CN103285926A - Catalyst composition for ethylene oligomerization and application thereof - Google Patents
Catalyst composition for ethylene oligomerization and application thereof Download PDFInfo
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- CN103285926A CN103285926A CN2012100517428A CN201210051742A CN103285926A CN 103285926 A CN103285926 A CN 103285926A CN 2012100517428 A CN2012100517428 A CN 2012100517428A CN 201210051742 A CN201210051742 A CN 201210051742A CN 103285926 A CN103285926 A CN 103285926A
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- ethylene oligomerization
- chromium
- diphenyl
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- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 239000005977 Ethylene Substances 0.000 title claims abstract description 26
- 238000006384 oligomerization reaction Methods 0.000 title claims abstract description 26
- 239000003054 catalyst Substances 0.000 title abstract description 20
- 239000000203 mixture Substances 0.000 title abstract description 4
- 239000011651 chromium Substances 0.000 claims abstract description 7
- JYLPOJPHFDVWCY-UHFFFAOYSA-K oxolane;trichlorochromium Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3].C1CCOC1 JYLPOJPHFDVWCY-UHFFFAOYSA-K 0.000 claims abstract description 7
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims abstract description 6
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 5
- 125000003118 aryl group Chemical group 0.000 claims abstract description 4
- XEHUIDSUOAGHBW-UHFFFAOYSA-N chromium;pentane-2,4-dione Chemical compound [Cr].CC(=O)CC(C)=O.CC(=O)CC(C)=O.CC(=O)CC(C)=O XEHUIDSUOAGHBW-UHFFFAOYSA-N 0.000 claims abstract description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims abstract description 4
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims abstract description 3
- 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 abstract description 3
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 claims abstract description 3
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims abstract description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims abstract description 3
- 125000001624 naphthyl group Chemical group 0.000 claims abstract description 3
- 125000005647 linker group Chemical group 0.000 claims abstract 2
- 238000006243 chemical reaction Methods 0.000 claims description 57
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- -1 isooctyl Chemical group 0.000 claims description 7
- 229910052804 chromium Inorganic materials 0.000 claims description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 3
- 239000012190 activator Substances 0.000 claims description 3
- 150000001845 chromium compounds Chemical class 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 abstract description 32
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 abstract description 22
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 abstract description 16
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 10
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- YVSMQHYREUQGRX-UHFFFAOYSA-N 2-ethyloxaluminane Chemical compound CC[Al]1CCCCO1 YVSMQHYREUQGRX-UHFFFAOYSA-N 0.000 abstract 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 abstract 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 abstract 1
- 125000001183 hydrocarbyl group Chemical group 0.000 abstract 1
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 27
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 24
- 238000003756 stirring Methods 0.000 description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- 235000010290 biphenyl Nutrition 0.000 description 13
- 239000004305 biphenyl Substances 0.000 description 13
- 125000006267 biphenyl group Chemical group 0.000 description 13
- 238000006073 displacement reaction Methods 0.000 description 13
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 13
- 238000002360 preparation method Methods 0.000 description 13
- XGRJZXREYAXTGV-UHFFFAOYSA-N chlorodiphenylphosphine Chemical compound C=1C=CC=CC=1P(Cl)C1=CC=CC=C1 XGRJZXREYAXTGV-UHFFFAOYSA-N 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 5
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- LGECWBPIYVTLMF-UHFFFAOYSA-N [N].C1(=CC=CC=C1)[P]C1=CC=CC=C1 Chemical compound [N].C1(=CC=CC=C1)[P]C1=CC=CC=C1 LGECWBPIYVTLMF-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 150000004822 1,4-dichlorobenzenes Chemical class 0.000 description 2
- IBUWSVDQGMTMLO-UHFFFAOYSA-N C(C)(C)[P].[N].C1(=CC=CC=C1)[P]C1=CC=CC=C1 Chemical compound C(C)(C)[P].[N].C1(=CC=CC=C1)[P]C1=CC=CC=C1 IBUWSVDQGMTMLO-UHFFFAOYSA-N 0.000 description 2
- ZSIINFPCJLEZND-UHFFFAOYSA-N C(CCC)[P].[N].C1(=CC=CC=C1)[P]C1=CC=CC=C1 Chemical compound C(CCC)[P].[N].C1(=CC=CC=C1)[P]C1=CC=CC=C1 ZSIINFPCJLEZND-UHFFFAOYSA-N 0.000 description 2
- FAVTXBAMLQPDID-UHFFFAOYSA-N C1(=CC=CC=2C3=CC=CC=C3CC12)[P].[N].C1(=CC=CC=C1)[P]C1=CC=CC=C1 Chemical compound C1(=CC=CC=2C3=CC=CC=C3CC12)[P].[N].C1(=CC=CC=C1)[P]C1=CC=CC=C1 FAVTXBAMLQPDID-UHFFFAOYSA-N 0.000 description 2
- RHLYKLPLFQNWFO-UHFFFAOYSA-N C1(CC1)[P].[N].C1(=CC=CC=C1)[P]C1=CC=CC=C1 Chemical compound C1(CC1)[P].[N].C1(=CC=CC=C1)[P]C1=CC=CC=C1 RHLYKLPLFQNWFO-UHFFFAOYSA-N 0.000 description 2
- LSRLLOZBJURIHL-UHFFFAOYSA-N C1(CCCCC1)[P].[N].C1(=CC=CC=C1)[P]C1=CC=CC=C1 Chemical compound C1(CCCCC1)[P].[N].C1(=CC=CC=C1)[P]C1=CC=CC=C1 LSRLLOZBJURIHL-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 239000013638 trimer Substances 0.000 description 2
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 1
- QXSZNDIIPUOQMB-UHFFFAOYSA-N 1,1,2,2-tetrabromoethane Chemical compound BrC(Br)C(Br)Br QXSZNDIIPUOQMB-UHFFFAOYSA-N 0.000 description 1
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical class ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical class ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- CYSPWCARDHRYJX-UHFFFAOYSA-N 9h-fluoren-1-amine Chemical compound C12=CC=CC=C2CC2=C1C=CC=C2N CYSPWCARDHRYJX-UHFFFAOYSA-N 0.000 description 1
- HTJDQJBWANPRPF-UHFFFAOYSA-N Cyclopropylamine Chemical compound NC1CC1 HTJDQJBWANPRPF-UHFFFAOYSA-N 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 235000013355 food flavoring agent Nutrition 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a catalyst composition for ethylene oligomerization and application thereof, wherein a is chromium acetylacetonate, tetrahydrofuran chromium chloride and/or chromium isooctanoate; b has the formula
R1、R2、R3、R4Is phenyl, benzyl or naphthyl; r5Is isopropyl, butyl, cyclopropyl, cyclopentyl, cyclohexyl or fluorenyl; c is methyl aluminoxane, ethyl aluminoxane, propyl aluminoxane and/or butyl aluminoxane; d has the formula X1R6X2，X1，X2Is F, Cl, Br, I or alkoxy, R6Is an alkyl or aryl group; e has the formula
R is a linking group selected from hydrocarbyl and derivatives thereof, aryl and derivatives thereof; the molar ratio is 1: 0.5-10: 50-3000: 0.5-10; the catalyst has catalytic activity greater than 5.0 × 106g product mol- 1Cr·h-1The mass of 1-hexene and 1-octene is > 93%.
Description
Technical field
The present invention relates to a kind of catalyst system and catalyzing that adopts chromium compounds a, part b, activator c, promoter d and the second part e to form, be used for carbon monoxide-olefin polymeric of ethylene oligomerization and uses thereof.
Background technology
As everyone knows, linear alpha-alkenes such as 1-octene, 1-hexene are important chemical product and intermediate, are widely used in fields such as polyethylene comonomer, plasticizer alcohol, essence and flavoring agent, synthetic lubricant fluid and oil dope.1-octene, 1-hexene are used as comonomer can obviously improve poly density, improves mechanical performances such as its tear-proof and hot strength.When being used as plasticizer alcohol, can make low-temperature pliability, processability, the outdoor weather resistance of polyethylene products better, be particularly useful for making cable and wire, auto parts machinery or decoration etc.
Be worth although 1-hexene and 1-octene have important use in chemical industry, also do not have the technology of the synthetic 1-hexene of ethylene oligomerization high selectivity and 1-octene at present.The carbon number distribution of the product that traditional ethylene oligomerization technology obtains meets Schulz-Flory and distributes, and this distribution makes the content of 1-hexene and 1-octene in the oligomerization product can not be too high.For example US6184428 discloses a kind of Raney nickel, and the employing boron compound is co-catalyst, can the catalyzed ethylene oligomerisation obtains the mixture of linear alpha-alkene, and wherein the content of 1-octene accounts for 19%.SHOP technology (US3676523, US3635937) is used similar catalyst system and catalyzing, and the content of 1-octene accounts for 11% in the oligomerization product.Other typical ethylene oligomerization technology, (BP/Amoco, the content of 1-octene is generally 13～25% in ethylene oligomerization technology US3906053) as Chevron technology (DE1443927), the ethyl corporation of Gulf Oil Corporation.The chromium-based catalysts system is mainly used in ethylene trimer, and the content of 1-octene is (＜3%) seldom.Fe-series catalyst (J.Am.Chem.Soc., 1998, the 120:7143 of nearest report; Chem.Commun.1998,849; WO 99/02472) be used for ethylene oligomerization, the oligomerization product that obtains also is wide distribution, and the content of its 1-octene is lower (＜20%) also.In ethene four polymerizing technologies of WO2004/05647, the content of 1-hexene and 1-octene is the highest to have only 80%.
Summary of the invention
The purpose of this invention is to provide carbon monoxide-olefin polymeric of a kind of ethylene oligomerization and uses thereof, by selecting two kinds of parts for use, make the selective raising of 1-hexene and 1-octene, catalyst activity improves.
Carbon monoxide-olefin polymeric for ethylene oligomerization of the present invention is the composition that contains following component:
(1) chromium compounds a is chromium acetylacetonate, oxolane chromium chloride and/or isooctyl acid chromium;
(2) part b, general formula is
R wherein
1, R
2, R
3, R
4Be phenyl, benzyl, fluorenyl or naphthyl;
R
5Be isopropyl, butyl, cyclopropyl, cyclopenta or cyclohexyl;
(3) activator c is MAO, ethyl aikyiaiurnirsoxan beta, propyl group aikyiaiurnirsoxan beta and/or butyl aikyiaiurnirsoxan beta;
(4) promoter d, general formula are X
1R
6X
2, X
1, X
2Be F, Cl, Br, I and/or alkoxyl, R
6Be alkyl or aromatic radical;
(5) second part e, general formula is:
Wherein R is a connection
Group can be selected from alkyl and derivative thereof, aryl and derivative thereof;
Can with a, b, c, d and five kinds of components of e after mixing 10 minutes under the nitrogen, add in the reactor, feed ethene and carry out oligomerisation reaction; Also a, b, c, d and five kinds of components of e directly can be added in the reactor, feed ethene and carry out oligomerisation reaction, reaction temperature is 30～200 ℃, is preferably 30～90 ℃, more preferably 30～70 ℃; Reaction pressure is 0.5～10MPa, is preferably 1～10MPa, more preferably 2～6MPa; Reaction time is 0.1～2 hour, is preferably 0.3～1 hour, more preferably 0.5～0.7 hour.
The mol ratio of a: b: c: d: e is 1: 0.5～10: 50～3000: 0.5～10: 0.5～10.
The ethylene oligomerization reaction is mainly carried out in atent solvent, and selectable solvent comprises alkane, aromatic hydrocarbons, halogenated hydrocarbons or alkene.Typical solvent includes, but are not limited to benzene,toluene,xylene, isopropylbenzene, normal heptane, n-hexane, hexahydrotoluene, cyclohexane, 1-hexene, 1-octene, ionic liquid etc.
Major advantage of the present invention and effect:
Ethylene trimer and four poly-reactions because the effect of two kinds of parts is arranged, take place in chromium-based catalysts of the present invention simultaneously, thereby be conducive to highly selective and generate 1-hexene and 1-octene, therefore catalyst has active height, and the few characteristics of accessory substance polyethylene, catalytic activity is greater than 5.0 * 10
6G product mol
-1Crh
-1, selective＞93% of 1-hexene and 1-octene.
The specific embodiment
Embodiment 1
1, preparation (diphenyl) phosphorus nitrogen (cyclopropyl) phosphorus (diphenyl) part
Through N
2Fully add the carrene (20mL) through processed in the 100mL reactor that the band of displacement stirs, triethylamine (3.75mL), (1.326mL 7.2mmol), is cooled to 0 ℃ to diphenyl phosphorus chloride, slowly adds cyclopropylamine (3.6mmol).Rise to room temperature behind the stirring reaction 30min and continue reaction 12 hours.Filtration, drying obtain product (0.87g, 56.6%).
2, the two (N (P (phenyl) of preparation 1,4-
2)
2)-benzene part
Through N
2Fully add the carrene (20mL) through processed in the 100mL reactor that the band of displacement stirs, triethylamine (3.75mL), diphenyl phosphorus chloride (1.326mL 7.2mmol), is cooled to 0 ℃, slowly add 1,4 phenylenediamine (0.19g, 1.8mmol).Rise to room temperature behind the stirring reaction 30min and continue reaction 12 hours.Filtration, drying obtain product (0.8g, 52.3%).
3, Preparation of catalysts
Through N
2Fully add the toluene (10mL) through processed in the 100mL reactor that the band of displacement stirs, in a: b: c: d: e=1: 0.5: 300: 1: 0.5 ratio added the MAO toluene solution c of 1.4mol/L successively, (diphenyl) phosphorus nitrogen (cyclopropyl) phosphorus (diphenyl) b, isooctyl acid chromium a, 1,1,2,2-tetrachloroethanes d, the two (N (P (phenyl) of 1,4-
2)
2)-benzene part e, standby behind the room temperature reaction 10min.
4, ethylene oligomerization
The autoclave of 500mL is heated to and vacuumizes 2 hours, charges into ethene through nitrogen replacement for several times, cools to predetermined temperature, adds toluene (200mL) and above-mentioned catalyst through processed.Carrying out oligomerisation reaction under 40 ℃, the pressure of 5.0MPa, with ice bath cooling, release, is 10% acidifying ethanol cessation reaction with mass fraction behind the reaction 30min.The results are shown in subordinate list 1.
Embodiment 2
1, preparation (diphenyl) phosphorus nitrogen (cyclopenta) phosphorus (diphenyl) part
Through N
2Fully add the carrene (20mL) through processed in the 100mL reactor that the band of displacement stirs, triethylamine (3.75mL), diphenyl phosphorus chloride (1.326mL 7.2mol), is cooled to 0 ℃, slowly add cyclopenta amine (0.415mL, 3.5mmol).Rise to room temperature behind the stirring reaction 30min and continue reaction 12 hours.Filtration, drying obtain product (0.55g, 32.68%).
2, Preparation of catalysts
Through N
2Fully add the cyclohexane (10mL) through processed in the 100mL reactor that the band of displacement stirs, in a: b: c: d: e=1: 0.5: 50: 0.5: 0.5 ratio added the MAO toluene solution c of 1.4mol/L successively, (diphenyl) phosphorus nitrogen (cyclopenta) phosphorus (diphenyl) b, oxolane chromium chloride a, 1,1,2,2-tetrabromoethane d, the two (N (P (phenyl) of 1,4-
2)
2)-benzene part e, standby behind the room temperature reaction 5min.
3, ethylene oligomerization
The autoclave of 500mL is heated to and vacuumizes 2 hours, charges into ethene through nitrogen replacement for several times, cools to predetermined temperature, adds cyclohexane (200mL) and above-mentioned catalyst through processed.Carrying out oligomerisation reaction under 30 ℃, the pressure of 6.0MPa, with ice bath cooling, release, is 10% acidifying ethanol cessation reaction with mass fraction behind the reaction 20min.The results are shown in subordinate list 1.
Embodiment 3
1, preparation (diphenyl) phosphorus nitrogen (fluorenyl) phosphorus (diphenyl) part
Through N
2Fully add the carrene (20mL) through processed in the 100mL reactor that the band of displacement stirs, triethylamine (3.75mL), diphenyl phosphorus chloride (1.326mL 7.2mol), is cooled to 0 ℃, slowly add fluorenamine (0.652g, 3.6mmol).Rise to room temperature behind the stirring reaction 30min and continue reaction 12 hours.Filtration, drying obtain product (0.48g, 24.3%).
2, Preparation of catalysts
Through N
2Fully add the cyclohexane (10mL) through processed in the 100mL reactor that the band of displacement stirs, in a: b: c: d: e=1: 1: 200: 3: 1 ratio added propyl group aikyiaiurnirsoxan beta c successively, (diphenyl) phosphorus nitrogen (fluorenyl) phosphorus (diphenyl) b, chromium acetylacetonate a, 1,2-dimethoxy-ethane d, the two (N (P (phenyl) of 1,4-
2)
2)-benzene part e, standby behind the room temperature reaction 5min.
3, ethylene oligomerization
The autoclave of 500mL is heated to and vacuumizes 2 hours, charges into ethene through nitrogen replacement for several times, cools to predetermined temperature, adds benzene (200mL) and above-mentioned catalyst through processed.Carrying out oligomerisation reaction under 20 ℃, the pressure of 2.0MPa, with ice bath cooling, release, is 10% acidifying ethanol cessation reaction with mass fraction behind the reaction 40min.The results are shown in subordinate list 1.
Embodiment 4
1, preparation (diphenyl) phosphorus nitrogen (n-pro-pyl) phosphorus (diphenyl) part
Through N
2Fully add the carrene (20mL) through processed in the 100mL reactor that the band of displacement stirs, triethylamine (3.75mL), (1.326mL 7.2mmol), is cooled to 0 ℃ to diphenyl phosphorus chloride, slowly adds n-propylamine (3.6mmol).Rise to room temperature behind the stirring reaction 30min and continue reaction 12 hours.Filtration, drying obtain product b (1.1g, 66.2%).
2, Preparation of catalysts
Through N
2Fully add the cyclohexane (10mL) through processed in the 100mL reactor that the band of displacement stirs, in a: b: c: d: e=1: 10: 300: 10: 10 ratio added the MAO toluene solution c of 1.4mol/L successively, 1, two (N (P (phenyl) 2) the 2)-benzene b of 4-, 2 ethyl hexanoic acid chromium a, 1,2-dichloroethanes d, two (N (the P (phenyl) of 1,4-
2)
2)-benzene part e, standby behind the room temperature reaction 10min.
3, ethylene oligomerization
The autoclave of 500mL is heated to and vacuumizes 2 hours, charges into ethene through nitrogen replacement for several times, cools to predetermined temperature, adds heptane ((200mL) and above-mentioned catalyst through processed.Carrying out oligomerisation reaction under 90 ℃, the pressure of 7.0MPa, with ice bath cooling, release, is 10% acidifying ethanol cessation reaction with mass fraction behind the reaction 20min.The results are shown in subordinate list 1.
Embodiment 5
1, preparation (diphenyl) phosphorus nitrogen (cyclohexyl) phosphorus (diphenyl) part
Through N
2Fully add the carrene (20mL) through processed in the 100mL reactor that the band of displacement stirs, triethylamine (3.75mL), (1.326mL 7.2mmol), is cooled to 0 ℃ to diphenyl phosphorus chloride, slowly adds cyclohexylamine (3.6mmol).Rise to room temperature behind the stirring reaction 30min and continue reaction 12 hours.Filtration, drying obtain product (0.89g, 69.6%).
2, Preparation of catalysts
Through N
2Fully add the dimethylbenzene (10mL) through processed in the 100mL reactor that the band of displacement stirs, in a: b: c: d: e=1: 5: 2000: 8: 5 ratio added the MAO toluene solution c of 1.4mol/L successively, (diphenyl) phosphorus nitrogen (cyclohexyl) phosphorus (diphenyl) b, oxolane chromium chloride a, 1,4-dichloro-benzenes d, the (two (N (P (phenyl) of 1,4-
2)
2)-benzene part e, standby behind the room temperature reaction 5min.
3, ethylene oligomerization
The autoclave of 500mL is heated to and vacuumizes 2 hours, charges into ethene through nitrogen replacement for several times, cools to predetermined temperature, adds dimethylbenzene ((200mL) and above-mentioned catalyst through processed.Carrying out oligomerisation reaction under 30 ℃, the pressure of 5.0MPa, with ice bath cooling, release, is 10% acidifying ethanol cessation reaction with mass fraction behind the reaction 50min.The results are shown in subordinate list 1.
Embodiment 6
1, preparation (diphenyl) phosphorus nitrogen (isopropyl) phosphorus (diphenyl) part
Through N
2Fully add the carrene (20mL) through processed in the 100mL reactor that the band of displacement stirs, triethylamine (3.75mL), (1.326mL 7.2mmol), is cooled to 0 ℃ to diphenyl phosphorus chloride, slowly adds isopropylamine (3.6mmol).Rise to room temperature behind the stirring reaction 30min and continue reaction 12 hours.Filtration, drying obtain product b (1.2g, 60.3%).
2, ethylene oligomerization
The autoclave of 500mL is heated to and vacuumizes 2 hours, charge into ethene through nitrogen replacement for several times, cool to predetermined temperature, adding is through the isopropylbenzene (200mL) of processed, in a: b: c: d: e=1: 2: 300: 3: 2 ratio added the MAO toluene solution c of 1.4mol/L successively, (diphenyl) phosphorus nitrogen (isopropyl) phosphorus (diphenyl) b, oxolane chromium chloride a, 1,4-dichloro-benzenes d, the two (N (P (phenyl) of 1,4-
2)
2)-benzene part e.Carrying out oligomerisation reaction under 50 ℃, the pressure of 7.0MPa, with ice bath cooling, release, is 10% acidifying ethanol cessation reaction with mass fraction behind the reaction 30min.The results are shown in subordinate list 1.
Embodiment 7
1, preparation (diphenyl) phosphorus nitrogen (butyl) phosphorus (diphenyl) part
Through N
2Fully add the carrene (20mL) through processed in the 100mL reactor that the band of displacement stirs, triethylamine (3.75mL), (1.326mL 7.2mmol), is cooled to 0 ℃ to diphenyl phosphorus chloride, slowly adds butylamine (3.6mmol).Rise to room temperature behind the stirring reaction 30min and continue reaction 12 hours.Filtration, drying obtain product (0.9g, 69.1%).
2, ethylene oligomerization
The autoclave of 500mL is heated to and vacuumizes 2 hours, charge into ethene through nitrogen replacement for several times, cool to predetermined temperature, add cyclohexane (200mL) through processed, in a: b: c: d: e=1: 1: 200: 3: 1 ratio added the MAO toluene solution c of 1.4mol/L successively, (diphenyl) phosphorus nitrogen (butyl) phosphorus (diphenyl) b, oxolane chromium chloride a, 1,1,2,2-HFC-134a d, the two (N (P (phenyl) of 1,4-
2)
2)-benzene part e.Carrying out oligomerisation reaction under 20 ℃, the pressure of 8.0MPa, with ice bath cooling, release, is 10% acidifying ethanol cessation reaction with mass fraction behind the reaction 20min.The results are shown in subordinate list 1.
Table 1
Claims (4)
1. carbon monoxide-olefin polymeric that is used for ethylene oligomerization, it is characterized in that: it comprises
Chromium compounds a, part b, activator c, promoter d and the second part e,
Wherein:
A is chromium acetylacetonate, oxolane chromium chloride and/or isooctyl acid chromium;
The general formula of b is
R wherein
1, R
2, R
3, R
4Be phenyl, benzyl or naphthyl; R
5Be isopropyl, butyl, cyclopropyl, cyclopenta, cyclohexyl or fluorenyl;
C is MAO, ethyl aikyiaiurnirsoxan beta, propyl group aikyiaiurnirsoxan beta and/or butyl aikyiaiurnirsoxan beta;
The general formula of d is X
1R
6X
2, middle X
1, X
2Be F, Cl, Br, I or alkoxyl, R
6Be alkyl or aromatic radical;
The general formula of e is
Wherein R is a linking group, is selected from alkyl and derivative thereof or aryl and derivative thereof;
The mol ratio of a, b, c, d and e is 1: 0.5～10: 50～3000: 0.5～10: 0.5～10.
2. the application of a kind of carbon monoxide-olefin polymeric for ethylene oligomerization according to claim 1, it is characterized in that: with a, b, c, d and five kinds of components of e after mixing 10 minutes under the inert environments, add in the reactor, feeding ethene carries out oligomerisation reaction or directly adds a, b, c, d and five kinds of components of e in the reactor, feed ethene and carry out oligomerisation reaction, reaction temperature is 30～200 ℃; Reaction pressure is 0.5～10MPa; Time is 0.1～2 hour.
3. the application of a kind of carbon monoxide-olefin polymeric for ethylene oligomerization according to claim 2, it is characterized in that: the condition of oligomerisation reaction is: 30～90 ℃ of reaction temperatures; Reaction pressure 1～10MPa; 0.3～1 hour time.
4. the application of a kind of carbon monoxide-olefin polymeric for ethylene oligomerization according to claim 2, it is characterized in that: the condition of oligomerisation reaction is: 30～70 ℃ of reaction temperatures; Reaction pressure 2～6MPa; 0.5～0.7 hour time.
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