CN105198922A - Phenoxy ketone coordinated transition metal organic complex and olefin polymerization catalytic system thereof as well as application of system in olefin polymerization - Google Patents

Abstract

The invention discloses a phenoxy ketone coordinated transition metal organic complex and an olefin polymerization catalytic system thereof as well as an application of the system in olefin polymerization. The catalytic system comprises (A) a transition metal organic complex in a formula (I) and (B) a main group metal organic compound, organic alkyl aluminum and an ionic compound which can be ionized. The transition metal organic complex is a complex in the formula (I), M in the formula refers to one or more of transitional metal elements in IV and V subgroups in the periodic table of the elements, m is an integer from one to three, n is a number which can meet M valence state, and X is halogen; R1 refers to a C1-20 linear chain, branched alkyl or C10-20 condensed ring aryl, and R2-R5 are same or different and are selected from hydrogen atom, halogen atom, hydrocarbyl, substitutional hydrocarbyl, alkoxy, aryloxy, hydrocarbyl silicyl, alkoxy silicyl and aryloxy silicyl. The catalytic system has high catalytic activity, good thermal stability, high copolymerization ability and the like, can catalyze olefin polymerization and copolymerization and can be used for various polymerization processes. (img file=' DDA0000808569130000011. TIF ' wi= ' 764 ' he= ' 640' /).

Description

Transition metal-organic complexes coordinated by phenoxyketone and its catalytic system for olefin polymerization and its application in olefin polymerization

technical field

The present invention relates to a novel phenoxyketone-coordinated transition metal organic complex and an olefin polymerization catalyst system in which the transition metal organic complex is the main catalyst; the present invention also relates to the application of the olefin polymerization system in olefin polymerization .

Background technique

Polyolefin is an important class of polymer materials. In recent years, the continuous updating of polyolefin products has brought revolutionary changes to people's lives and is widely used in industry, agriculture, national defense, transportation and people's daily life. The key to polyolefin technology lies in its catalyst, which is the key to regulating the structure and performance of polyolefin. Therefore, the effective molecular structure design of organic ligands and the improvement of catalyst performance occupy a core position in the field of catalyst research and development. The traditional Ziegler-Natta single titanium series catalyst is widely used in the industrial production of isotactic polypropylene, high-density polyethylene and linear low-density polyethylene, and its structure controllability and copolymerization ability are poor. Metallocene catalysts are a class of single-site catalysts whose structure can be designed and regulated. They can prepare resins that cannot be obtained with Ziegler-Natta catalysts, and meet the social demand for high-performance resins, thus occupying an increasing role in the production of polyolefins. Important position, it has been widely used in the industrial production of syndiotactic polypropylene, syndiotactic polystyrene, linear low-density polyethylene and long-chain branched polyethylene, but the molecular weight distribution of polyolefins synthesized by metallocene catalysts is narrow, The copolymerization ability is still not good enough, and it is extremely difficult to synthesize ultra-high molecular weight copolymers. For example, the effect of metallocene-catalyzed copolymerization of ethylene and styrene is not good, and the reactivity ratio of norbornene is low when catalyzing the copolymerization of ethylene and norbornene. With the requirement of polyolefin functionality and high activity of olefin polymerization catalysts, "non-cene" olefin polymerization catalysts have become the focus of attention. This type of catalyst has DuPont's post-transition metal Ni, Pd diimine catalyst system (WO9623010) and iron diimine pyridine catalyst system (WO9827124, WO9830612), Lyondell's 8-hydroxyquinoline titanium catalyst system (CN1188481A ), Sinopec Beijing Research Institute of Chemical Industry’s β-imino ketone bidentate transition metal catalyst system (CN1124287C), Mitsui Chemicals’ salicylaldimine-based transition metal catalyst system (CN1199052A), transition metal for olefin polymerization Compound catalyst (JP11199593A) and -2-hydroxybenzophenone titanium catalyst for synthesizing syndiotactic polystyrene and its preparation method (CN1473859A).

The innovation of this type of non-olefinocene polymerization catalyst lies in the use of a new multi-dentate ligand and transition metal coordination to form a transition metal organic complex main catalyst with a new structure. The types of existing multidentate ligand compounds include nitrogen-nitrogen type (such as imine ligand, polyamine ligand), nitrogen-phosphine type (imine-phosphine multidentate ligand), nitrogen-oxygen type (8-hydroxy quinoline ligands, β-iminoketone bidentate ligands, salicylaldimine ligands).

This type of non-cene catalyst has high catalytic activity, but its ability to catalyze olefin copolymerization is not strong. Therefore, it is particularly important to develop olefin polymerization catalysts with better structure controllability and stronger copolymerization ability, and to apply them to various polymerization processes.

Contents of the invention

One of the objectives of the present invention is to provide an olefin polymerization catalyst system with strong copolymerization ability.

A second object of the present invention is to provide novel oxygen-oxygen bidentate ligands, phenoxyketone-coordinated transition metal organic complexes, for use in such catalytic systems.

Another object of the present invention is to provide the application of said catalytic system in olefin polymerization.

Describe technical scheme of the present invention in detail below:

The structure of the transition metal organic complex of phenoxyketone coordination provided by the invention is as follows:

In the formula, R ₁ is a C _1-20 straight chain or branched alkyl group, a C _10-20 fused ring aryl group, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl Base, tert-butyl, pentyl, n-hexyl, cyclohexyl, naphthyl, fluorenyl, anthracenyl.

R ₂ -R ₅ are the same or different, and are selected from hydrogen atom, halogen atom, hydrocarbon group, substituted hydrocarbon group, heterocyclic compound-containing group, oxygen-containing group, silicon-containing group, nitrogen-containing group, boron-containing group, sulfur-containing group group, phosphorus-containing group (C _1-20 alkoxy group, aryloxy group, silyl group, siloxane group, alkylthio group, arylthio group, ester group, acyl group, amido group, imide group, cyano group , imine group). It is preferably selected from hydrogen atom, halogen atom, hydrocarbon group, substituted hydrocarbon group, pyrrolyl, pyridyl, quinolinyl, hydrocarbon silyl group, alkoxysilyl group, aryloxysilyl group, alkoxy group, aryloxy group, Amino. Specifically such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, n-hexyl, cyclohexyl, phenyl and substituted phenyl, naphthyl, biphenyl or terphenyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, phenoxy, trimethylsilyl, triethyl ylsilyl group, triisopropylsilyl group, triphenylsilyl group, dimethylphenylsilyl group, methyldiphenylsilyl group, tert-butyldiphenylsilyl group, tert-butyldimethylsilyl group , ethyldiphenylsilyl, trimethoxysilyl, triethoxysilyl, methylphenylmethoxysilyl, methylcyclohexylmethoxysilyl, ethylphenylmethoxysilane group, ethylcyclohexylmethoxysilyl, ethylphenylethoxysilyl, ethylcyclohexylethoxysilyl, diphenylmethoxysilyl, dicyclohexylmethoxysilyl.

M is one or several transition metal elements of subgroups III-VIII in the periodic table, preferably transition metals of subgroups IV and V, such as titanium, zirconium, hafnium, vanadium, niobium, and tantalum; Particularly preferred are titanium, zirconium, and vanadium.

X is a halogen;

m is an integer of 1-3, and n is a number satisfying the M valence.

Concrete transition metal organic complexes are as follows:

The transition metal organic complexes of the present invention can be prepared by any method without special limitation, for example, the following method is used: firstly, 2,6-dibromosubstituted phenol and trialkylchlorosilane and alkyl acid are used Methyl ester reaction prepares silyl-substituted o-hydroxybenzophenone ligands. Specifically, 2,6-dibromosubstituted phenol and trialkylchlorosilane were dissolved in a solvent and reacted at low temperature, then alkyl chloroformate was added dropwise, and the resulting solution was stirred at -78°C to room temperature for about 3 to 40 hours, the corresponding ligands can be obtained in good yields. As the solvent, those commonly used in this type of reaction can be used, preferably ethers such as diethyl ether and tetrahydrofuran, and hydrocarbon solvents such as toluene, dehydrated with molecular sieves before use. Catalysts such as triethylamine and n-butyllithium can be used in the preparation of the ligands. The ligand thus obtained is then reacted with a transition metal M-containing compound to synthesize the desired transition metal organic complex. Specifically, the ligand is dissolved in a solvent, mixed with a transition metal compound (such as a transition metal halide) at low temperature, and stirred at -78°C to room temperature or under reflux for about 3 to 120 hours. Any commonly used The solvent for this type of reaction is preferably a non-polar hydrocarbon solvent, such as toluene, and n-butyllithium can be used as a catalyst. In addition, the metal M in the synthesized transition metal organic complex can be replaced by other transition metals by conventional methods, and any one of R ₂ -R ₅ that is hydrogen can be used in any synthesis step except hydrogen Substituents are substituted.

A catalytic system for olefin polymerization, comprising the above transition metal organic complex and a cocatalyst: wherein said cocatalyst is at least one compound selected from the following compounds or a mixture thereof:

(B-1) The metal organic compound of the main group, which can be a metal organic compound of Group I, II, III, IB, IIB in the periodic table of elements, preferably a metal organic compound of Group I, II, III , such as alkylaluminum, haloalkylaluminum, alkylmagnesium, haloalkylmagnesium, alkyllithium, etc.; the molar ratio of it to the metal in the transition metal organic complex is 0.01:1-10000:1, and the preferred range is 1:1 -1000:1;

(B-2) organoaluminoxane, [-Al(R)O-]n, where R is a hydrocarbon group, preferably methyl, ethyl, propyl, butyl, most preferably methyl or ethyl; n is an integer of 5-30, preferably an integer of 10-30; the molar ratio of the organoaluminoxane to the metal M in the transition metal complex is in the range of 0.01:1-100000:1, preferably in the range of 1:1- 5000:1;

(B-3) Compounds that can react with transition metal organic complexes to form ion pairs, such as triphenylcarbon tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) lithium borate, tetrakis (pentafluorophenyl) base) lithium aluminate, the molar ratio of it to the metal in the transition metal organic complex is in the range of 0.01:1-1000:1, preferably in the range of 1:1-10:1.

When olefins are polymerized, the cocatalyst and the transition metal organic complex are added together or separately into the polymerization reactor for mixed use.

Wherein the solvent used for polymerization is selected from alkanes or aromatic hydrocarbons or halogenated hydrocarbons, preferably one of hexane, pentane, cyclohexane, benzene, toluene, xylene, methylene chloride, chloroform, and ethylene dichloride Or their mixtures, most preferably one of hexane, pentane, cyclohexane, toluene or their mixtures.

The concentration of the transition metal organic complex during polymerization is 1*10 ^-4 mol/L - 1*10 ^-1 mol/L, preferably 5*10 ^-3 mol/L - 1*10 ^-2 mol/L.

The olefin polymerization temperature is -50-200°C, preferably 0--100°C.

The olefin polymerization pressure is 0-10.0 MPa, preferably 0.1-4.0 MPa.

The transition metal organic complexes and cocatalysts described in the present invention can be loaded on the carrier simultaneously or separately, and the carrier can be inorganic materials such as silica gel, aluminum oxide, molecular sieve, magnesium oxide, magnesium chloride, or polyethylene, polystyrene, Polymer materials such as polypropylene.

The catalytic system of the present invention can be used in various polymerization methods, including gas phase polymerization and liquid phase polymerization, specifically slurry polymerization, solution polymerization, liquid phase bulk polymerization, gas phase polymerization and the like.

The catalytic system of the present invention can be used for homopolymerization and copolymerization of olefins, such as homopolymerization of ethylene, homopolymerization of propylene, and copolymerization of ethylene and α-olefin.

The beneficial effects of the present invention are: the developed novel oxygen-oxygen bidentate ligand-that is, the transition metal organic complex coordinated by phenoxyketone has both unique steric effect and flexible electronic effect. The substituent of the body and the central metal can realize the precise control of the polymerization reaction, and has the advantages of high catalytic activity, good thermal stability and strong copolymerization ability.

The present invention is further described below by examples, but the present invention is not limited by these examples. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present invention shall be included within the protection scope of the present invention.

Detailed ways

Example 1

Synthetic Ligand L1:

Add 2,6-dibromo-p-cresol (10mmol, 2.66g) and THF (10ml) into a 50mL schlenk bottle replaced with high-purity _N2 by high-temperature drying, and after cooling down to -20°C, add triethylamine (20.0 mmol, 2.78ml), followed by the addition of trimethylchlorosilane ( _Me3SiCl , 15.0mmol, 1.9ml) instantaneously. After the dropwise addition was completed, the temperature rose to room temperature within 1 h, and the reaction was continued for 3 h. Concentrate under reduced pressure, add 20ml of ether, filter, and wash the filter residue with 10ml of ether. The filtrate was concentrated to obtain 3.3 g of a transparent colorless oily liquid, namely (2,6-dibromo-4-methylphenoxy)trimethylsilane, with a yield of 97.8%.

(2,6-dibromo-4-methylphenoxy)trimethylsilane (1.5mmol, 0.507g) was added to a 50ml schlenk bottle replaced by _N2 by high temperature baking, and _Et2O (3.0ml) was added . At -60°C under good stirring conditions, TMEDA (1.8mmol, 0.27mL) was added first, then nBuLi (1.6M, ^1.8mmol , 1.13mL) was added dropwise, and the reaction was carried out at -60°C for 5h. The reaction system continued to drop to -78°C, methyl acetate (6.00 mmol, 0.48 mL) was added dropwise, and the reaction was continued to stir for 4 h. The reaction was quenched with saturated NH ₄ Cl (5.0ml), extracted with anhydrous Et ₂ O; the organic layer was washed successively with H ₂ O (2*15ml), saturated brine (25ml), dried over anhydrous MgSO ₄ , and concentrated to obtain crude product. The product L1 was separated by column chromatography.

Example 2

Synthetic Ligand L2:

2,6-dibromo-p-cresol (5mmol, 1.33g) and imidazole (5.0mmol, 0.34g) were added to a 50mlschlenk bottle replaced by _N2 after high-temperature baking, and _{CH2Cl2 (} 5ml) was added. Under the condition of stirring, the reaction system dropped to -78°C, triethylchlorosilane (20.0mmol, 3.36ml) was added instantly, the reaction system gradually rose to room temperature, and the reaction was continued for 6h. Dry the solvent in vacuo, add 100ml n-hexane and 50ml distilled water to the concentrated system, extract and separate, and wash the organic layer successively with hydrochloric acid solution (0.2N, 30ml), distilled water (30ml), saturated brine (30ml), and dry _over anhydrous MgSO , filtered to obtain a colorless oily crude product. After separation by column chromatography, (2,6-dibromo-4-methylphenoxy)triethylsilane was obtained as a colorless transparent oily liquid with a yield of 99%.

(2,6-Dibromo-4-methylphenoxy)triethylsilane (1.5mmol, 0.57g) was added to a 50ml schlenk bottle baked at high temperature and replaced with _N2 , and 3.0mlTHF was added. Under good stirring conditions at -30°C, TMEDA (1.8mmol, 0.27mL) was added first, followed by nBuLi (1.6M, ^1.8mmol , 1.13mL). After the dropwise addition, react at -30°C for 4h, the reaction system continues to drop to -78°C, add methyl acetate (6.00mmol, 0.48ml) dropwise, and continue stirring for 4h. The reaction was quenched with 5.0 ml of saturated NH ₄ Cl, extracted with 75 ml of anhydrous Et ₂ O; the organic layer was washed with H ₂ O (2*15 ml), 25 ml of saturated brine, dried over anhydrous MgSO ₄ , and concentrated to obtain a crude product. Column chromatographic separation gave the product L2.

Example 3

Synthetic Ligand L3:

2,6-dibromo-p-cresol (5mmol, 1.33g) and imidazole (5.0mmol, 0.34g) were added to a 50mlschlenk bottle replaced by _N2 after high-temperature baking, and _{CH2Cl2 (} 5ml) was added. Under the condition of stirring, the reaction system was lowered to -50°C, dimethylphenylchlorosilane (20.0 mmol) was added instantly, the reaction system was gradually raised to room temperature, and the reaction was continued for 6 hours. Dry the solvent in vacuo, add 100ml n-hexane and 50ml distilled water to the concentrated system, extract and separate, and wash the organic layer successively with hydrochloric acid solution (0.2N, 30ml), distilled water (30ml), saturated brine (30ml), and dry _over anhydrous MgSO , filtered to obtain a colorless oily crude product. After separation by column chromatography, (2,6-dibromo-4-methylphenoxy)dimethylphenylsilane was obtained as a colorless transparent liquid with a yield of 97%.

(2,6-dibromo-4-methylphenoxy)dimethylphenylsilane (1.5mmol, 0.608g) was added to a 50ml schlenk bottle baked under _N2 displacement at high temperature, and 3.0mlTHF was added. Under good stirring conditions at -30°C, TMEDA (1.8mmol, 0.27mL) was added first, followed by nBuLi (1.6M, ^1.8mmol , 1.13mL). After the dropwise addition was completed, react at -30°C for 4h, then continue to drop the reaction system to -78°C, add 6.00mmol of methyl 2-naphthoate solution dropwise, and continue stirring for 4h. The reaction was quenched with 5.0 ml of saturated NH ₄ Cl, extracted with 75 ml of anhydrous Et ₂ O; the organic layer was washed with H ₂ O (2*15 ml), 25 ml of saturated brine, dried over anhydrous MgSO ₄ , and concentrated to obtain a crude product. Column chromatography separated to obtain the product L3.

Example 4

Synthetic Ligand L4:

2,6-dibromo-p-cresol (5mmol, 1.33g) and imidazole (5.0mmol, 0.34g) were added to a 50mlschlenk bottle replaced by _N2 after high-temperature baking, and _{CH2Cl2 (} 5ml) was added. Under the condition of stirring, the reaction system was lowered to -50°C, methylphenylmethoxychlorosilane (20.0 mmol) was added instantly, the reaction system was gradually raised to room temperature, and the reaction was continued for 6 hours. Dry the solvent in vacuo, add 100ml n-hexane and 50ml distilled water to the concentrated system, extract and separate, and wash the organic layer successively with hydrochloric acid solution (0.2N, 30ml), distilled water (30ml), saturated brine (30ml), and dry _over anhydrous MgSO , filtered to obtain a colorless oily crude product. After separation by column chromatography, (2,6-dibromo-4-methylphenoxy)methylphenylmethoxysilane was obtained as a colorless transparent liquid with a yield of 97.6%.

(2,6-Dibromo-4-methylphenoxy)methylphenylmethoxysilane (1.5mmol, 0.624g) was added to a 50ml schlenk bottle baked at high temperature and replaced with _N2 , and 3.0mlTHF was added. Under good stirring conditions at -30°C, TMEDA (1.8mmol, 0.27mL) was added first, followed by nBuLi (1.6M, ^1.8mmol , 1.13mL). After the dropwise addition was completed, react at -30°C for 4h, then continue to drop the reaction system to -78°C, add 6.00mmol of methyl 2-naphthoate solution dropwise, and continue stirring for 4h. The reaction was quenched with 5.0 ml of saturated NH ₄ Cl, extracted with 75 ml of anhydrous Et ₂ O; the organic layer was washed with H ₂ O (2*15 ml), 25 ml of saturated brine, dried over anhydrous MgSO ₄ , and concentrated to obtain a crude product. Separation by column chromatography gave the product L4.

Example 5

Synthesis of transition metal organic complex C1:

Ligand L1 (1.0 mmol, 0.222 g) and 5 mL of toluene were added to a 100 ml schlenk bottle baked at high temperature and replaced with N ₂ . At -50°C and under good stirring conditions, add 0.625 mL of ⁿ -BuLi solution in n-hexane with a concentration of 1.6 mol/L dropwise within 10 min. After the dropwise addition, it was allowed to rise to room temperature naturally, and the stirring reaction was continued for 8 h to obtain a toluene solution of Ligand Li salt. At 0°C and under good stirring conditions, 0.5ml of TiCl ₄ with a concentration of 1mol/L was added dropwise, the temperature of the mixed system was gradually raised to 50°C, and the stirring reaction was continued for 16h. Dry the solvent under reduced pressure, add 20 mL of freshly distilled n-hexane, stir for 15 min, filter, and wash the filter residue with n-hexane (2*5 mL). The combined filtrates were concentrated under reduced pressure to obtain a red solid. Add 15mL ether, and stir the reaction for 30min. After filtration, the solid powder was washed with diethyl ether (2*5mL), and the solvent was dried under reduced pressure to obtain the red complex C1.

Aggregation method:

The polymerization reaction was carried out in a 500 mL reactor, and the reactor was purged with nitrogen before the polymerization reaction. Then 200 mL of hexane was added, ethylene-propylene mixed gas (ethylene/propylene molar ratio: 1/3) was introduced to make the pressure 0.1 MPa, and 20 mL of MAO with a concentration of 1.5 mmol/mL and 1 mL of MAO with a concentration of 0.01 mmol/mL were added. The toluene solution of complex C1 and 1 mL of toluene solution of triphenylcarbon tetrakis (pentafluorophenyl) borate with a concentration of 0.01 mmol/mL were reacted at 10 ° C for 40 min at 0.1 MPa to obtain 16 g of ethylene-propylene copolymer material, the activity is 50kg/gTi·h, and other data are listed in Table 1.

Example 6

Synthesis of transition metal organic complex C2:

Ligand L2 (1.0 mmol, 0.264 g) and 5 mL of toluene were added to a 100 ml schlenk bottle baked at high temperature and replaced with N ₂ . At -50°C and under good stirring conditions, add 0.625 mL of ⁿ -BuLi solution in n-hexane with a concentration of 1.6 mol/L dropwise within 10 min. After the dropwise addition, it was allowed to rise to room temperature naturally, and the stirring reaction was continued for 8 h to obtain a toluene solution of Ligand Li salt. At 0°C and under good stirring conditions, 0.5ml of TiCl ₄ solution with a concentration of 1mol/L was added dropwise, the temperature of the mixed system was gradually raised to 50°C, and the stirring reaction was continued for 16h. Dry the solvent under reduced pressure, add 20 mL of freshly distilled n-hexane, stir for 15 min, filter, and wash the filter residue with n-hexane (2*5 mL). The combined filtrates were concentrated under reduced pressure to obtain a red solid. Add 15mL ether, and stir the reaction for 30min. After filtration, the solid powder was washed with ether (2*5mL), and the solvent was dried under reduced pressure to obtain red complex C2.

Aggregation method:

The polymerization reaction was carried out in a 500 mL reactor, and the reactor was purged with nitrogen before the polymerization reaction. Then add 200mL of hexane, feed ethylene and propylene mixed gas (ethylene/propylene molar ratio: 1/3), make the pressure 0.5MPa, and add 5mL concentration of 1.5mmol/mL AlEt ₃ hexane solution and 1mL concentration of The toluene solution of 0.01mmolm/L complex C2 and the toluene solution of 1mL tetrakis(pentafluorophenyl)lithium borate with a concentration of 0.01mmol/mL were reacted at 60°C and 0.5MPa for 20min to obtain 19.1g of ethylene-propylene Copolymer, the activity is 120kg/gTi·h, and other data are listed in Table 1.

Example 7

Synthesis of transition metal organic complex C3:

Ligand L2 (1.0 mmol, 0.264 g) and 5 mL of toluene were added to a 100 ml schlenk bottle baked at high temperature and replaced with N ₂ . At -50°C and under good stirring conditions, add 0.625 mL of ⁿ -BuLi solution in n-hexane with a concentration of 1.6 mol/L dropwise within 10 min. After the dropwise addition, it was allowed to rise to room temperature naturally, and the stirring reaction was continued for 8 h to obtain a toluene solution of Ligand Li salt. At 0°C and under good stirring conditions, the above-mentioned Ligand Li salt solution was added dropwise to a solution of ZrCl ₄ (0.5mmol, 0.12g) in toluene (6mL), the temperature of the mixed system was gradually raised to 50°C, and the stirring reaction was continued 16h. Dry the solvent under reduced pressure, add 20 mL of freshly distilled n-hexane, stir for 15 min, filter, and wash the filter residue with n-hexane (2*5 mL). The combined filtrates were concentrated under reduced pressure to obtain a light yellow solid. Add 15mL ether, and stir the reaction for 30min. After filtration, the solid powder was washed with diethyl ether (2*5 mL), and the solvent was dried under reduced pressure to obtain light yellow complex C3.

Aggregation method:

The polymerization reaction was carried out in a 500 mL reactor, and the reactor was purged with nitrogen before the polymerization reaction. Then add 200mL of hexane, feed ethylene to make the pressure reach 2.0MPa, add 10mL of MAO with a concentration of 1.5mmol/mL and 1mL of toluene solution of complex C4 with a concentration of 0.01mmol/mL, and react at 40°C and 2.0MPa 30min, the polyethylene that obtains 27g, activity is 59kg/gZr h, other data are listed in table 1.

Example 8

Synthesis of transition metal organic complex C4:

Ligand L2 (1.0 mmol, 0.264 g) and 5 mL of toluene were added to a 100 ml schlenk bottle baked at high temperature and replaced with N ₂ . At -50°C and under good stirring conditions, add 0.625 mL of ⁿ -BuLi solution in n-hexane with a concentration of 1.6 mol/L dropwise within 10 min. After the dropwise addition, it was allowed to rise to room temperature naturally, and the stirring reaction was continued for 8 h to obtain a toluene solution of Ligand Li salt. At 0°C and under good stirring conditions, 0.5ml of VCl ₄ solution with a concentration of 1mol/L was added dropwise, the temperature of the mixed system was gradually raised to 50°C, and the stirring reaction was continued for 16h. Dry the solvent under reduced pressure, add 20 mL of freshly distilled n-hexane, stir for 15 min, filter, and wash the filter residue with n-hexane (2*5 mL). The combined filtrates were concentrated under reduced pressure to obtain a dark red solid. Add 15mL ether, and stir the reaction for 30min. After filtration, the solid powder was washed with diethyl ether (2*5 mL), and the solvent was dried under reduced pressure to obtain deep red complex C4.

Aggregation method:

The polymerization reaction was carried out in a 500 mL reactor, and the reactor was purged with nitrogen before the polymerization reaction. Then add 200mL of hexane, pass through propylene, heat up to make the pressure reach 3.2MPa, and add 3mL of AlEt ₃ hexane solution with a concentration of 1.5mmol/mL and 1mL of toluene solution of complex C4 with a concentration of 0.01mmol/mL, at 70 ℃, 3.2MPa and reacted for 60min to obtain 67g of polypropylene with an activity of 132kg/gV·h. Other data are listed in Table 1.

Example 9

Synthesis of transition metal organic complex C5:

Add L3 (1.0 mmol, 0.397 g) and 5 mL of toluene to a 100 ml schlenk bottle baked with N ₂ at high temperature. At -50°C and under good stirring conditions, add 0.625 mL of ⁿ -BuLi solution in n-hexane with a concentration of 1.6 mol/L dropwise within 10 min. After the dropwise addition, it was allowed to rise to room temperature naturally, and the stirring reaction was continued for 8 h to obtain a toluene solution of Ligand Li salt. At 0°C and under good stirring conditions, 0.1ml of TiCl ₄ was added dropwise, the temperature of the mixed system was gradually raised to 50°C, and the stirring reaction was continued for 16 hours. Dry the solvent under reduced pressure, add 20 mL of freshly distilled n-hexane, stir for 15 min, filter, and wash the filter residue with n-hexane (2*5 mL). The combined filtrates were concentrated under reduced pressure to obtain a red solid. Add 15mL ether, and stir the reaction for 30min. After filtration, the solid powder was washed with diethyl ether (2*5mL), and the solvent was dried under reduced pressure to obtain the red complex C5.

Aggregation method:

The polymerization reaction was carried out in a 500 mL reactor, and the reactor was purged with nitrogen before the polymerization reaction. Then add 200mL of hexane, feed a mixed gas of ethylene and propylene (ethylene/propylene molar ratio: 1/3), make the pressure reach 1.0MPa, and add 20mL of MAO with a concentration of 1.5mmol/mL and 10mL of a concentration of 0.01mmol/mL The toluene solution of the complex C5 and the toluene solution of 50mL tetrakis(pentafluorophenyl)lithium borate with a concentration of 0.01mmol/mL were reacted at 30°C and 1.0MPa for 10min to obtain 8.7g of ethylene-propylene copolymer. It is 110kg/gTi·h, and other data are listed in Table 1.

Example 10

Synthesis of transition metal organic complex C6:

Add L5 (1.0 mmol, 0.413 g) and 5 mL of toluene to a 100 ml schlenk bottle baked at high temperature and replaced with N ₂ . At -50°C and under good stirring conditions, add 0.625 mL of ⁿ -BuLi solution in n-hexane with a concentration of 1.6 mol/L dropwise within 10 min. After the dropwise addition, it was allowed to rise to room temperature naturally, and the stirring reaction was continued for 8 h to obtain a toluene solution of Ligand Li salt. At 0°C and under good stirring conditions, 0.1ml of TiCl ₄ was added dropwise, the temperature of the mixed system was gradually raised to 50°C, and the stirring reaction was continued for 16 hours. Dry the solvent under reduced pressure, add 20 mL of freshly distilled n-hexane, stir for 15 min, filter, and wash the filter residue with n-hexane (2*5 mL). The combined filtrates were concentrated under reduced pressure to obtain a red solid. Add 15mL of diethyl ether and stir the reaction for 30min. After filtration, the solid powder was washed with diethyl ether (2*5mL), and the solvent was dried under reduced pressure to obtain the red complex C6.

Aggregation method:

The polymerization reaction was carried out in a 500 mL reactor, and the reactor was purged with nitrogen before the polymerization reaction. Then add 200mL of hexane, feed a mixed gas of ethylene and propylene (ethylene/propylene molar ratio: 1/3), make the pressure reach 1.0MPa, and add 10mL of AlEt ₃ with a concentration of 1.5mmol/mL and 10mL of AlEt with a concentration of 0.01mmol/mL mL of toluene solution of complex C7 and 50mL of toluene solution of tetrakis(pentafluorophenyl)lithium borate with a concentration of 0.01mmol/mL were reacted at 10°C and 1.0MPa for 50min to obtain 34g of ethylene-propylene copolymer with active It is 85kg/gZr·h, and other data are listed in Table 1.

Table 1 olefin homopolymerization/copolymerization reaction results

Claims (10)

1. an Organotransitionmetal complex, is characterized in that, the following general structure of described Organotransitionmetal complex represents:

Wherein, R ₁for C _1-20straight or branched alkyl or C _10-20fused ring aryl, R ₂-R ₅identical or different, be selected from hydrogen atom, halogen atom, alkyl, substituted hydrocarbon radical, alkoxyl group, aryloxy, silicon alkyl alkyl, alkoxysilane group, aryloxy silane base;

M is one or more of the IVth subgroup or the Vth B transition metal element in periodictable;

X is halogen;

M is an integer of 1-3, and n is the number meeting M valence state.

2. Organotransitionmetal complex according to claim 1, is characterized in that R ₁for methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, amyl group, cyclopentadienyl, n-hexyl, cyclohexyl, naphthyl, fluorenyl, anthryl.

3. Organotransitionmetal complex according to claim 1, is characterized in that R ₂-R ₅identical or different, and be selected from hydrogen atom respectively, halogen atom, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, amyl group, n-hexyl, cyclohexyl, phenyl and substituted-phenyl, naphthyl, xenyl or terphenyl, methoxyl group, oxyethyl group, positive propoxy, isopropoxy, n-butoxy, isobutoxy, tert.-butoxy, phenoxy group, TMS, triethyl silyl, tri isopropyl silane base, tri-phenyl-silane base, dimethylphenylsilaneand base, methyldiphenyl base silane base, tert-butyldiphenylsilanyl, t-butyldimethylsilyi, ethyl diphenyl silylation, Trimethoxy silane base, triethoxysilicane alkyl, methyl phenyl methoxy silane base, methyl cyclohexane methoxylsilane base, ethylphenyl methoxy silane base, cyclohexyl methoxylsilane base ethylphenyl Ethoxysilane base, ethylcyclohexyl Ethoxysilane base, diphenylmethyl TMOS base, dicyclohexyl methoxy silane base.

4. Organotransitionmetal complex according to claim 1, is characterized in that described M is one or more in titanium, zirconium, hafnium, vanadium.

5. Organotransitionmetal complex according to claim 1, is characterized in that described X is halogen.

6. an olefin polymerization catalyst system, is characterized in that, described catalyst system comprises:

(A) general formula is the Organotransitionmetal complex of (I), and

(B) cocatalyst component, is selected from one or more in following component:

(B-1) main group metal organic compound, is selected from organoaluminum, organic-magnesium, organic zinc;

(B-2) Organoaluminoxy alkane, [-Al (R) O-] n, in formula, R is methyl, ethyl, propyl group, butyl; N is the integer of 5-30;

(B-3) compound that can be right with Organotransitionmetal complex reacting forming ion, is selected from triphenylcarbenium four (pentafluorophenyl group) borate, four (pentafluorophenyl group) lithium tetraborate, four (pentafluorophenyl group) lithium aluminate;

In formula, R ₁for C _1-20straight or branched alkyl or C _10-20fused ring aryl or silicon alkyl alkyl, R ₂-R ₅identical or different, be selected from hydrogen atom, halogen atom, alkyl, substituted hydrocarbon radical, alkoxyl group, aryloxy, silicon alkyl alkyl, alkoxysilane group, aryloxy silane base;

M is one or more of the transition metal of the IVth subgroup or the Vth subgroup or the VIIIth subgroup in periodictable;

X is halogen;

M is an integer of 1-3, and n is the number meeting M valence state.

7. catalytic systems for polymerization of olefins according to claim 6, it is characterized in that, described cocatalyst component is main group metal organic compound, and in described cocatalyst component main group metal organic compound and transition metal complex, the molar ratio range of M is 1:1-1000:1.

8. catalytic systems for polymerization of olefins according to claim 6, is characterized in that, described cocatalyst component is Organoaluminoxy alkane, and in described cocatalyst component Organoaluminoxy alkane and transition metal complex, the molar ratio range of M is 1:1-5000:1.

9. a catalyst system application in olefin polymerization, catalyst system adopts olefin polymerization catalyst system according to claim 6.

10. catalytic systems for polymerization of olefins according to claim 9 application in olefin polymerization, is characterized in that, described catalytic systems for polymerization of olefins is used for slurry polymerization, solution polymerization or mass polymerization.