CN112209962B - Synthesis method of CGC-type titanium dichloride complex - Google Patents
Synthesis method of CGC-type titanium dichloride complex Download PDFInfo
- Publication number
- CN112209962B CN112209962B CN202011082679.5A CN202011082679A CN112209962B CN 112209962 B CN112209962 B CN 112209962B CN 202011082679 A CN202011082679 A CN 202011082679A CN 112209962 B CN112209962 B CN 112209962B
- Authority
- CN
- China
- Prior art keywords
- cgc
- type titanium
- titanium dichloride
- reaction
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- ZWYDDDAMNQQZHD-UHFFFAOYSA-L titanium(ii) chloride Chemical compound [Cl-].[Cl-].[Ti+2] ZWYDDDAMNQQZHD-UHFFFAOYSA-L 0.000 title claims abstract description 22
- 238000001308 synthesis method Methods 0.000 title claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 239000000243 solution Substances 0.000 claims abstract description 23
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000010936 titanium Substances 0.000 claims abstract description 18
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 18
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 16
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 14
- 239000003446 ligand Substances 0.000 claims abstract description 12
- 239000012266 salt solution Substances 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 7
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 7
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 238000002360 preparation method Methods 0.000 claims abstract description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 32
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 13
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 7
- 239000000706 filtrate Substances 0.000 claims description 7
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims 3
- 150000001336 alkenes Chemical class 0.000 abstract description 5
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 5
- 239000012535 impurity Substances 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 238000006116 polymerization reaction Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000001953 recrystallisation Methods 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000012968 metallocene catalyst Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002685 polymerization catalyst Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- HWSZZLVAJGOAAY-UHFFFAOYSA-L lead(II) chloride Chemical compound Cl[Pb]Cl HWSZZLVAJGOAAY-UHFFFAOYSA-L 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 238000004611 spectroscopical analysis Methods 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Substances C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 1
- CZOJMXXOMUJZPH-UHFFFAOYSA-K [Cl-].[Cl-].[Cl-].[Ti+3].C1CCOC1 Chemical compound [Cl-].[Cl-].[Cl-].[Ti+3].C1CCOC1 CZOJMXXOMUJZPH-UHFFFAOYSA-K 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/003—Compounds containing elements of Groups 4 or 14 of the Periodic Table without C-Metal linkages
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
Abstract
The invention discloses a synthesis method of a CGC-type titanium dichloride complex, which relates to the technical field of olefin polymerization and comprises the following steps: preparation (Me) 4 C 5 H)SiMe 2 Lithium salt solution of NH-t-Bu ligand; tiCl is added under anhydrous and anaerobic condition 4 Adding the titanium complex solution and the strong coordination solvent into a hydrocarbon solvent for mixing and stirring reaction to obtain titanium complex solution; will (Me) 4 C 5 H)SiMe 2 Adding lithium salt solution of NH-t-Bu ligand into the titanium complex solution for reaction to obtain CGC-type titanium dichloride complex. The invention can effectively avoid TiCl 4 The tetravalent titanium in the catalyst is reduced into trivalent titanium by lithium salt, so that the reaction yield is improved, other metal impurities are avoided being introduced, the post-treatment is simple, and the purity of the product obtained by the purification treatment is high. The invention has the advantages of easily available raw materials, low cost and easy realization of technological production.
Description
Technical Field
The invention relates to the technical field of olefin polymerization, in particular to a synthesis method of a CGC-type titanium dichloride complex.
Background
Olefin polymerization catalysts are the core of polyolefin polymerization technology, and in recent years, as the demand for polyolefin materials has increased, the demand for olefin polymerization catalysts has also increased. The variety of olefin polymerization catalysts is increasing from traditional Ziegler-Natta catalysts to metallocene catalysts to non-metallocene catalysts. The traditional Ziegler-Natta catalyst has the problems of low catalytic efficiency, partial process defects and the like, and the single catalytic center of the metallocene catalyst and the variety of catalytic monomers are incomparable with the traditional catalyst. The CGC type titanium catalyst has a rigid framework, so that the CGC type titanium catalyst has stable space specificity effect and thermal stability, brings diversified products, and can be widely applied to industrial production.
The CGC type titanium dichloride complex is a novel CGC titanium catalyst, and has excellent catalytic efficiency. Currently, there are mainly the following two methods for its preparation. The synthetic route for method one is shown below, which is to prepare (Me 4 C 5 H)SiMe 2 NH-t-Bu (ligand) lithium salt solution, and adding the solution into another anhydrous and anaerobic TiCl at-40 DEG C 4 And (3) carrying out reaction in diethyl ether solution, filtering after the reaction is finished, concentrating the filtrate to dryness, and adding n-hexane for low-temperature recrystallization. The method has low yield and the comprehensive yield is 15-20% because tetravalent titanium is easily reduced into trivalent titanium by lithium salt.
The synthetic route for method two is shown below, also by first preparing (Me 4 C 5 H)SiMe 2 Adding lithium salt solution of NH-t-Bu (ligand) into titanium trichloride-tetrahydrofuran complex at 0 ℃, reacting for 8 hours, adding anhydrous lead chloride, stirring for 8 hours, filtering after the reaction is finished, concentrating the filtrate to dryness, and adding normal hexane for low-temperature recrystallization. The method has the advantages that the yield is about 60-70%, the yield is improved, but lead impurities are very easy to introduce due to the fact that anhydrous lead chloride is used as an oxidant, and the method uses expensive titanium trichloride as a raw material, so that the industrialization cost is high, and the method is not easy to amplify.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides a synthesis method of a CGC-type titanium dichloride complex, which has high yield, no introduction of other metal impurities, simple post-treatment and low preparation cost.
The invention provides a synthesis method of a CGC-type titanium dichloride complex, which comprises the following steps:
s1, preparation (Me) 4 C 5 H)SiMe 2 Lithium salt solution of NH-t-Bu ligand;
s2, under the anhydrous and anaerobic condition, tiCl is added 4 Adding the titanium complex solution and the strong coordination solvent into a hydrocarbon solvent for mixing and stirring reaction to obtain titanium complex solution;
s3, will (Me) 4 C 5 H)SiMe 2 Adding lithium salt solution of NH-t-Bu ligand into the titanium complex solution for reaction to obtain CGC-type titanium dichloride complex.
Preferably, in S2, the strongly coordinating solvent is one or more than one of DME, TMEDA, THF.
Preferably, in S2, the hydrocarbon solvent is one or more of n-hexane, n-heptane, petroleum ether, ISOPAR-E and cyclohexane; n-hexane is preferred.
Preferably, in S1, (Me 4 C 5 H)SiMe 2 The lithium salt solution of the NH-t-Bu ligand was prepared as follows: will (Me) 4 C 5 H)SiMe 2 Adding NH-t-Bu and n-hexane into a reaction vessel, dropwise adding n-butyllithium, controlling the dropwise adding temperature to be less than or equal to minus 30 ℃, and stirring at room temperature for reaction for 6 hours after the dropwise adding is finished, thus obtaining the catalyst.
Preferably, in S3, the reaction temperature is-10-30 ℃; preferably 5 ℃.
Preferably, the method further comprises the steps of purifying the CGC-type titanium dichloride complex obtained in the step S3, and specifically comprises the following steps: filtering the reaction product in the step S3, washing filter residues by adopting toluene, mixing the washing liquid and the filtrate, spin-drying, then adding n-hexane for low-temperature recrystallization, filtering and vacuum drying to obtain the catalyst.
Preferably, low temperature recrystallization at-60 to 0 ℃; preferably at-40 ℃.
In the invention, all organic solvents such as normal hexane, toluene, hydrocarbon solvents, strong ligand solvents and the like are dehydrated.
The beneficial effects are that: the invention provides a synthesis method of CGC-type titanium dichloride complex, tiCl is reacted in hydrocarbon solvent 4 Complexing with a strongly coordinating solvent, and then combining it with (Me) 4 C 5 H)SiMe 2 Lithium salt of NH-t-Bu ligand reacts effectivelyAvoiding TiCl 4 The tetravalent titanium in the catalyst is reduced into trivalent titanium by lithium salt, so that the reaction yield is improved, other metal impurities are avoided being introduced, the post-treatment is simple, and the purity of the product obtained by the purification treatment is high and can reach more than 98%. In addition, the raw materials used in the invention are easy to obtain, the cost is low, and the technological production is easy to realize.
Drawings
FIG. 1 is an H1 NMR chart of CGC-type titanium dichloride complex prepared in example 1 of the present invention.
Detailed Description
The technical scheme of the invention is described in detail through specific embodiments.
Example 1
Into a 250ml three port round bottom reaction flask, 10g (Me 4 C 5 H)SiMe 2 NH-t-Bu (0.04 mol), 100ml of dry n-hexane and a stirrer, 32ml of n-butyllithium (0.08 mol) is dropwise added at-30 ℃ and the temperature is controlled below-30 ℃ for half an hour, and the mixture is stirred for 6 hours at room temperature, so that the solution becomes white turbid liquid; the solution was then added to another anhydrous and anaerobic solution containing 12.7g TiCl at 5 ℃ 4 (2 THF) (0.038 mol) in a 500ml three port round bottom reaction flask, 40 minutes was completed, stirring 3 hours at room temperature, the solution turned from pale yellow to brown yellow, filtering first after the reaction was completed, washing with dry toluene, and then, the filtrate was dried by rotating a glove box-40 ℃ and recrystallized at low temperature with dry n-hexane. Vacuum drying at 35 ℃ for two hours to obtain 6g of yellow powder, namely CGC-type titanium dichloride complex, with the yield of 41% and the purity of 98%.
The obtained product is subjected to nuclear magnetic resonance hydrogen spectrum, which is shown in FIG. 1, H1 NMR (400 MHz, C 6 D 6 ):2.00(m,12H,CH 3 in Cp-CH 3 ),1.42(s,9H,CH in N-CH 3 ),0.43(s,6H,CH 3 in SiCH 3 )。
Example 2
Into a 250ml three port round bottom reaction flask, 10g (Me 4 C 5 H)SiMe 2 NH-t-Bu (0.04 mol), 100ml of dry n-hexane and a stirrer, 32ml of n-butyllithium (0.08 mol) is added dropwise at-30 ℃, the temperature is controlled below-30 ℃ and after half an hour of addition, the mixture is stirred for 6 hours at room temperature, and the solution becomesForming white turbid liquid; in another anhydrous and oxygen-free container 7.1g TiCl 4 Adding 4.1g (0.046 mol) of dry DME into (0.037 mol) of dry n-hexane solution dropwise at-10 ℃, stirring for 1h at room temperature after the dropwise addition, cooling to 5 ℃, adding lithium salt solution into the system at 5 ℃, turning the solution from bright yellow to brown yellow, filtering at the end of the reaction, washing with dry toluene, rotating a glove box of the filtrate at-40 ℃, adding dry n-hexane, and recrystallizing at low temperature. Vacuum drying at 35 ℃ for two hours to obtain 12.9g of yellow powder, namely CGC-type titanium dichloride complex, with the yield of 88% and the product purity of 98%.
The resulting product was subjected to nuclear magnetic resonance hydrogen spectroscopy, H1 NMR (400 MHz, C 6 D 6 ):2.00(m,12H,CH3in Cp-CH 3 ),1.42(s,9H,CH in N-CH 3 ),0.43(s,6H,CH 3 in SiCH 3 )。
Example 3
Into a 250ml three port round bottom reaction flask, 10g (Me 4 C 5 H)SiMe 2 NH-t-Bu (0.04 mol), 100ml of dry n-hexane and a stirrer, 32ml of n-butyllithium (0.08 mol) is dropwise added at-30 ℃ and the temperature is controlled below-30 ℃ for half an hour, and the mixture is stirred for 6 hours at room temperature, so that the solution becomes white turbid liquid; in another anhydrous and oxygen-free container 7.1g TiCl 4 5.3g (0.046 mol) TMEDA is added dropwise into (0.037 mol) dry normal hexane solution at-10 ℃, the temperature is reduced to 5 ℃ after the dropwise addition is completed and the room temperature is restored, the stirring is carried out for 1h, lithium salt solution is added into the system at 5 ℃, the solution is changed from light yellow to brown yellow, the solution is filtered firstly after the reaction is finished, the solution is washed by dry toluene, and the filtrate is dried by rotating a glove box to-40 ℃ and is recrystallized at low temperature by the dry normal hexane. Vacuum drying at 35 ℃ for two hours to obtain 13.3g yellow powder, namely CGC-type titanium dichloride complex, with the yield of 91% and the product purity of 99%.
The resulting product was subjected to nuclear magnetic resonance hydrogen spectroscopy, H1 NMR (400 MHz, C 6 D 6 ):2.00(m,12H,CH 3 in Cp-CH 3 ),1.42(s,9H,CH in N-CH 3 ),0.43(s,6H,CH 3 in SiCH 3 )。
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (5)
1. The synthesis method of the CGC-type titanium dichloride complex is characterized by comprising the following steps of:
s1, preparation (Me) 4 C 5 H)SiMe 2 Lithium salt solution of NH-t-Bu ligand;
s2, under the anhydrous and anaerobic condition, tiCl is added 4 Adding the titanium complex solution and the strong coordination solvent into a hydrocarbon solvent for mixing and stirring reaction to obtain titanium complex solution; wherein the strong coordination solvent is one or more of ethylene glycol dimethyl ether DME and tetramethyl ethylenediamine TMEDA;
s3, will (Me) 4 C 5 H)SiMe 2 Adding lithium salt solution of NH-t-Bu ligand into the titanium complex solution for reaction to obtain CGC-type titanium dichloride complex.
2. The method for synthesizing the CGC-type titanium dichloride complex according to claim 1, wherein in the S2, the hydrocarbon solvent is one or more of n-hexane, n-heptane, petroleum ether, ISOPAR-E and cyclohexane.
3. The method for synthesizing a CGC-type titanium dichloride complex according to claim 1, wherein in S1, (Me 4 C 5 H)SiMe 2 The lithium salt solution of the NH-t-Bu ligand was prepared as follows: will (Me) 4 C 5 H)SiMe 2 Adding NH-t-Bu and n-hexane into a reaction vessel, dropwise adding n-butyllithium, controlling the dropwise adding temperature to be less than or equal to minus 30 ℃, and stirring at room temperature for reaction for 6 hours after the dropwise adding is finished, thus obtaining the catalyst.
4. The method for synthesizing a CGC-type titanium dichloride complex according to claim 1, wherein in S3, the reaction temperature is-10 to 30 ℃.
5. The method for synthesizing the CGC-type titanium dichloride complex according to claim 1, further comprising the steps of purifying the CGC-type titanium dichloride complex obtained in the step S3, wherein the specific operation is as follows: filtering the reaction product in the step S3, washing filter residues by adopting toluene, mixing the washing liquid and the filtrate, spin-drying, adding n-hexane, recrystallizing at a low temperature of between 60 ℃ below zero and 0 ℃, filtering, and drying in vacuum to obtain the catalyst.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202011082679.5A CN112209962B (en) | 2020-10-12 | 2020-10-12 | Synthesis method of CGC-type titanium dichloride complex |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202011082679.5A CN112209962B (en) | 2020-10-12 | 2020-10-12 | Synthesis method of CGC-type titanium dichloride complex |
Publications (2)
Publication Number | Publication Date |
---|---|
CN112209962A CN112209962A (en) | 2021-01-12 |
CN112209962B true CN112209962B (en) | 2023-05-30 |
Family
ID=74054412
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202011082679.5A Active CN112209962B (en) | 2020-10-12 | 2020-10-12 | Synthesis method of CGC-type titanium dichloride complex |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN112209962B (en) |
-
2020
- 2020-10-12 CN CN202011082679.5A patent/CN112209962B/en active Active
Non-Patent Citations (3)
Title |
---|
Constrained geometry complexes of titanium (IV) and zirconium (IV) involving cyclopentadienyl fused to thiophene ring;Alexey N. Ryabov et al.,;《Journal of Organo metallic Chemistry》;20050805;第690卷;4213-4221 * |
Synthesis and X-ray crystal structure of [Me2Si(C5Me2H2)(tBuN)]MCl2 (M = Ti, Zr) bearing a 3,4-dimethylcyclopentadienyl ring: Investigation of the substitution effect on the cyclopentadienyl (Cp) ring for catalytic performance in ethylene/1-octene (co)poly;Chun Ji Wu et al.,;《Polyhedron》;20130917;第67卷;199-204,参见第200页右栏2.3.3-2.3.4 * |
Synthesis, structure and ethylene polymerisation activity of {g5:g1(N)-1-[(tert-butylamido)diphenylsilyl)]-2,3,4,5 tetramethylcyclopentadienyl}dichlorotitanium(IV);Jiri Pinkas et al.,;《Polyhedron》;20200716;第188卷;114704 * |
Also Published As
Publication number | Publication date |
---|---|
CN112209962A (en) | 2021-01-12 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Sun et al. | Ethylene polymerization by 2-iminopyridylnickel halide complexes: synthesis, characterization and catalytic influence of the benzhydryl group | |
JP6806973B2 (en) | Chromium compound, catalyst system using this, and method for producing ethylene oligomer | |
Jia et al. | Unsymmetrical α-diiminonickel bromide complexes: synthesis, characterization and their catalytic behavior toward ethylene | |
Akhbari et al. | Reversible solid state structural transformation of a polyhapto lead (ii) polymeric chain to a tetrahapto lead (ii) two-dimensional network by thermal dehydration with no change in nanoplate morphology | |
KR100586118B1 (en) | Tridentate ligand-containing metal catalyst complexes for olefin polymerization | |
Song et al. | Nickel (ii) complexes bearing 4, 5-bis (arylimino) pyrenylidenes: synthesis, characterization, and ethylene polymerization behaviour | |
WO2007080081A2 (en) | Process for the preparation of unsymmetric bis(imino) compounds | |
CN101348501B (en) | 2-imino-9-phenyl-1,10-phenanthroline transient metal complex, and preparation and use thereof | |
Jing et al. | Synthesis and characterization of aminopyridine iron (II) chloride catalysts for isoprene polymerization: Sterically controlled monomer enchainment | |
EP1925623A1 (en) | Polymerisation of ethylene and alpha-olefins with pyrrol-iminophenol complexes. | |
González‐Gallardo et al. | Preparation of molecular alumoxane hydrides, hydroxides, and hydrogensulfides | |
JP2019504838A (en) | Process for producing transition metal-Schiff base (imine) ligand complex | |
US20050037918A1 (en) | Non-metallocenes, method for the production thereof and use thereof in the polymerization of olefins | |
Mack et al. | A pyridine dialkoxide titanium dichloride complex. Synthesis and molecular structure of 2, 6-bis (2, 2-diphenyl-2-trimethylsilyloxy-ethyl) pyridine | |
Yao et al. | Synthesis, characterization and polymerization activity of copper complexes with N, O-chelate ligands | |
CN112209962B (en) | Synthesis method of CGC-type titanium dichloride complex | |
CN116410224B (en) | Synthesis process of cyclopentadiene titanium trichloride | |
Hao et al. | Nickel complexes bearing N, N, N-tridentate quinolinyl anilido–imine ligands: Synthesis, characterization and catalysis on norbornene addition polymerization | |
Gao et al. | Synthesis of benzoxazolylpyridine nickel complexes and their efficient dimerization of ethylene to α-butene | |
Lee et al. | Preparation of zwitterion-type chromium (II) complexes for ethylene oligomerization | |
Xu et al. | Binuclear half-metallocene chromium (III) complexes mediated ethylene polymerization with alkylaluminium as cocatalyst | |
Liu et al. | Binuclear zirconium complexes with bidentate N-(ortho-dimethylaminobenzyl) anilide ligands: Synthesis, characterization, and catalytic properties for ethylene polymerization and copolymerization with 1-hexene | |
Braunschweig et al. | Synthesis and structure of boron-bridged constrained geometry complexes of titanium | |
Lee et al. | Novel zirconium complexes containing a bidentate phenoxybenzotriazole ligand | |
CN103012629B (en) | Synthetic method of bridged metallocene Zr-RE (rare earth) dinuclear catalyst |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |