CN114789067A - Ethylene selective oligomerization catalyst composition and preparation method thereof - Google Patents
Ethylene selective oligomerization catalyst composition and preparation method thereof Download PDFInfo
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- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 239000005977 Ethylene Substances 0.000 title claims abstract description 52
- 239000003054 catalyst Substances 0.000 title claims abstract description 41
- 238000006384 oligomerization reaction Methods 0.000 title claims abstract description 23
- 239000000203 mixture Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 239000003446 ligand Substances 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 10
- 230000008569 process Effects 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 31
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 26
- 150000001875 compounds Chemical class 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 12
- 150000003623 transition metal compounds Chemical class 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 8
- 238000005829 trimerization reaction Methods 0.000 claims description 8
- 125000005234 alkyl aluminium group Chemical group 0.000 claims description 7
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 5
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- BHIIGRBMZRSDRI-UHFFFAOYSA-N [chloro(phenoxy)phosphoryl]oxybenzene Chemical compound C=1C=CC=CC=1OP(=O)(Cl)OC1=CC=CC=C1 BHIIGRBMZRSDRI-UHFFFAOYSA-N 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 150000001845 chromium compounds Chemical class 0.000 claims description 2
- 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 claims description 2
- CYOMBOLDXZUMBU-UHFFFAOYSA-K chromium(3+);oxolane;trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3].C1CCOC1.C1CCOC1.C1CCOC1 CYOMBOLDXZUMBU-UHFFFAOYSA-K 0.000 claims description 2
- 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 description 2
- 150000002506 iron compounds Chemical class 0.000 claims description 2
- 239000005078 molybdenum compound Substances 0.000 claims description 2
- 150000002752 molybdenum compounds Chemical class 0.000 claims description 2
- 150000002816 nickel compounds Chemical class 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 150000003609 titanium compounds Chemical class 0.000 claims description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 2
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 2
- 150000003755 zirconium compounds Chemical class 0.000 claims description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims 3
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims 1
- 238000001704 evaporation Methods 0.000 claims 1
- 238000001914 filtration Methods 0.000 claims 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 abstract description 51
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 abstract description 25
- -1 polyethylene Polymers 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 11
- 239000006227 byproduct Substances 0.000 abstract description 8
- PEPLJBVSFALOCU-UHFFFAOYSA-N n-diphenylphosphanyl-n-pyridin-2-ylpyridin-2-amine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)N(C=1N=CC=CC=1)C1=CC=CC=N1 PEPLJBVSFALOCU-UHFFFAOYSA-N 0.000 abstract description 7
- 239000004698 Polyethylene Substances 0.000 abstract description 6
- 229920000573 polyethylene Polymers 0.000 abstract description 6
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 239000007789 gas Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 7
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 239000004711 α-olefin Substances 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- HMMPCBAWTWYFLR-UHFFFAOYSA-N n-pyridin-2-ylpyridin-2-amine Chemical compound C=1C=CC=NC=1NC1=CC=CC=N1 HMMPCBAWTWYFLR-UHFFFAOYSA-N 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- 239000012494 Quartz wool Substances 0.000 description 2
- 150000003927 aminopyridines Chemical class 0.000 description 2
- 239000013522 chelant Substances 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000008030 elimination Effects 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 239000004700 high-density polyethylene Substances 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000012263 liquid product Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 229920006124 polyolefin elastomer Polymers 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 125000004076 pyridyl group Chemical group 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910001868 water Inorganic materials 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 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
- B01J31/18—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
-
- 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
-
- 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
- C07C2531/22—Organic complexes
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention provides an ethylene selective oligomerization catalyst composition and a preparation method thereof, which take di- (2-pyridyl) (diphenyl phosphino) amine as a ligand of an ethylene tetramerization catalyst, have higher selectivity of 1-octene prepared by ethylene tetramerization, lower generation amount of oligomer and outstanding oligomerization activity, can effectively form a bimetal center in the catalysis process to improve the selectivity of 1-octene, and can effectively inhibit the generation of polyethylene by-products.
Description
Technical Field
The invention belongs to the field of ethylene oligomerization preparation, and particularly relates to an ethylene selective oligomerization catalyst composition and a preparation method thereof.
Background
Alpha-olefins (LAO) such as 1-octene and 1-hexene are used as important organic raw materials and chemical intermediates, and are mainly used for producing high-quality polyethylene, such as High Density Polyethylene (HDPE), Linear Low Density Polyethylene (LLDPE), polyolefin elastomer (POE) and the like.
Despite the importance of 1-octene, the 1-octenes currently used in industry are mainly obtained by non-selective oligomerization of ethylene, the alpha-olefins produced by such processes being C 4 -C 20 The product of the mixture mainly accords with Schulz-Flory distribution, so that pure 1-octene can be obtained only by continuous rectification at the end of the process, and a large amount of energy is consumed. The selective oligomerization of ethylene is a process for preparing alpha olefin opposite to non-selective oligomerization, the process selectively generates one to two kinds of alpha olefin, and the preparation of 1-butene by ethylene dimerization and the preparation of 1-hexene by trimerization are realized by domestic key technology. However, the technology for preparing 1-octene by ethylene tetramerization is only published in 2014 by Sasol to build a first set of equipment for producing 1-octene by ethylene tetramerization in Lake Charles, Louisiana at present, the production scale is 10 ten thousand tons/year of 1-octene (8 ten thousand tons/year) and 1-hexene (2 ten thousand tons/year), the operation condition of the plant is not reported in detail, and the operation condition from China to China isSo far, industrialization is not realized, and the key technology is still mastered abroad.
Currently, the development of ethylene selective tetramerization catalysts is mainly based on a high-activity and high-selectivity chromium/PNP ligand catalytic system. From the disclosed patents, the patents disclosed by the Sasol corporation, Shell corporation, petrochemistry, petroleum, marylar, tianjin science and technology university, college, etc. are representative in terms of ethylene selective tetramerization. Patents such as PTCZA200300187, PTCZA200300188, PCTZA2003000186, PCTZA2003000185 from Sasol are all Cr/PNP/alkylaluminoxane system catalysts, and the selectivity of 1-octene is around 70%. PCT/EP2006061425 from SHELL corporation uses two ligands, with a 1-octene selectivity of 69.4%. Domestic research institutions also make great contributions in ethylene tetramerization, wherein patents CN108097322A, CN108607612A, CN108607613A, CN109174190A, CN109174191A, CN109331878A, CN110449186A, WO2019113748A1, CN106582851B, CN105289742B and CN110368994A published by Tianjin scientific and technical university protect different types of catalysts, and the selectivity of 1-octene can reach 75 percent at most. Researches on selective tetramerization of ethylene by medium petrochemical are well established, CN102040624B, CN102451758B, CN102451759B and the like all relate to a synthetic method of a ligand for an ethylene trimerization or tetramerization catalyst, and the selectivity of 1-octene is 60-75%. The medium petroleum oil has also been studied and applied for the ethylene oligomerization, and CN 108686706A, CN 100443178C and CN 101450326B are all used as catalyst for protecting the selective oligomerization of ethylene, wherein the selectivity of 1-octene can be more than 70%.
However, the above techniques still have problems of low catalyst activity and high content of polyolefin as a by-product. Analysis shows that the key point of the technology for preparing 1-octene by ethylene tetramerization is to select a proper ligand to provide a proper electron donating ability and spatial configuration, thereby facilitating the synthesis of 1-octene. However, the current mainstream technology is to use PNP (bis (diarylphosphino) -amine) or similar derivatives disclosed by SASOL as ligand (US 7511183) to form ethylene tetramerization catalyst system with organochromium and MAO. The effect achieved is not ideal because of the limited ability of a single ligand to provide a point of application.
According to a large number of published patents or reports, the prior art still has the problem of high content of by-product polyolefin, resulting in difficulty in continuous production of ethylene tetramer. The present invention aims to obtain more excellent ethylene selective oligomerization performance than PNP by synthesizing a novel ligand.
Disclosure of Invention
In order to solve the technical problems, the invention discloses a synthesis method of diphenylphosphine amine compound and application thereof in ethylene tetramerization, and the di- (2-pyridyl) (diphenylphosphino) amine claimed by the invention is used as a ligand of an ethylene tetramerization catalyst, has higher selectivity of 1-octene prepared by ethylene tetramerization, lower oligomer generation amount and outstanding oligomerization activity, can effectively form a bimetal center in the catalysis process to improve the selectivity of 1-octene, and can effectively inhibit the generation of polyethylene byproducts. In addition, the diphenyl phosphine dipyridine amine compound disclosed by the invention has strong rigidity, a plurality of coordination sites are arranged on a pyridyl group, and the coordination sites can be directionally coordinated with metal elements, so that the high activity and high selectivity of 1-octene of the catalyst are ensured, and the generation of polymer byproducts can be reduced. The phosphorus-functionalized aminopyridine can be effectively and diversely prepared by parallel synthesis, and the ligand can form a stable eight-membered ring chelate tetramer precursor with metallic chromium, thereby facilitating the generation of beta-H elimination and finally producing the target product 1-octene with high selectivity.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention claims a catalyst composition for selective oligomerization of ethylene, which comprises a ligand compound shown in formula (I), a transition metal compound and an alkyl aluminum cocatalyst, wherein the ligand compound is particularly bis- (2-pyridyl) (diphenylphosphino) amine (CAS: 472959-76-5), and the structure of the catalyst composition is shown as follows:
formula (1)
The synthesis method of the compound di- (2-pyridyl) (diphenyl phosphino) amine comprises the following steps:n-hexane containing n-BuLi (2.5M, 1.6 mL,4 mmol) was added to a solution of 2,2' -dipyridylamine (0.68 g, 4 mmol) (CAS number: 1202-34-2) in diethyl ether (10 mL) at-78 ℃ under nitrogen. After 1 hour, a solution of diphenylphosphoryl chloride (0.72 mL, 0.882 g, 4 mmol) in diethyl ether (4 mL) was added dropwise thereto. During the dropwise addition, the reaction mixture gradually turned bright yellow. After the addition was complete, the reaction was stirred at room temperature for 48 hours, after which the solution was filtered, the filter residue was transferred to another Schlenk flask and evaporated to dryness, the residue was extracted twice with a mixture (1:1) of diethyl ether (10 mL) and tetrahydrofuran (10 mL), and the mixed solution was left to stand at-40 o And C, recrystallizing in a refrigerator to obtain a light yellow solid compound, namely the ligand compound, wherein the yield is 87%.
Further, the alkyl aluminum cocatalyst is one of methylaluminoxane, modified aluminum methyl siloxane, dried methylaluminoxane, triethylaluminum and trimethylaluminum;
further, the transition metal compound is at least one selected from a chromium compound, a molybdenum compound, an iron compound, a titanium compound, a zirconium compound and a nickel compound, preferably at least one selected from chromium acetylacetonate, chromium isooctanoate and chromium tri (tetrahydrofuran) trichloride;
further, the molar ratio of the alkyl aluminum cocatalyst to the transition metal compound is 100: 1-1000: 1;
further, the molar ratio of the ligand compound to the transition metal compound is 0.01: 1-100: 1; preferably 0.1: 1-10: 1;
the application comprises the following steps: in the presence of said catalyst composition, an oligomerization reaction of ethylene, preferably in an organic solvent, more preferably in an alkane solvent;
further, in the ethylene oligomerization reaction, the reaction temperature is 0-200 ℃, and preferably 30-100 ℃; the ethylene pressure is 0.1-20.0MPa, preferably 0.5-6.0 MPa; the reaction time is 0.5-4 h;
further, ethylene trimerization and/or tetramerization is carried out in the presence of the catalyst composition, preferably in an organic solvent, more preferably in an alkane;
further, the application of the catalyst composition in ethylene oligomerization comprises the following steps:
(1) before reaction, the kettle body and the lining of the reaction kettle are firstly placed in an oven 120 o C drying overnight, connecting to an evaluation system, sealing, heating to 100 ℃ under vacuum condition o And C, keeping the temperature constant for 1h (closing a tail gas valve), and removing residual water, oxygen and oxygen-containing impurities. Then the temperature is set as the reaction temperature, so that the reaction temperature is naturally reduced, nitrogen is filled at the same time, and then the reaction is vacuumized and repeated for three times to ensure that the air is completely replaced. Then, the nitrogen gas was evacuated by a vacuum pump, and the filling with ethylene was repeated three times to ensure that the autoclave body was filled with ethylene.
(2) Opening a tail gas valve, sequentially injecting a dehydrated and deoxidized solvent and a certain amount of cocatalyst by using an injector under the stirring condition, after the temperature is stabilized to the reaction temperature, injecting a transition metal compound and a ligand by using the injector, closing the tail gas valve, adjusting a pressure reducing valve, starting timing after the pressure is increased to a preset pressure value, recording mass flowmeter data, adding an alkyl aluminum assistant, after reacting for a certain time, closing ethylene gas, recording mass flowmeter data, stopping the reaction, closing a gas inlet valve, detaching a reaction kettle body, soaking the reaction kettle body into an ice water bath, and cooling the reaction kettle to 10 DEG C o C is less than C.
(3) After the reaction kettle is opened, the total weight of liquid and solid is weighed as soon as possible, a proper amount of quartz wool is plugged into an injector, 1-2 ml of liquid sample is filtered and then transferred to a sample bottle, and the components and the proportion of the product are analyzed by GC-MS. The remaining sample was filtered, the filter paper weighed in advance and the mass recorded, then the polymer on the paddle was scraped off with a spoon, washed into a beaker with solvent, and all the polymer was placed in a vacuum oven 60 o C, drying overnight, respectively weighing, and calculating to obtain pure mass. The liquid product composition can be calibrated by MS. The selectivity of each component can be calculated by combining the total weight of liquid and solid, the mass of solid and the GC result, and the catalyst activity can be calculated by combining the catalyst usage amount.
The invention has the advantages that:
(1) bis- (2-pyridyl) (diphenyl phosphino) amine compound is used as ligand of tetramerization catalyst for the first time, and forms a catalyst system with a metal center for ethylene selective oligomerization reaction;
(2) the selectivity of 1-octene in the product is high;
(3) the polyethylene content in the product is very low.
(4) The ligand compound claimed by the invention is used as a ligand of an ethylene tetramerization catalyst, can effectively form a bimetallic center in a catalysis process to improve the selectivity of 1-octene, and can effectively inhibit the generation of polyethylene byproducts.
(5) The bis- (2-pyridyl) (diphenyl phosphino) amine as the ligand of the tetramerization catalyst can improve the selectivity of 1-octene and reduce the action principle of polyethylene byproduct generation: the diphenyl phosphine dipyridine compound disclosed by the invention has strong rigidity, a plurality of coordination sites are arranged on a pyridyl group, and the diphenyl phosphine dipyridine compound can be directionally coordinated with a metal element, so that the generation of a polymer byproduct can be reduced while the high activity and high 1-octene selectivity of the catalyst are ensured. The phosphorus-functionalized aminopyridine can be effectively and diversely prepared by parallel synthesis, and the ligand can form a stable eight-membered ring chelate tetramer precursor with metallic chromium, thereby facilitating the generation of beta-H elimination and finally producing the target product 1-octene with high selectivity.
Detailed Description
In order to make the aforementioned and other features and advantages of the invention more comprehensible, embodiments accompanying figures are described in detail below. The method of the present invention is a method which is conventional in the art unless otherwise specified.
Examples
The synthesis steps of bis- (2-pyridyl) (diphenylphosphino) amine are as follows: under the condition of nitrogen atmosphere and-78 deg.Cn-BuLi (2.5M, 1.6 mL,4 mmol) in n-hexane was added to a solution of 2,2' -dipyridylamine (0.68 g, 4 mmol) in diethyl ether (10 mL). After 1h, a solution of diphenylphosphoryl chloride (0.72 mL, 0.882 g, 4 mmol) in diethyl ether (4 mL) was added dropwise. During the dropwise addition, the reaction mixture turned bright yellow. After stirring at room temperature for 48 h, the solution was filtered and the residue was transferred to another Schlenk bottle and evaporated to drynessA mixed solvent of ether (10 mL) and tetrahydrofuran (10 mL) was extracted twice. Placing the mixed solution at-40 o Recrystallizing in a refrigerator to obtain a light yellow solid compound with the yield of 87 percent.
Application examples and comparative examples:
the ethylene oligomerization reaction was carried out in a 300 mL autoclave. Before reaction, the reaction kettle body is placed in an oven 120 o C drying overnight, connecting to evaluation system, sealing, heating to 100 degree under vacuum condition o And C, keeping the temperature constant for 1h (closing a tail gas valve), and removing residual water, oxygen and oxygen-containing impurities. Then the temperature is set as the reaction temperature, so that the reaction temperature is naturally reduced, nitrogen is filled at the same time, then the reaction is vacuumized, and the steps are repeated for three times, so that the air is completely replaced. Then, the nitrogen gas was evacuated by a vacuum pump, and the filling with ethylene was repeated three times to ensure that the autoclave body was filled with ethylene. The tail gas valve is opened, a syringe is used for injecting 90 mL of cyclohexane solvent, a certain amount of methylaluminoxane (the methylaluminoxane is a toluene solution of 1.5 mol/L) and a certain amount of ligand compound solution in sequence under the stirring condition, after the temperature is stabilized to the set temperature, the transition metal compound solution is injected into the reaction kettle, and then the syringe is washed by 10 mL of cyclohexane to ensure that all catalyst components are injected into the reactor. After stirring for 3-5 min, closing the tail gas valve, adjusting the pressure reducing valve, starting timing after the pressure is increased to a set pressure, closing the ethylene gas after reacting for a certain time, recording mass flow meter data, stopping the reaction, closing the gas inlet valve, detaching the reaction kettle body, soaking the reaction kettle body in ice-water bath to cool the reaction kettle to 10 DEG o C is less than C. After the reaction kettle is opened, the total weight of liquid and solid is weighed as soon as possible, a proper amount of quartz wool is plugged into an injector, 1-2 ml of liquid sample is filtered and transferred to a sample bottle, and the sample bottle is placed on a GC-MS (gas chromatography-Mass spectrometer) for analyzing the components and the proportion of the product. The remaining sample was filtered, the filter paper was weighed in advance and the mass recorded, then the polymer on the paddle was scraped off with a spoon, washed into a beaker with solvent, and all the polymer was placed in a vacuum oven 60 o C, drying overnight, respectively weighing, and calculating to obtain pure mass. The liquid product composition can be calibrated by MS. The selectivity of each component can be calculated by combining the total weight of liquid and solid, the mass of solid and GC results, and the combination catalysisThe catalyst activity can be calculated by the amount of the catalyst used. The relevant reaction conditions for examples 1 to 4 and comparative examples are summarized in Table 1.
TABLE 1 summary of reaction conditions for examples and comparative examples
TABLE 2 ethylene oligomerization activity and product distribution for inventive and comparative examples
Note: application examples 1 to 3 the catalyst systems corresponding to examples 1 to 3, respectively, were used for the oligomerization of ethylene.
The results in Table 1 and Table 2 show that when the catalyst composition of the present invention is used in the ethylene trimerization and/or tetramerization reaction, the catalyst activity is significantly higher than that of the conventional catalyst, the 1-octene selectivity is equivalent to that of the conventional catalyst, and the polymer content is significantly reduced, which is beneficial to the long-term operation of the ethylene oligomerization reaction, and is expected to realize the continuous operation of the ethylene trimerization and/or tetramerization reaction.
The above description is only a preferred embodiment of the present invention, and all the equivalent changes and modifications made according to the claims of the present invention should be covered by the present invention.
Claims (9)
1. The ethylene selective oligomerization catalyst composition is characterized by comprising a ligand compound shown as a formula (I), a transition metal compound and an alkyl aluminum cocatalyst, wherein the ligand compound has the following structure:
formula (1)
The alkyl aluminum cocatalyst is one of methylaluminoxane, modified aluminum methylaluminoxane, pumped-out methylaluminoxane, triethylaluminum and trimethylaluminum;
the transition metal compound is at least one selected from the group consisting of a chromium compound, a molybdenum compound, an iron compound, a titanium compound, a zirconium compound, and a nickel compound.
2. The catalyst composition of claim 1, wherein the transition metal compound is at least one of chromium acetylacetonate, chromium isooctanoate, and chromium tris (tetrahydrofuran) trichloride.
3. The catalyst composition of claim 1, wherein the ligand compound is prepared by a process comprising the steps of: adding n-hexane solution containing n-butyllithium into diethyl ether solution containing 2,2' -dipyridine at-78 deg.C under nitrogen, dropwise adding diethyl ether solution containing diphenylphosphoryl chloride for 1 hr, stirring at room temperature for 48 hr, filtering, evaporating the residue to dryness, extracting the residue with diethyl ether and tetrahydrofuran for two times, and standing the mixed solution at-40 deg.C o And C, recrystallizing to obtain a light yellow solid compound, namely the ligand compound.
4. The catalyst composition of claim 1, characterized in that: the molar ratio of the alkyl aluminum cocatalyst to the transition metal compound is 100: 1-1000: 1.
5. The catalyst composition of claim 1, characterized in that: the molar ratio of the ligand compound to the transition metal compound is 0.01: 1-100: 1.
6. Use of a catalyst composition according to claim 1, wherein the catalyst composition is used in an alkane solvent for ethylene trimerization and/or tetramerization.
7. Use according to claim 6, characterized in that the alkane solvent is n-hexane, cyclohexane, n-heptane.
8. The use according to claim 6, wherein in the ethylene trimerization and/or tetramerization reaction, the reaction temperature is 0-200 ℃, the ethylene pressure is 0.1-20.0MPa, and the reaction time is 0.5-4 h.
9. Use according to claim 8, wherein the ethylene trimerization and/or tetramerization reaction is carried out at a temperature of 30-100 ℃ and an ethylene pressure of 0.5-6.0 MPa.
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