C10 products yield poorly.
It should be noted that embodiment described above is applied to explain the present invention, do not constitute to any of the present invention
Limitation.By referring to above-mentioned exemplary embodiments, invention has been described, it should be appreciated that wherein all words are
Descriptive and explanatory vocabulary, rather than limited vocabulary.Can be according to the rules within the scope of the claims to this
Modification is made in invention, and the present invention is revised in without departing substantially from scope and spirit of the present invention.Although described in it
The present invention relates to specific method, material and embodiment, it is not intended that the present invention is limited to wherein disclosed particular case, phase
Instead, the present invention can be extended to other all methods and applications with identical function.
Claims (10)
1. a kind of ethylene oligomerization catalyst, including as led to major catalyst shown in formula (I) and containing aluminum cocatalyst,
In formula, described A, B and D, one of those is S, and other two is independently selected from CR1And CR2；The R1And R2It is identical or not
Together, the atom being respectively selected from hydrogen, alkyl, cycloalkyl and halogen, and the alkyl and cycloalkyl is optionally exchanged for heteroatoms
Or do not replace；Ar is aryl or substituted aryl.
2. catalyst according to claim 1, it is characterised in that the major catalyst shown in the formula (I) includes formula (II)
And/or the major catalyst shown in formula (III),
3. catalyst according to claim 1 or 2, it is characterised in that the R1And R2It is identical or different, be respectively selected from hydrogen,
C1-C10Alkyl, C3-C10Carbon atom on cycloalkyl and halogen, and the alkyl and cycloalkyl be optionally exchanged for heteroatoms or
Do not replace, the hetero atom is selected from sulphur, silicon, nitrogen and oxygen；It is preferred that R1And R2Selected from hydrogen, methyl, ethyl, butyl, hexyl, octyl group, ring
Amyl group, cyclohexyl and trimethyl silicon substrate；
Or Ar is C5-C20Aryl or substituted aryl, preferably phenyl or substituted-phenyl.
4. the catalyst according to any one of claim 1-3, it is characterised in that described to be selected from alkyl containing aluminum cocatalyst
Aluminium compound and alkoxy aluminum compound.
5. the catalyst according to any one of claim 1-4, it is characterised in that the alkyl aluminum compound is selected from front three
Base aluminium, triethyl aluminum, tri-propyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum, tri-n-octylaluminium, diethylaluminum chloride and dichloride
At least one of aluminium ethide；And/or, the aluminum alkoxide is selected from MAO, modified methylaluminoxane, ethylaluminoxane
At least one of with isobutyl aluminium alkoxide.
6. the catalyst according to any one of claim 1-5, it is characterised in that aluminium and main catalytic in the co-catalyst
The mol ratio of chromium is (20-1500) in agent:1, preferably (50-1000):1, more preferably (100-500):1.
7. a kind of ethylene oligomerization method, including：Using the catalyst any one of claim 1-6, in organic solvent
Carry out ethylene oligomerization reaction.
8. method according to claim 7, it is characterised in that the organic solvent comprising aliphatic hydrocarbon compound and/or
Arene compounds；Preferably, aliphatic hydrocarbon compound preferably is selected from least one of following compound：Linear paraffin, side chain
At least one of alkane and cycloalkane, more preferably pentane, heptane, hexane, hexamethylene and hexahydrotoluene；Or aromatic hydrocarbons chemical combination
Thing preferably is selected from least one of following compound：Benzene,toluene,xylene, monochlor-benzene, dichlorobenzene, trichloro-benzene, a chlorine
First benzene and its derivative.
9. the method according to claim 7 or 8, it is characterised in that using the volume of organic solvent as calculating benchmark, the master
Catalyst concn is 2-500 μm of ol/L, preferably 5-50 μm ol/L.
10. the method according to any one of claim 7-9, it is characterised in that the reaction temperature of the reaction is 0-200
DEG C, preferable reaction temperature is 20-150 DEG C, and more preferably reaction temperature is 30-100 DEG C；Reaction pressure 0.1-20MPa, preferably 1-
10MPa。
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| CN109701650A (en) * | 2017-10-26 | 2019-05-03 | 中国石油化工股份有限公司 | A kind of preparation method and applications of olefin(e) oligomerization co-catalyst |
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