CN110964049B - Transition metal compound, olefin polymerization catalyst composition containing same, preparation method and application - Google Patents
Transition metal compound, olefin polymerization catalyst composition containing same, preparation method and application Download PDFInfo
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- C07F9/02—Phosphorus compounds
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- C07F9/50—Organo-phosphines
- C07F9/505—Preparation; Separation; Purification; Stabilisation
- C07F9/5063—Preparation; Separation; Purification; Stabilisation from compounds having the structure P-H or P-Heteroatom, in which one or more of such bonds are converted into P-C bonds
- C07F9/5077—Preparation; Separation; Purification; Stabilisation from compounds having the structure P-H or P-Heteroatom, in which one or more of such bonds are converted into P-C bonds from starting materials having the structure P-Metal, including R2P-M+
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
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- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention discloses a transition metal compound shown in formula (I) and an olefin polymerization catalyst composition containing the transition metal compound, wherein the catalyst composition also comprises an organic aluminum compound, a carrier and an activator. The catalyst composition comprising the transition metal compound shown in the formula (I) is used for ethylene homopolymerization or copolymerization, has the characteristics of high activity and excellent copolymerization performance, and can be used for preparing bimodal polyethylene
Description
Technical Field
The invention belongs to the field of polyolefin catalysts, and particularly relates to a transition metal compound, an olefin polymerization catalyst composition containing the transition metal compound and application of the catalyst composition in ethylene polymerization.
Background
The polyethylene resin is used as the most widely used synthetic resin with the largest yield and the widest application, and is widely applied to the fields of films, pipes, injection molding products and the like. Currently, the polyethylene produced by Ziegler-Natta catalysts still occupies the largest market share in industry, mainly for slurry and gas phase ethylene polymerization processes. The industrial application of the metallocene catalyst can obviously change the molecular structure, the performance and the quality of the polyethylene. Compared with a Ziegler-Natta catalyst, the metallocene catalyst has higher catalytic activity, shows more excellent ethylene/alpha-olefin copolymerization performance, can optimize and precisely control the molecular chain structure of polyethylene through the adjustment of the spatial structure of a ligand, and can prepare a polyethylene product with target performance. However, metallocene catalysts are homogeneous catalysts, which require a support treatment for their use in heterogeneous slurry or gas phase polymerization processes. Moreover, as a single-site catalyst, the metallocene catalyst produces a polyethylene with a narrow molecular weight distribution, and the single catalyst component and single reactor conditions cannot be used to produce bimodal polyethylene with excellent processability.
EP0416815, EP0420436, EP0923589, WO9806728, EP2980104, etc. disclose a series of homogeneous metallocene catalysts, which are prepared by linking tetramethylcyclopentadiene or a derivative of tetramethylcyclopentadiene to an active center metal through a bridging group and another heteroatom group, have high ethylene polymerization activity and excellent ethylene/α -olefin copolymerization performance, can prepare copolymers with high comonomer content, but cannot be directly used in heterogeneous ethylene polymerization processes.
AHMADI M et al (Macromolecular Reaction Engineering,2007,1(6):604-610.) load metallocene catalyst and Ziegler-Natta catalyst on magnesium chloride carrier at the same time to prepare bimodal polyethylene, but because two active centers interfere with each other, the polymerization activity is very low.
HONG S C et al (Polymer Engineering & Science,2007,47(2): 131-.
CN102180977 discloses a preparation method of heterobinuclear metallocene catalyst, which is used for producing bimodal polyethylene with wide molecular weight distribution, but the catalyst synthesis method is complicated and the yield is low.
Disclosure of Invention
In view of the problems in the prior art as described above, the present invention provides a transition metal compound and an olefin polymerization catalyst composition comprising the same. The polymerization catalyst composition has the characteristics of high activity and excellent homopolymerization or copolymerization performance when being used for ethylene homopolymerization or copolymerization, and can realize the preparation of bimodal polyethylene in a single reactor.
In one aspect of the present invention, there is provided a transition metal compound represented by formula (I):
wherein R is 1 ～R 13 Each independently hydrogen or an alkyl group, preferably C 1 -C 20 Linear or branched or cyclic alkyl groups of (a); further preferred is R 2 、R 8 、R 10 Or R 12 Each independently is C 1 -C 5 Alkyl groups of (a), especially tert-butyl;
a is C 1 -C 20 Preferably butadienyl, 1, 3-pentadienyl, 2, 3-dimethyl-1, 3-pentadienyl or 1, 4-diphenyl-1, 3-butadienyl, more preferably 1, 3-pentadienyl or 2, 3-dimethyl-1, 3-pentadienyl;
m is a group IVB-IIB transition metal atom, preferably titanium, zirconium or hafnium;
d is a VIA group element, preferably O or S;
e is C 1 -C 20 Linear or branched or cyclic alkyl groups of, preferably C 1 -C 10 Linear or branched or cyclic alkyl groups of (a);
g and L are the same or different and are each independently a group VA element, preferably each independently N or P.
In a preferred embodiment of the present invention, the transition metal compound is:
in another aspect of the present invention, there is provided a method for preparing a transition metal compound represented by formula (I), which comprises the steps of:
1) slowly adding tert-butyldimethylchlorosilane (TBSCl) into an inert solvent containing the compound 1, and stirring for reaction to generate a compound 2; slowly adding an alkane solution of n-butyllithium into the reaction solution, and continuously stirring for reaction to obtain a solution component I containing a compound 3;
2) slowly adding the compound 5 into an inert solvent containing the compound 4, stirring for reaction to obtain a suspension, and filtering to obtain a liquid component II containing the compound 6;
3) slowly adding the component I into the component II, and stirring for reaction to obtain a compound 7; adding the compound 8 into the reaction solution, and continuously stirring for reaction; adding tetra-n-butylammonium fluoride (TBAF), continuing the reaction, filtering and collecting liquid, and removing the solvent to obtain a ligand compound component 9;
4) slowly adding the alkane solution of n-butyllithium into an inert solvent containing a ligand compound component 9, and stirring for reaction; the resulting reaction solution was slowly added to a solution containing MCl 4 ·(THF) 2 The reaction is continued in the inert solvent; adding the compound A (namely C in the compound of the formula (I) above) into the reaction solution in sequence 1 -C 20 Before reaction of the diolefin groups C 1 -C 20 Diolefin (b) and n-butyl ethyl magnesium, continuously reacting, filtering and removing the solvent to obtain a transition metal compound 11, namely the compound shown in the formula (I)A transition metal compound.
In a specific embodiment of the present invention, in the method for producing a transition metal compound represented by the above formula (I):
in the step 1), the reaction conditions of the tert-butyldimethylsilyl chloride and the compound 1 are as follows: the temperature is 0-60 ℃, the time is 6-24h, and the stirring speed is 10-100 rpm; the temperature is reduced to-20-0 ℃ before the n-butyllithium alkane solution is added, and the conditions for continuing the reaction after the n-butyllithium alkane solution is added are as follows: the temperature is 0-60 ℃, the time is 6-12h, and the stirring speed is 10-100 rpm;
in the step 2), the compound 5 is added into an inert solvent containing the compound 4 at the temperature of-20-0 ℃, and the reaction conditions of the compound 5 and the compound 4 are as follows: the temperature is 0-60 ℃, the time is 6-24h, and the stirring speed is 10-100 rpm;
in step 3), the component I is added into the component II at the temperature of-20-0 ℃, and the reaction conditions of the component I and the component II are as follows: the temperature is 0-60 ℃, the time is 6-12h, and the stirring speed is 10-100 rpm; the time for continuing the reaction after the compound 8 is added is 6-12h, and the time for continuing the reaction after the tetra-n-butylammonium fluoride (TBAF) is added is 12-24 h;
in the step 4), the n-butyllithium alkane solution is added into an inert solvent containing the ligand compound component 9 at a temperature of-20 to 0 ℃, and the reaction conditions of the n-butyllithium and the ligand compound component 9 are as follows: the temperature is 0-60 ℃, the time is 6-12h, and the stirring speed is 10-100 rpm; adding the obtained reaction solution to MCl 4 ·(THF) 2 Is carried out at a temperature of-20 to 0 ℃, and the reaction solution is added to MCl 4 ·(THF) 2 The conditions for the subsequent reaction were: the temperature is 0-60 ℃, and the time is 12-24 h; adding the compound A and the n-butyl ethyl magnesium at the temperature of-20-0 ℃, wherein the conditions for continuing the reaction after adding the compound A and the n-butyl ethyl magnesium are as follows: the temperature is 0-60 ℃, and the time is 12-24 h.
In a specific embodiment of the present invention, in the above preparation method, the inert solvent in the step 1), the step 2) and the step 4) is the same or different from diethyl ether, tetrahydrofuran, ethylene glycol dimethyl ether, 2-methylfuran, 2, 5-dimethylfuran and 2, 3-benzofuranPreferably tetrahydrofuran, and the addition amount of the inert solvent is not particularly limited, and the corresponding materials can be completely dissolved; the alkane solution in the step 1) and the step 4) has the same or different solvent and is C 5 -C 10 The alkane of (a) is one or more, preferably n-hexane, and the amount of the alkane solvent added is not particularly limited, and the corresponding material can be completely dissolved.
In the method for producing a transition metal compound represented by formula (I) of the present invention, those skilled in the art can appropriately mix the reaction raw materials according to the reaction formula and the ordinary techniques in the art. For example, in step 1), the molar ratio of tert-butyldimethylsilyl chloride (TBSCl) to compound 1 is about 1: 1; in step 2), the molar ratio of compound 5 to compound 4 is about 1: 1; in step 3), the molar ratio of compound 3 in component I to compound 6 in component II is about 1:1, the molar ratio of compound 8 to compound 7 is about 1:1, and the molar ratio of tetra-n-butylammonium fluoride (TBAF) to compound 8 is about 1: 1; in step 4), the molar ratio of n-butyllithium to the ligand compound component 9 is about 2:1, MCl 4 ·(THF) 2 The molar ratio to the ligand compound component 9 is about 1: 1. Although the molar ratio of each raw material in the process for producing the transition metal compound represented by the formula (I) is exemplified, those skilled in the art can reasonably adjust the molar ratio within a reasonable range according to actual needs, and such adjustment is within the scope of the present invention.
In another aspect of the present invention, there is provided an olefin polymerization catalyst composition comprising one or more transition metal compounds, a support, an organoaluminum compound and an activator, wherein the ratio of the organoaluminum compound to the transition metal compound is 1 to 500:1, preferably 50 to 200:1, such as 400:1, 300:1, 200:1 or 100:1, etc., on a molar basis; the ratio of the activating agent to the transition metal compound is 1-50: 1, preferably 3-10: 1, such as 40:1, 30:1, 20:1, 5:1, etc. on a molar basis; the support comprises 40% to 90%, such as 50%, 70%, 80% or 85% etc. by weight of the catalyst composition, wherein the transition metal compound is one or more of the compounds of formula (I), preferably one or more of the compounds (1) to (6) described above, or one or more of the transition metal compounds prepared according to the aforementioned method.
In a specific embodiment of the present invention, the support is one or more of silica gel, magnesium chloride, alumina, aluminum phosphate and titanium dioxide. In a preferred embodiment, the carrier is silica gel calcined at a temperature of 500-900 ℃ for 6-10 hours under the protection of an inert atmosphere.
In a specific embodiment of the present invention, the organoaluminum compound is one or more of trimethylaluminum, triethylaluminum, triisobutylaluminum, methylaluminoxane and modified aluminoxane, preferably triisobutylaluminum and/or methylaluminoxane.
In a particular embodiment of the invention, the activator is:
B(C 6 F 5 ) 3 、[(C 6 H 5 ) 3 C] + [B(C 6 F 5 ) 4 ] - 、[(C 18 H 37 ) 2 N(CH 3 )H] + [B(C 6 F 5 ) 4 ] - and [ (CH) 3 ) 2 PhNH 3 ] + [B(C 6 F 5 ) 4 ] - Preferably B (C) 6 F 5 ) 3 And/or [ (C) 6 H 5 ) 3 C] + [B(C 6 F 5 ) 4 ] - 。
In another aspect of the present invention, there is provided a method for preparing the aforementioned olefin polymerization catalyst composition, comprising the steps of:
1) under the protection of inert atmosphere, slowly adding the organic aluminum compound into an inert liquid medium 1 under stirring, adding a carrier, and stirring, mixing and contacting to form an emulsion component 1;
2) under the protection of inert atmosphere, adding the transition metal compound and the activating agent into an inert liquid medium 2, stirring, mixing and dissolving to form a solution component 2;
3) under the protection of inert atmosphere, slowly adding the solution component 2 into the emulsion component 1 under stirring, and stirring and mixing; cooling to room temperature, slowly adding an inert liquid medium 3, and continuously stirring and uniformly mixing to obtain an emulsion component 3;
4) the emulsion component 3 was dried under vacuum to give a viscous solid catalyst composition.
In a specific embodiment of the present invention, in step 1) and step 2), the inert liquid medium 1 and the inert liquid medium 2 are each independently one or more of toluene, xylene, methylcyclohexane and dichloromethane, preferably toluene, and the amount added is not particularly limited, and the corresponding materials can be completely dissolved; in step 3), the inert liquid medium 3 is hexane, heptane and C 8 -C 10 The addition amount of one or more of the mixed isoparaffins is 2-3 times of the toluene dosage, preferably n-hexane.
In a specific embodiment of the invention:
in the step 1), the conditions of stirring, mixing and contacting are as follows: the temperature is 0-60 ℃; the time is 0.1 to 6 hours; the stirring speed is 300-;
in step 2), the stirring, mixing and dissolving conditions are as follows: the temperature is 10-100 ℃; the time is 0.1-1 h; the stirring speed is 200-600 rpm;
in step 3), the conditions for stirring and mixing after slowly adding the solution component 2 into the emulsion component 1 are as follows: the temperature is 0-100 ℃, the time is 0.1-6h, and the stirring speed is 500-; cooling to room temperature, slowly adding the inert liquid medium 3, and continuously stirring and mixing under the following conditions: the time is 0.1 to 6 hours; the stirring speed is 300-;
in step 4), the vacuum drying conditions are as follows: the pressure is 1-10 KPa; the temperature is 60-80 ℃.
A further aspect of the invention provides the use of the aforementioned catalyst composition or a catalyst composition prepared according to the aforementioned process in homo-or co-polymerisation of ethylene.
Compared with the prior art, the beneficial effects of the invention are mainly embodied in the following aspects:
the mode of combining the transition metal compound with the organic aluminum compound, the carrier and the activator solves the application defect of a homogeneous metallocene catalyst in a heterogeneous ethylene polymerization process, further improves the polymerization activity and copolymerization performance of the catalyst compared with a Ziegler-Natta catalyst, and can realize the preparation of bimodal polyethylene by a single reactor through the combination of various transition metal compounds; the preparation method of the olefin polymerization catalyst composition provided by the invention is simple, low in energy consumption and high in yield.
Detailed Description
The process provided by the present invention is described in further detail below, but the present invention is not limited thereto.
Raw materials
TABLE 1 Source and Specifications of raw materials
| Name (R) | Specification of | Source |
| 2-bromo-4, 6-di (tert-butyl) phenol | 97％ | Bailingwei Tech Co Ltd |
| Tert-butyldimethylsilyl chloride | 98％ | Bailingwei Tech Co Ltd |
| Tetra-n-butylammonium fluoride | 1.0M | Bailingwei Tech Co Ltd |
| N-butyl lithium | 2.5M | Bailingwei Tech Co Ltd |
| 2-bromo-1, 4-cyclohexanedione | 97％ | Debye technologies Ltd |
| Butyl magnesium bromide | 1.0M | Taishiai (Shanghai) chemical industry development Limited |
| N-butyl ethyl magnesium | 0.9M | Bailingwei Tech Co Ltd |
| Zirconium tetrachloride tetrahydrofuran complex | 95％ | SHANGHAI ALADDIN BIOCHEMICAL TECHNOLOGY Co.,Ltd. |
| Titanium tetrachloride tetrahydrofuran complex | 95％ | SHANGHAI ALADDIN BIOCHEMICAL TECHNOLOGY Co.,Ltd. |
| Piperylene of piperylene | 97％ | Shanghai Mairuier Chemical Technology Co., Ltd. |
| Nitrogen gas | 99.9995％ | Beijing He Pubei gas industry Co Ltd |
| Toluene | Analytical purity | SINOPHARM CHEMICAL REAGENT Co.,Ltd. |
| N-hexane | Analytical purity | SINOPHARM CHEMICAL REAGENT Co.,Ltd. |
| Tetrahydrofuran (THF) | Analytical purity | SINOPHARM CHEMICAL REAGENT Co.,Ltd. |
| Toluene solution of triisobutylaluminum | 1.0M | Aladdin Biotechnology Ltd |
| Toluene solution of methylaluminoxane | 1.5M | Yanfeng technology (Beijing GmbH) |
| Tris (pentafluorophenyl) boron | 98％ | Taishiai (Shanghai) chemical industry development Limited |
| Trityl tetrakis (pentafluorophenyl) borate | 98％ | Taishiai (Shanghai) chemical industry development Limited |
| Silica gel | 100％ | Kabot blue Star chemical (Jiangxi) Co Ltd |
| [(Me 4 Cp)SiMe 2 NtBu]Ti(CH 3 )Cl 2 | 98％ | Yanfeng technology (Beijing) Co Ltd |
Test method
Method for structural characterization of transition metal compounds measured by 1H-NMR (Bruker ADVANCE III 400M) in deuterated chloroform with a nitrogen reflux in calcium hydride.
The polymerization activity is calculated as the ratio of the weight of the dried polymer product obtained from the polymerization reaction to the weight of the catalyst composition added during the reaction.
Polymer molecular weight (Mw) and molecular weight distribution (PDI) were determined by high temperature gel permeation chromatography (PL-GPC220) using 1,2, 4-trichlorobenzene as the mobile phase and polystyrene as the standard at 150 ℃, with a standard concentration of 0.1mg/mL, a solvent flow rate of 1.0mL/min, using a standard K of 59.1, a of 0.69, a sample K of 14.1, a of 0.70.
The comonomer insertion in the ethylene/alpha-olefin copolymer was measured by 13C-NMR (Bruker ADVANCE III 400M). The polymer was formulated in a solution of deuterated 1, 2-o-dichlorobenzene at 130 deg.C at about 100 mg/mL. The instrument parameters are pulse angle of 30 degrees, whole process decoupling is realized, pulse delay time is 3s, and a high-temperature nuclear magnetic spectrum is obtained by continuously scanning a sample for more than 3000 times. The carbon spectrum of the copolymer is assigned by adopting an ASTM D5017-96 method, and the sequence distribution and the average comonomer composition of the copolymer are calculated.
Examples
Preparation of transition metal compounds
Example 1: preparation of transition Metal Compound 1
Adding 1.20g (0.0042mol) of 2-bromo-4, 6-di (tert-butyl) phenol into 50mL of tetrahydrofuran solvent, adding 0.64g of tert-butyldimethylsilyl chloride (0.0042mol) at a stirring speed of 10rmp, stirring and reacting for 6h at room temperature (about 25 ℃) and a rotating speed of 100rmp, cooling the reaction temperature to 0 ℃, slowly dropwise adding 1.72mL of 2.5M n-BuLi hexane solution, heating to room temperature after dropwise adding, and stirring and reacting for 6h to obtain a solution component 1;
adding 0.79g of 2-bromo-1, 4-cyclohexanedione (0.0042mol) into 50mL of tetrahydrofuran solvent, slowly dropwise adding 4.20mL of 1.0M tetrahydrofuran solution of butyl magnesium bromide at the temperature of 0 ℃ and the stirring speed of 10rmp, heating to room temperature (about 25 ℃) after dropwise adding is finished, stirring and reacting for 12 hours at the rotating speed of 100rmp, and filtering the obtained white turbid suspension to obtain a liquid component 2;
slowly dropwise adding the component 1 into the component 2 under the condition of slowly stirring at 0 ℃ and 10rmp, after dropwise adding, heating the temperature to room temperature (about 25 ℃), stirring at the rotating speed of 100rmp for reaction for 12h, adding 0.87g of aniline compound (0.0042mol), continuously stirring for reaction for 6h, continuously adding 1.10g of tetra-n-butylammonium fluoride (0.0042mol), continuously reacting for 12h, filtering and collecting liquid, and evaporating the solvent by rotary evaporation to dryness to obtain 1.53g of ligand component 3, wherein the yield is 67%;
1 H-NMR(400MHz,CHCl 3 ,TMS,δin ppm):4.02(s,1H,NH),5.36(s,1H,OH),6.52(d,2H,C 6 H 4 N),7.02(d,2H,C 6 H 4 N),3.35(s,2H,NC 3 H 6 N),1.58(s,2H,NC 3 H 6 N),1.46(s,2H,NC 3 H 6 N),2.72(s,2H,NC 6 H 6 )2.99(s,2H,NC 6 H 6 ),2.50(s,1H,NC 6 H 6 C 6 ),2.96(s,1H,NC 6 H 6 ),7.19(s,1H,C 6 H 4 O),7.02(s,1H,C 6 H 4 O),1.35(s,18H,C(CH 3 ) 3 C 6 O),1.35(s,9H,C(CH 3 ) 3 C 6 N),1.35(s,3H,C(CH 3 ) 3 C 6 N),1.20(s,6H,C(CH 3 ) 3 C 6 N).
adding 1.0g of component 3(0.0018mol) into 40mL of THF solvent, dropwise adding 1.5mL of 2.5M n-BuLi hexane solution under the condition of slowly stirring at 0 ℃ and 10rmp, heating to room temperature after dropwise adding, and stirring for reacting for 10h to obtain a brown yellow transparent solution; the temperature was then cooled to 0 ℃ and the clear solution was slowly added dropwise to a solution containing 0.68g of ZrCl 4 (THF) 2 (0.0018mol) in 40mL of THF solvent, after the dropwise addition, raising the temperature to about 25 ℃, reacting for 12h at the rotation speed of 100rmp, then reducing the temperature to 0 ℃, adding 0.18g of piperylene (0.0027mol) and 3mL of 0.9M n-butyl ethyl magnesium in sequence, raising the temperature to room temperature, stirring and reacting for 12h, filtering, and removing the solvent through reduced pressure distillation to obtain 1.03g of brown transition metal compound 1, wherein the yield is 82%.
1 H-NMR(400MHz,CHCl 3 ,TMS,δin ppm):6.22(d,2H,C 6 H 4 N),6.89(d,2H,C 6 H4N),3.21(s,2H,NC 3 H 6 N),1.50(s,2H,NC 3 H 6 N),1.26(s,2H,NC 3 H 6 N),2.72(s,2H,NC 6 H 6 )2.99(s,2H,NC 6 H 6 ),2.50(s,1H,NC 6 H 6 C 6 ),2.96(s,1H,NC 6 H 6 ),7.12(s,1H,C 6 H 4 O),7.01(s,1H,C 6 H 4 O),1.34(s,18H,C(CH 3 ) 3 C 6 O),1.34(s,9H,C(CH 3 ) 3 C 6 N),1.34(s,3H,C(CH 3 ) 3 C 6 N),1.20(s,6H,C(CH 3 ) 3 C 6 N),5.60(m,6H,C 5 H 8 )。
Example 2: preparation of transition Metal Compound 5
According to the preparation process of the transition metal compound 1, the difference is that: the aniline compound was replaced with 1.0g of a phenylphosphorus compound to give 1.35g of ligand component 3 with a yield of 56%;
1 H-NMR(400MHz,CHCl 3 ,TMS,δin ppm):4.23(s,1H,PH),5.35(s,1H,OH),7.30(d,2H,C 6 H 4 P),7.46(d,2H,C 6 H 4 N),1.42(s,1H,PC 4 H 8 N),1.34(s,1H,PC 4 H 8 N),0.97(s,3H,PC 4 H 8 N),1.06(s,3H,PC 4 H 8 N),2.75(s,2H,NC 6 H 6 )2.99(s,2H,NC 6 H 6 ),2.50(s,1H,NC 6 H 6 C 6 ),2.96(s,1H,NC 6 H 6 ),7.21(s,1H,C 6 H 4 O),7.02(s,1H,C 6 H 4 O),1.35(s,18H,C(CH 3 ) 3 C 6 O),1.35(s,9H,C(CH 3 ) 3 C 6 P),1.35(s,3H,C(CH 3 ) 3 C 6 N),1.20(s,6H,C(CH 3 ) 3 C 6 N)。
1.04g of ligand component 3(0.0018mol) was added and ZrCl was added 4 (THF) 2 The change was 0.60g of TiCl 4 (THF) 2 Thus, 1.08g of brown transition metal compound 5 was obtained, representing a yield of 86%.
1 H-NMR(400MHz,CHCl 3 ,TMS,δin ppm):7.24(d,2H,C 6 H 4 P),7.26(d,2H,C 6 H 4 N),1.41(s,1H,PC 4 H 8 N),1.36(s,1H,PC 4 H 8 N),0.97(s,3H,PC 4 H 8 N),1.06(s,3H,PC 4 H 8 N),2.75(s,2H,NC 6 H 6 )2.99(s,2H,NC 6 H 6 ),2.50(s,1H,NC 6 H 6 C 6 ),2.96(s,1H,NC 6 H 6 ),7.21(s,1H,C 6 H 4 O),7.02(s,1H,C 6 H 4 O),1.35(s,18H,C(CH 3 ) 3 C 6 O),1.35(s,9H,C(CH 3 ) 3 C 6 P),1.35(s,3H,C(CH 3 ) 3 C 6 N),1.20(s,6H,C(CH 3 ) 3 C 6 N)。
Preparation of the catalyst composition
Example 3
1) Preparation of component 1
Under the protection of nitrogen atmosphere, adding 100mL of anhydrous and anaerobic purification-treated toluene solvent into a purified 250mL three-neck flask with mechanical stirring, starting stirring at 800rpm, slowly dropwise adding 1.5M of methylaluminoxane toluene solution (0.1mL) at the temperature of 20 ℃, adding a silica gel carrier (3.6g) calcined at the high temperature of 600 ℃ for 8 hours under the protection of nitrogen atmosphere, and stirring and mixing at room temperature for 6 hours to obtain an emulsion component 1;
2) preparation of component 2
Under the protection of nitrogen atmosphere, a purified 100mL three-neck flask with mechanical stirring is added with a transition metal compound 1(0.08g) and an activating agent [ (C) 6 H 5 ) 3 C] + [B(C 6 F 5 ) 4 ] - (5.16g) and 20mL of anhydrous and anaerobic purified toluene solvent, starting stirring at 600rpm, and stirring and mixing at 40 ℃ for 10min to obtain a uniform solution component 2;
3) preparation of component 3
Under the protection of nitrogen atmosphere, firstly adding the emulsion component 1 prepared in the step 1) into a purified 500mL three-neck flask with mechanical stirring, starting stirring at 900rpm, then slowly dropwise adding the solution component 2 prepared in the step 2), and stirring and mixing for 1h at the temperature of 50 ℃ after dropwise adding; the temperature was then lowered to room temperature, 100mL of n-hexane solvent was slowly added, and mixing was continued at 900rpm for 2 h.
After stirring was stopped and the supernatant liquid was poured off, the mixture was dried under vacuum at a vacuum degree of 1KPa and a temperature of 80 ℃ for 1 hour to obtain 8.7g of a viscous solid catalyst composition 1.
Example 4
1) Preparation of component 1
The procedure is followed for the preparation of component 1 of example 1, with the difference that: the dosage of the 1.5M toluene solution of methylaluminoxane is 55.9mL, the dosage of the silica gel carrier is 8.4g, and the conditions of stirring, mixing and contacting are as follows: the temperature is 0 ℃, the time is 0.1h, and the stirring speed is 1000rmp, so as to prepare an emulsion component 1;
2) preparation of component 2
The procedure is followed for the preparation of component 2 of example 1, with the difference that: the amount of the transition metal compound 1 used was 0.12gReagent [ (C) 6 H 5 ) 3 C] + [B(C 6 F 5 ) 4 ] - The dosage of the compound is 0.15g, and the stirring, mixing and dissolving conditions are as follows: the temperature is 10 ℃, the time is 1h, and the stirring speed is 200rmp, so that a uniform solution component 2 is prepared;
3) preparation of component 3
The procedure is followed for the preparation of component 3 in example 1, with the difference that: the conditions for mixing the emulsion component 1 and the solution component 2 are as follows: the temperature is 0 ℃, the time is 6h, and the stirring speed is 500 rmp; after the hexane solvent was added, the mixing was continued with stirring under the following conditions: time 0.1h, stirring speed 300 rmp.
12.9g of viscous solid catalyst composition 2 were obtained.
Example 5
1) Preparation of component 1
The procedure is followed for the preparation of component 1 of example 1, with the difference that: the dosage of the 1.5M toluene solution of methylaluminoxane is 9.3mL, the dosage of the silica gel carrier is 9.0g, and the conditions of stirring, mixing and contacting are as follows: the temperature is 60 ℃, the time is 1h, and the stirring speed is 300rmp, so that an emulsion component 1 is prepared;
2) preparation of component 2
The procedure is followed for the preparation of component 2 of example 1, with the difference that: the amount of the transition metal compound 1 used was 0.1g, and the activator [ (C) 6 H 5 ) 3 C] + [B(C 6 F 5 ) 4 ] - The dosage of the compound is 0.65g, and the stirring, mixing and dissolving conditions are as follows: the temperature is 100 ℃, the time is 0.1h, the stirring speed is 600rmp, and a uniform solution component 2 is prepared;
3) preparation of component 3
The procedure is followed for the preparation of component 3 in example 1, with the difference that: the conditions for mixing the emulsion component 1 and the solution component 2 are as follows: the temperature is 100 ℃, the time is 0.1h, and the stirring speed is 1000 rmp; after the hexane solvent was added, the mixing was continued with stirring under the following conditions: time 6h, stirring speed 1000 rmp.
10.2g of a viscous solid catalyst composition 3 were obtained.
Example 6
1) Preparation of component 1
The procedure is followed for the preparation of component 1 of example 1, with the difference that: the dosage of the 1.5M methyl aluminoxane toluene solution is 9.4mL, and the dosage of the silica gel carrier is 7.2g, so as to prepare an emulsion component 1;
2) preparation of component 2
The procedure is followed for the preparation of component 2 of example 1, with the difference that: the transition metal compound was replaced with a mixture of 1 and 5, both in an amount of 0.1g, and an activator [ (C) 6 H 5 ) 3 C] + [B(C 6 F 5 ) 4 ] - The amount of (b) was 0.78g to prepare homogeneous solution component 2;
3) preparation of component 3
The procedure is followed for the preparation of component 3 in example 1, with the difference that: the vacuum drying conditions were: vacuum 10KPa, temperature 60 ℃.
8.6g of viscous solid catalyst composition 4 were obtained.
Example 7
1) Preparation of component 1
The procedure is followed for the preparation of component 1 of example 1, with the difference that: replacing 1.5M of methylaluminoxane in toluene solution with 1.0M of triisobutylaluminum in toluene solution, wherein the dosage is 12.6mL, and the silica gel carrier is calcined at the high temperature of 500 ℃ for 10 hours under the protection of nitrogen, and the dosage is 8.4g, so as to prepare an emulsion component 1;
2) preparation of component 2
The procedure is followed for the preparation of component 2 of example 1, with the difference that: the amount of the transition metal compound 1 used was 0.09g, and the activator [ (C) 6 H 5 ) 3 C] + [B(C 6 F 5 ) 4 ] - The amount of (b) was 0.58g to prepare homogeneous solution component 2;
3) preparation of component 3
The procedure for the preparation of component 3 of example 1 was followed.
11.2g of viscous solid catalyst composition 5 were obtained.
Example 8
1) Preparation of component 1
The procedure is followed for the preparation of component 1 of example 1, with the difference that: the dosage of 1.5M methyl aluminoxane toluene solution is 4.7mL, the silica gel carrier is calcined for 6 hours at 900 ℃ under the protection of nitrogen, and the dosage is 6.0g, thus obtaining emulsion component 1;
2) preparation of component 2
The procedure is followed for the preparation of component 2 of example 1, with the difference that: the amount of the transition metal compound 1 used was 0.1g, and the activator was replaced with B (C) 6 F 5 ) 3 The using amount is 0.15g, and a uniform solution component 2 is prepared;
3) preparation of component 3
The procedure for the preparation of component 3 of example 1 was followed.
6.1g of a viscous solid catalyst composition 6 was obtained.
Comparative example 1
Preparation of component 1
The procedure is followed for the preparation of component 1 of example 1, with the difference that: the dosage of the toluene solution of 1.5M methylaluminoxane is 20.4mL, and the dosage of the silica gel carrier is 19g, so that an emulsion component 1 is prepared;
2) preparation of component 2
The procedure is followed for the preparation of component 2 of example 1, with the difference that: replacement of transition Metal Compound 1 with [ (Me) 4 Cp)SiMe 2 N t Bu]TiCl 2 In an amount of 0.1g, an activator [ (C) 6 H 5 ) 3 C] + [B(C 6 F 5 ) 4 ] - The amount of (A) was 1.4g to prepare homogeneous solution component 2;
3) preparation of component 3
The procedure for the preparation of component 3 of example 1 was followed.
22.0g of a viscous solid catalyst composition 7 was obtained.
TABLE 2 catalyst compositions preparation of catalyst compositions examples 3-8 and comparative example 1 raw materials and compounding ratios
The catalyst compositions 1 to 7 prepared in examples 3 to 8 and comparative example 1 were used in the subsequent polymerization examples 9 to 14 and comparative polymerization example 2.
Polymerization of ethylene
Example 9
Ethylene slurry polymerization was carried out in a 2L stainless steel batch reactor with mechanical agitation.
Under the protection of nitrogen, 1000mL of anhydrous and anaerobic purified n-hexane solvent and 5mL of 1.1M triisobutylaluminum hexane solution are added into a reaction kettle, water and oxygen impurities in the reaction kettle are rapidly stirred and treated, and after unloading, the mixture is dried at high temperature in vacuum and is replaced by ethylene gas for three times. Keeping the micro-positive pressure in the kettle, weighing 150mg of the catalyst composition 1 prepared in the example 3, mixing with 1000mL of purified hexane solvent, adding into the reaction kettle in a negative pressure extraction mode, then heating to the reaction temperature of 70 ℃, starting stirring at 500rpm, introducing ethylene gas after the temperature is stable, keeping the pressure in the kettle stable at the required polymerization pressure of 1.0Mpa, and starting the polymerization reaction for 1 h. After the polymerization reaction, ethylene was turned off, the reaction vessel was cooled to 40 ℃ or lower, unreacted ethylene in the vessel was discharged, and the reaction slurry was discharged into 1L of pure water, washed and filtered, and the polymer was collected and vacuum-dried at 80 ℃ to a constant weight, and weighed to obtain 109.4g of a polymer product, the polymer test results of which are shown in Table 3.
Example 10
The polymerization was carried out as in example 9, with the difference that: catalyst composition 2 was used to obtain 162.8g of polymer product, the polymer test results are shown in Table 3.
Example 11
The polymerization was carried out as in example 9, with the difference that: catalyst composition 3 was used and 50g of 1-butene were added to give 205.9g of a polymer product, the polymer test results are shown in Table 3.
Example 12
The polymerization was carried out as in example 9, with the difference that: catalyst composition 4 was used in an amount of 75mg to yield 245.9g of polymer product having a molecular weight distribution of 36.21, as shown in Table 3, which is significantly higher than the molecular weight distributions of the polymers prepared in the other examples, to produce bimodal polyethylene.
Example 13
The polymerization was carried out as in example 9, with the difference that: catalyst composition 5 was used to obtain 187.5g of polymer product, the polymer test results are shown in Table 3.
Example 14
The polymerization was carried out as in example 9, with the difference that: catalyst composition 6 was used to obtain 344.3g of polymer product, the polymer test results are shown in Table 3.
Comparative example 2
The polymerization was carried out as in example 9, with the difference that: catalyst composition 7 was used and 50g of 1-butene were added to obtain 104.0g of a polymer product, the polymer test results are shown in Table 3.
TABLE 3 polymerization results
As can be seen from the results of the polymerization reactions in the above examples and by comparison with comparative examples, the olefin polymerization catalyst composition of the present invention exhibits very high polymerization activity and excellent copolymerization performance when used for ethylene homopolymerization or ethylene/1-butene copolymerization, and can produce bimodal polyethylene products with wide molecular weight distribution.
Although the invention has been described in detail in the foregoing for the purpose of illustration, it is to be understood that such detail is solely for that purpose and that variations can be made therein by those skilled in the art without departing from the spirit and scope of the invention except as it may be limited by the claims.
Claims (13)
1. A transition metal compound represented by the formula (I):
wherein R is 1 、R 3 ～R 7 、R 9 、R 11 Or R 13 Each independently is hydrogen or C 1 -C 20 Linear or branched or cyclic alkyl radicals of R 2 、R 8 、R 10 Or R 12 Each independently is C 1 -C 5 An alkyl group of (a);
a is C 1 -C 20 A diene group of (a);
m is titanium, zirconium or hafnium;
d is O or S;
e is C 1 -C 10 Linear or branched or cyclic alkyl groups of (a);
g and L are the same or different and are each independently N or P.
2. The transition metal compound according to claim 1,
R 1 ～R 13 each independently hydrogen, methyl or tert-butyl;
a is butadienyl, 1, 3-pentadienyl, 2, 3-dimethyl-1, 3-pentadienyl or 1, 4-diphenyl-1, 3-butadienyl.
3. The transition metal compound according to claim 1, wherein the transition metal compound is:
4. a process for preparing the transition metal compound of claim 1, comprising the steps of:
1) slowly adding tert-butyldimethylsilyl chloride into an inert solvent containing the compound 1, and stirring for reaction to generate a compound 2; slowly adding an alkane solution of n-butyllithium into the reaction solution, and continuously stirring for reaction to obtain a solution component I containing a compound 3;
2) slowly adding the compound 5 into an inert solvent containing the compound 4, stirring for reaction to obtain a suspension, and filtering to obtain a liquid component II containing the compound 6;
3) slowly adding the component I into the component II, and stirring for reaction to obtain a compound 7; adding the compound 8 into the reaction solution, and continuously stirring for reaction; adding tetra-n-butylammonium fluoride, continuing to react, filtering and collecting liquid, and removing the solvent to obtain a ligand compound component 9;
4) slowly adding the alkane solution of n-butyllithium into an inert solvent containing a ligand compound component 9, and stirring for reaction; the resulting reaction solution was slowly added to a solution containing MCl 4 ·(THF) 2 The reaction is continued in the inert solvent; and adding the compound A and n-butyl ethyl magnesium into the reaction solution in sequence, continuing to react, filtering, and removing the solvent to obtain a transition metal compound 11, namely the transition metal compound shown in the formula (I).
5. The method of claim 4,
in the step 1), the reaction conditions of the tert-butyldimethylsilyl chloride and the compound 1 are as follows: the temperature is 0-60 ℃, and the time is 6-24 h; the temperature is reduced to-20-0 ℃ before the n-butyllithium alkane solution is added, and the conditions for continuing the reaction after the n-butyllithium alkane solution is added are as follows: the temperature is 0-60 ℃, and the time is 6-12 h;
in the step 2), the compound 5 is added into an inert solvent containing the compound 4 at the temperature of-20-0 ℃, and the reaction conditions of the compound 5 and the compound 4 are as follows: the temperature is 0-60 ℃, and the time is 6-24 h;
in step 3), the component I is added into the component II at the temperature of-20-0 ℃, and the reaction conditions of the component I and the component II are as follows: the temperature is 0-60 ℃, and the time is 6-12 h; the time for continuing the reaction after the compound 8 is added is 6-12h, and the time for continuing the reaction after the tetra-n-butylammonium fluoride is added is 12-24 h;
in the step 4), the n-butyllithium alkane solution is added into an inert solvent containing the ligand compound component 9 at a temperature of-20 to 0 ℃, and the reaction conditions of the n-butyllithium and the ligand compound component 9 are as follows: the temperature is 0-60 ℃, and the time is 6-12 h; adding the obtained reaction solution to a reaction solution containing MCl 4 ·(THF) 2 Is carried out at a temperature of-20 to 0 ℃, and the reaction solution is added to MCl 4 ·(THF) 2 The conditions for the subsequent reaction were: the temperature is 0-60 ℃, and the time is 12-24 h; adding the compound A and the n-butyl ethyl magnesium at the temperature of-20-0 ℃, wherein the conditions for continuing the reaction after adding the compound A and the n-butyl ethyl magnesium are as follows: the temperature is 0-60 ℃, and the time is 12-24 h.
6. The method according to claim 4 or 5, wherein the inert solvent in step 1), step 2) and step 4) is the same or different and is one or more of diethyl ether, tetrahydrofuran, ethylene glycol dimethyl ether, 2-methylfuran, 2, 5-dimethylfuran and 2, 3-benzofuran, and the solvent of the alkane solution in step 1) and step 4) is the same or different and is C 5 -C 10 One or more of (a) an alkane.
7. An olefin polymerization catalyst composition, characterized in that the composition comprises a transition metal compound, a support, an organoaluminum compound and an activator, wherein the ratio of the organoaluminum compound to the transition metal compound is 1-500: 1 by mol; the ratio of the activating agent to the transition metal compound is 1-50: 1 in terms of moles; the support comprises 40-90% by weight of the catalyst composition, wherein the transition metal compound is selected from one or more transition metal compounds represented by formula (I) in claim 1, or the transition metal compound is selected from one or more transition metal compounds prepared by the method according to any one of claims 4-6.
8. The catalyst composition according to claim 7, wherein the ratio of the organoaluminum compound to the transition metal compound is 50 to 200: 1; the ratio of the activating agent to the transition metal compound is 3-10: 1 in terms of moles; wherein the transition metal compound is selected from one or more of the transition metal compounds of claim 3.
9. The catalyst composition of claim 7, wherein the support is one or more of silica gel, magnesium chloride, alumina, aluminum phosphate, and titanium dioxide; and/or the organic aluminum compound is one or more of trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, methyl aluminoxane and modified aluminoxane; and/or the activator is: b (C) 6 F 5 ) 3 、[(C 6 H 5 ) 3 C] + [B(C 6 F 5 ) 4 ] - 、[(C 18 H 37 ) 2 N(CH 3 )H] + [B(C 6 F 5 ) 4 ] - And [ (CH) 3 ) 2 PhNH 3 ] + [B(C 6 F 5 ) 4 ] - One or more of (a).
10. The catalyst composition of claim 9, wherein the support is silica gel calcined at a temperature of 500 to 900 ℃ for 6 to 10 hours under protection of an inert atmosphere; and/or the organoaluminum compound is triisobutylaluminum and/or methylaluminoxane; and/or the activator is B (C) 6 F 5 ) 3 And/or [ (C) 6 H 5 ) 3 C] + [B(C 6 F 5 ) 4 ] - 。
11. A process for preparing the catalyst composition of any one of claims 7-10, characterized in that the process comprises the steps of:
1) under the protection of inert atmosphere, slowly adding the organic aluminum compound into an inert liquid medium 1 under stirring, adding a carrier, and stirring, mixing and contacting to form an emulsion component 1;
2) adding the transition metal compound and the activating agent into an inert liquid medium 2 under the protection of inert atmosphere, stirring, mixing and dissolving to form a solution component 2;
3) under the protection of inert atmosphere, slowly adding the solution component 2 into the emulsion component 1 under stirring, and stirring and mixing; cooling to room temperature, slowly adding an inert liquid medium 3, and continuously stirring and uniformly mixing to obtain an emulsion component 3;
4) the emulsion component 3 was dried under vacuum to give a viscous solid catalyst composition.
12. The method of claim 11,
in the step 1), the conditions of stirring, mixing and contacting are as follows: the temperature is 0-60 ℃, and the time is 0.1-6 h;
in step 2), the stirring, mixing and dissolving conditions are as follows: the temperature is 10-100 ℃, and the time is 0.1-1 h;
in step 1) and step 2), the inert liquid medium 1 and inert liquid medium 2 are each independently one or more of toluene, xylene, methylcyclohexane and dichloromethane; in step 3), the inert liquid medium 3 is hexane, heptane and C 8 -C 10 One or more of the mixed isoparaffins of (a);
in step 3), the conditions for stirring and mixing after slowly adding the solution component 2 into the emulsion component 1 are as follows: the temperature is 0-100 ℃, and the time is 0.1-6 h; cooling to room temperature, slowly adding the inert liquid medium 3, and continuously stirring and mixing under the following conditions: the time is 0.1 to 6 hours;
in step 4), the vacuum drying conditions are as follows: the pressure is 1-10 KPa; the temperature is 60-80 ℃.
13. Use of the catalyst composition according to any one of claims 7-10 or the catalyst composition prepared according to the process of claim 11 or 12 for homo-or co-polymerization of ethylene.
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