CN106046208A - Silicohydroxyoxy-bridged bimetallic semimetallocene catalyst, preparation method therefor and application of silicohydroxyoxy-bridged bimetallic semimetallocene catalyst - Google Patents

Abstract

The double metallocene catalyst of siloxyl bridged and its preparation method and application belong to the field of olefin polymerization catalyst and olefin coordination polymerization, and the structure of the main catalyst of the double metallocene catalyst of siloxyl bridge conforms to the general formula (1 ): Wherein R ₁ , R ₁ ′, R ₂ , R ₂ ′, R ₃ , R ₃ ′, R ₄ , R ₄ ′, R ₅ , R ₅ ′ are the same or different substituents, independently representing hydrogen, C1 -C20 alkyl, C3-C20 cycloalkyl, C6-C20 aryl, C6-C20 halogenated aryl, C2-C20 heterocycloalkyl or C6-C20 arheteroalkyl, M ₁ or _M2 are the same or different transition metal atoms. The catalyst of the invention has low cost, high activity at a temperature of 30°C-200°C, high comonomer insertion amount, low density of olefin polymerization products and excellent performance.

Description

Silicon oxyhydroxide bridged double metallocene catalyst, preparation method and application

technical field

The invention belongs to the field of olefin polymerization catalysts and olefin coordination polymerization, and in particular relates to a double metallocene catalyst for ethylene or propylene homopolymerization, ethylene/α-olefin copolymerization or propylene/α-olefin copolymerization silicon hydroxyoxy bridging and applications.

Background technique

Metallocene catalysts have received widespread attention because of their single active center, catalyst activity, polymer stereoregularity, molecular weight, and molecular weight distribution can be controlled by changing the ligand structure; and the polymers synthesized by metallocene catalysts have excellent properties. Performance has been unanimously approved.

Polyolefin products have many advantages, such as easy processing, good thermal stability, good weather resistance, good chemical corrosion resistance and long service life, etc., and are very popular in the market. However, polyolefins (such as PE, PP, etc.) have poor low temperature resistance and high crystallinity, which limits their application range. If a certain amount of advanced α-olefin (such as 1-octene, etc.) is inserted into the polyolefin molecular chain to prepare a block copolymer, the structure and properties of the polyolefin will change significantly: the polymer density can be made higher than that of ordinary polyolefin The density is between 0.85 and 0.92g/ ^cm3 ; the glass transition temperature is low, the low temperature resistance is good, and the dispersion, weather resistance, flexibility, flexibility and processing performance are good. The performance of ethylene/1-octene copolymer is superior to that of ethylene/propylene copolymer and ethylene/1-butene copolymer, and ethylene/1-octene copolymer replaces ethylene/propylene copolymer and ethylene/1-butene The era of copolymers is coming.

Chien [Chien J, et al. Journal of Polymer Science, Part A: Polymer Chemistry, 1991, 29, 1603] adopts rac-anti-Et(Me ₄ C ₅ )(Ind)TiCl ₂ /rac-syn-Et(Me ₄ C ₅ )(Ind)TiCl ₂ Equimolar Mixture and rac-anti-Et(Me ₄ C ₅ )(Ind)TiMe ₂ Asymmetric Bridged Metallocene Catalyst Synthesis of Thermoplastic PP with Crystalline-Amorphous Stereo-Multiblock Structure elastomer. Gauthier[Gauthier WJ.Macromolecules,1995,28,3779] adopts Me ₂ C(Cp)(Ind)TiCl ₂ , Me ₂ Si(Cp)(Ind)ZrCl ₂ and Me ₂ Si(Cp)(Ind)HfCl ₂ Metal catalysts synthesized PP elastomers. _{The weight - average _ _ _} A completely amorphous PP elastomer with a relative molecular weight of 100,000 to 400,000 and good elastic and optical properties.

Patent [application number: DE 19850898] using 1-(9-fluorenyl)-1,2,3,6-tetrahydro-1,3,3-trimethylcyclopentadiene zirconium dichloride/MAO catalyst The system prepares ethylene/propylene/5-ethylidene-2-norbornene copolymer, the polymerization temperature is 20-80°C, the polymerization pressure is 0.3-3.0MPa, the mass fraction of ethylene in the copolymer is 0.4-0.9, and the mass fraction of propylene is 0.095-0.59, and the mass fraction of non-conjugated dienes is 0.005-0.12. Patent [application number: WO 2000022005] uses metallocene catalysts to synthesize EPM with high molecular weight, narrow molecular weight distribution and low T _g . The polymerization temperature is 30-80°C, the polymerization pressure is 0.07-21MPa, and the ethylene mass fraction of EPM is 0.35-0.8 , the mass fraction of propylene is 0.15-0.6.

Bergemann [Bergemann C, et al. Journal of Molecular Catalysis A: Chemical, 1996, 105, 87] used Me ₂ Si(H ₄ Ind) ₂ ZrCl ₂ /MAO to compare ethylene and propylene at 0.1-150MPa, 120-220°C , the copolymerization of 1-butene, 1-hexene and 1-decene, it is found that the higher the carbon number is, the more difficult it is to copolymerize α-olefin with ethylene, and the ratio of reactivity ratio of ethylene and 1-butene is r _e /r _b ＝53.45/0.02, the ratio of reactivity ratio when ethylene and 1-hexene are copolymerized is r _e /r _h ＝62.70/0.02, the ratio of reactivity ratio when ethylene and 1-decene is copolymerized is r _e /r _d = 80.02/0.01. Shan [Shan CL P, et al. macromolecular chemistry and physics, 2000, 201, 2195] used a supported metallocene catalyst Et(Ind) ₂ ZrCl ₂ to catalyze the copolymerization of ethylene and 1-hexene under a pressure of 10 MPa, and the catalytic activity was as high as 4341.7kg P/(mol Zr.h), the molar content of 1-hexene in the copolymer is about 3%. Losio [Losio S, etal. Macromolecules, 2008, 41, 1104] uses a bridged metallocene catalyst to catalyze the copolymerization of ethylene and 4-methyl-1-pentene, and the amount of comonomer inserted is between 0.15mol% and 5.59mol%. between.

The above research results show that despite the use of metallocene catalysts (except those with restricted geometry) and high α-olefin feed ratio, the copolymerization ability of α-olefins (above C ₄ ) and ethylene is still low.

However, the patent [Application No.: US5218071] uses an ethyl-bridged metallocene/MAO catalytic system under normal pressure to 5.0 MPa, with toluene as a solvent, to catalyze the copolymerization of ethylene and α-olefins to synthesize the polyolefin elastomer Tafmer. The molar content of α-olefin in the molecular chain of the product is high (up to 9%), the density of the product is low, which is 0.85-0.92g/cm ³ , and the molecular weight distribution is 1.2-4.0; Silicone compounds are added. Lin [Lin SA, et al. macromolecular chemistry and physics, 2001, 202, 1935] Synthesized ethylene/1-butene with high randomness and high molecular weight using monotanocene Cp*Ti(OR) ₃ /mMAO catalytic system The copolymer elastomer has a reactivity ratio of r _e /r _b = 1.08/0.29 when ethylene and 1-butene are copolymerized, and the molar content of 1-butene in the copolymer reaches 25.4%. DuPont-Dow Elastomets developed polyolefin elastomer Engage by using limited geometry metallocene catalysts, including 8 new varieties that can be blow molded and extruded, and belong to high melt strength ethylene/1-butene, Ethylene/1-hexene copolymer.

Patent 201510082857.7 discloses that a double metallocene compound is composed of a bridging C3-C30 hydrocarbon group or its derivatives, a C3-C30 cycloalkyl group or its derivatives, a C6-C30 aryl group or its derivatives, or a C6-C30 hetero The ring aryl group or its derivatives are connected to form a double metallocene catalyst, which has high catalytic activity and can effectively catalyze the homo (co)polymerization of ethylene and the homo (co)polymerization of propylene. However, patent 201510082857.7 does not involve alcohol-oxygen-bridged double metallocene catalysts.

In summary, adding organosilicon compounds, electron donors or Cp*M(OR) type ₃ metallocene catalysts to the catalyst system, metallocene catalysts (constrained geometric configuration)/MAO (or other co-catalysts) catalytic system When catalyzing the copolymerization of ethylene and C ₄ or higher α-olefins, the molar content of α-olefins in the copolymer can be significantly increased, and the density of the copolymer is low.

Although there are many reports on the use of metallocene catalysts to catalyze the copolymerization of ethylene and α-olefins, the molecular structure of metallocenes is becoming more and more complex, which is a challenge for industrial production costs. The invention discloses a double metallocene catalyst, which combines a metallocene catalyst with a simple structure and a silicon oxyhydroxide group. When catalyzing olefin polymerization at high temperature, the catalyst has high catalytic activity, and can also increase the insertion amount of comonomer α-olefin in the copolymer and improve the performance of polyolefin.

Contents of the invention

The object of the present invention is to provide a kind of double metallocene catalyst of silanoloxy bridge, and its application for ethylene homopolymerization, propylene homopolymerization, ethylene and α-olefin copolymerization or propylene and α-olefin copolymerization and preparation method.

The double metallocene catalyst of olefin polymerization siloxyl bridge bridge provided by the present invention, its structure conforms to general formula (1);

In general formula (1), R ₁ , R ₁ ′, R ₂ , R ₂ ′, R ₃ , R ₃ ′, R ₄ , R ₄ ′, R ₅ , R ₅ ′ are the same or different substituents, respectively independently represent hydrogen, C1-C20 alkyl, C3-C20 cycloalkyl, C6-C20 aryl, C6-C20 halogenated aryl, C2-C20 heterocycloalkyl or C6-C20 aryl Heteroalkyl, wherein substituents R ₁ , R ₂ , R ₃ , R ₄ , R ₅ or R ₁ ′, R ₂ ′, R ₃ ′, R ₄ ′, R ₅ ′ are closed to each other to form a single or condensed ring Or not closed; for example, the single ring is C3-C20 cycloalkane, C3-C20 heterocycloalkane or benzene ring; the fused ring is C8-C20 fused ring, such as naphthalene, pyrene;

Wherein, M ₁ and M ₂ are the same or different transition metal atoms, respectively selected from one of IIIB, IVB, VB, VIB or VIIB, preferably Ti, Zr, Hf, Sc, Y, Nd, La, Sm , Ru, Rh, Fe, Co, Ni or Pd;

Wherein, X, X' are the same or different halogen atoms selected from Cl, Br, F;

Wherein, R is a C1 _- C30 silicon-containing hydrocarbon group or its derivatives, a C3-C30 silicon-containing cycloalkyl group or its derivatives, a C6-C30 silicon-containing aryl group or its derivatives, or a C6-C30 silicon-containing aryl group or its derivatives, or a C6-C30 silicon-containing Silicon heterocyclic aryl or derivatives thereof.

In one aspect of the present invention, the double metallocene catalyst of described siloxyl bridge is preferably as follows:

Cat.1

Cat.2

Cat.3

Cat.4

Cat.5

Cat.6

Cat.7

Cat.8

Cat.9

Cat.10

Cat.11

Cat.12

Cat.13

Cat.14

Cat.15

Cat.16

Cat.17

Cat.18

Cat 19

Cat 20

The present invention also provides a catalyst for olefin polymerization, which is composed of a main catalyst and a co-catalyst, and is characterized in that the main catalyst is the aforementioned silicon oxy-hydroxy bridged double metallocene catalyst.

In one aspect of the present invention, the cocatalyst is aluminum alkyl, methylalumoxane (MAO) or modified methylalumoxane (MMAO), etc.

In yet another aspect of the present invention, the molar ratio of the main catalyst to the co-catalyst is 1:(100-5000).

The present invention provides the preparation method of the double metallocene catalyst of described general formula (1) silanoloxy bridging, it is characterized in that comprising the following steps:

1) Dissolving or dispersing the compound according to the general formula (2) in an organic solvent at 0°C to 150°C;

Among them, R ₁ , R ₂ , R ₃ , R ₄ , and R ₅ are the same or different substituents, independently representing a hydrogen atom, a C1-C20 alkyl group, a C3-C20 cycloalkyl group, and a C6-C20 aromatic group. group, C6-C20 halogenated aryl group, C1-C20 alkoxy group, C3-C20 cycloalkoxy group and C6-C20 aryloxy group, wherein substituents R ₁ , R ₂ , R ₃ , R ₄ , R ₅ are mutually closed into single ring or condensed ring or not closed; the compound meeting general formula (2a) or (2b) is preferably selected from cyclopentadiene and its derivatives, indene and its derivatives, fluorene and its derivatives thing;

Where M is a transition metal atom selected from Group IIIB, IVB, VB, VIB or VIIB, preferably Ti, Zr, Hf, Sc, Y, Nd, La, Sm, Ru, Rh, Fe, Co, Ni, Cr or Pd ; Wherein, X is a halogen atom selected from Cl, Br, F;

2) At -50°C-110°C, add a silicon-containing compound with a carbon number of C1 to C20, and react at -20°C-110°C for 0.5h-24h; remove the solvent and dry to obtain a compound having the general formula (1 )compound of.

Wherein the molar ratio of the compound conforming to the general formula (2) to the silicon-containing compound with carbon number from C1 to C30 is 1.8-2.5:1.

Wherein, the compound meeting the general formula (2) is a metallocene compound, including a single metallocene compound, a double metallocene compound, a bridged metallocene compound or a constrained geometry metallocene compound (CGC), etc., preferably as follows:

Among them, the silicon-containing compound is a C1-C30 silicon-containing dihydroxy aliphatic hydrocarbon or its derivatives, a C3-C30 silicon-containing dihydroxy cycloalkane or its derivatives, a C6-C30 silicon-containing dihydroxy aromatic compound or its derivatives Compounds or C6-C30 silicon-containing dihydroxy heterocyclic aromatic compounds or derivatives thereof, preferably as follows:

Wherein, the application of the double metallocene catalysts linked by silicon hydroxyoxy groups is characterized in that the double metallocene catalysts linked by silicon hydroxyl groups are used to catalyze homopolymerization or copolymerization of olefins, wherein the The olefins are C2-C20 olefins, preferably ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-decene, dodec-1-ene, octadec-1-ene, styrene , cyclopentene, 3-methyl-1-butene, 4-methyl-1-pentene, isoprene, 1,3-butadiene, α-methylstyrene, norbornene.

Wherein, the organic solvent is a saturated alkane with a carbon number of C5 to C30, a saturated cycloalkane with a C5 to C30, an aromatic hydrocarbon with a C6 to C30 or a mixed solvent thereof.

The double metallocene catalyst provided by the present invention is used to catalyze the polymerization of olefins. The polymerization conditions are that the polymerization temperature is 30°C-200°C, the olefin polymerization pressure is 0.1MPa-30MPa, and the polymerization reaction time is 5min- 240min.

The olefin polymerization catalyst provided by the invention has the following beneficial effects.

The double metallocene catalyst of the present invention is low in cost and still has high activity at high temperature; it is used for homopolymerization or copolymerization of ethylene, or homopolymerization or copolymerization of propylene, and has high comonomer insertion rate ; Excellent performance of polyolefin.

The present invention will be further described below in conjunction with specific embodiments, but the protection scope of the present invention is not limited to the following examples.

detailed description

Example 1

1) Preparation of the double metallocene catalyst: add 100mL of toluene to a dry reaction flask with a magnet under nitrogen protection, add 4.4g (0.02mol) of the metallocene compound 1 and stir to dissolve, add 2.16g (0.01mol) of compound 1 at 10°C ) silicon compound 1, kept at 10°C for 30 minutes, and then raised the temperature to 40°C for 3 hours. After the reaction finishes, filter, wash 4 times at 40 ℃ with normal hexane, suction filter, obtain main catalyst Cat.1:

2) Ethylene polymerization: Under anhydrous and oxygen-free conditions, add 100 mL of toluene, 10 mg of main catalyst (Cat.1), and 3.8 mL of MAO solution (1.5 mol/L) in sequence in a 250 mL reaction flask. After exchanging air three times, keep the ethylene polymerization at 120°C and 2atm for 30min, stop the reaction with ethanol solution containing 10% (volume fraction, the same below) hydrochloric acid, filter, wash with ethanol three times, and dry the polymer in vacuum at 40°C for 24h .

3) Copolymerization of ethylene: under anhydrous and oxygen-free conditions, add 100 mL of toluene, 10 mg of main catalyst (Cat.1), and 3.8 mL of MAO solution (1.5 mol/L) in sequence in a 250 mL reaction flask. After exchanging air three times, keep at 120°C, 2atm ethylene and 2atm propylene polymerize for 30min, stop the reaction with ethanol solution containing 10% hydrochloric acid, filter, wash 3 times with ethanol, and vacuum dry the polymer at 40°C for 24h.

Example 2

1) Preparation of the double metallocene catalyst: Add 100 mL of toluene to a dry reaction flask with magnets under the protection of anhydrous, oxygen and nitrogen, add 4.4 g (0.02 mol) of the metallocene compound 2 and stir to dissolve, add at 10 °C 1.20 g (0.01 mol) of silicon compound 2 was kept at 10°C for 30 minutes, and then the temperature was raised to 40°C for 3 hours. After the reaction finishes, filter, wash 4 times at 30 ℃ with normal hexane, suction filter, obtain main catalyst Cat.2:

2) Ethylene polymerization: Under anhydrous and oxygen-free conditions, add 100 mL of toluene, 10 mg of main catalyst (Cat.2), and 4.0 mL of MAO solution (1.5 mol/L) in sequence in a 250 mL reaction flask. After exchanging air three times, keep the ethylene polymerization at 160°C and 2atm for 30min, stop the reaction with ethanol solution containing 10% (volume fraction, the same below) hydrochloric acid, filter, wash with ethanol three times, and dry the polymer in vacuum at 40°C for 24h .

3) Copolymerization of ethylene: under anhydrous and oxygen-free conditions, add 100 mL of toluene, 10 mg of main catalyst (Cat.2), and 4.8 mL of MAO solution (1.5 mol/L) in sequence in a 250 mL reaction flask. After exchanging air three times, keep at 160°C, 1 atm of ethylene and 2 atm of propylene for 30 minutes, stop the reaction with ethanol solution containing 10% hydrochloric acid, filter, wash with ethanol three times, and dry the polymer in vacuum at 40°C for 24 hours.

Example 3

1) Preparation of the double metallocene catalyst: Add 100 mL of toluene to a dry reaction flask with magnets under anhydrous, oxygen-free and nitrogen protection, add 5.25 g (0.02 mol) of the metallocene compound 2 and stir to dissolve, add at 10 °C 1.66g (0.01mol) of silicon compound 3 was kept at 10°C for 30min, and then heated to 40°C for 3h. After the reaction finishes, filter, wash 4 times at 20 ℃ with normal hexane, suction filter, obtain main catalyst Cat.3:

2) Ethylene copolymerization: under anhydrous and oxygen-free conditions, add 100mL toluene, 10mg main catalyst (Cat.3), 4.5mL MAO solution (1.5mol/L), 5mL α-methylstyrene to a 250mL reaction flask in sequence . After exchanging air three times, keep the ethylene polymerization at 170°C and 2atm for 1h, stop the reaction with ethanol solution containing 10% hydrochloric acid, filter, wash with ethanol three times, and dry the polymer in vacuum at 40°C for 24h.

Example 4

1) Preparation of the double metallocene catalyst: Add 100 mL of toluene to a dry reaction flask with magnets under anhydrous, oxygen-free and nitrogen protection, add 5.25 g (0.02 mol) of the metallocene compound 2 and stir to dissolve, add at 10 °C 2.26g (0.01mol) of silicon compound 6 was kept at 10°C for 1 hour, and then the temperature was raised to 50°C for 3 hours. After the reaction finishes, filter, wash 4 times at 50 ℃ with normal hexane, suction filter, obtain main catalyst Cat.4:

2) Ethylene copolymerization: under anhydrous and oxygen-free conditions, in a 250mL reaction flask, add 100mL toluene, 10mg main catalyst (Cat.4), 6.7mL MAO solution (1.5mol/L), and 35g 1-butene in sequence. After exchanging air three times, keep the ethylene polymerization at 180°C and 2atm for 1h, stop the reaction with ethanol solution containing 10% hydrochloric acid, filter, wash with ethanol three times, and dry the polymer in vacuum at 40°C for 24h.

Example 5

3) Preparation of the double metallocene catalyst: Add 100 mL of toluene to a dry reaction flask with magnets under the protection of anhydrous, oxygen and nitrogen, add g (0.02 mol) of the metallocene compound 3 and stir to dissolve, add 2.16 g (0.01mol) of silicon compound 4 was kept at 5°C for 60 minutes, and then heated to 50°C for 3 hours. After the reaction finishes, filter, wash 5 times at 40 ℃ with normal hexane, suction filter, obtain main catalyst Cat.5:

2) Ethylene copolymerization: under anhydrous and oxygen-free conditions, add 100mL toluene, 10mg main catalyst (Cat.4), 9.7mL MAO solution (1.5mol/L), and 5mL acrylonitrile in sequence in a 250mL reaction flask. After exchanging air three times, keep ethylene polymerization at 135°C and 2atm for 60min, stop the reaction with ethanol solution containing 10% hydrochloric acid, filter, wash with ethanol three times, and dry the polymer in vacuum at 40°C for 24h.

Example 6

1) Preparation of the double metallocene catalyst: add 100mL of toluene to a dry reaction flask with a magnet under nitrogen protection, add 5.261g (0.02mol) of the metallocene compound 4 and stir to dissolve, add 2.16g (0.01mol) of compound 4 at 20°C ) silicon compound 4, kept at 20°C for 30 minutes, and then raised the temperature to 50°C for 3 hours. After the reaction finishes, filter, wash 3 times at 40 ℃ with normal hexane, suction filter, obtain main catalyst Cat.6:

2) Ethylene copolymerization: Under anhydrous and oxygen-free conditions, in a 250mL reaction flask, add 100mL toluene, 10mg main catalyst (Cat.6), 4.2mL MAO solution (1.5mol/L), and 15mL 1-hexene in sequence. After exchanging air three times, keep the ethylene polymerization at 100°C and 2atm for 1h, stop the reaction with ethanol solution containing 10% hydrochloric acid, filter, wash with ethanol three times, and dry the polymer in vacuum at 40°C for 24h.

Example 7

1) Preparation of the double metallocene catalyst: Add 100 mL of toluene to a dry reaction flask with magnets under the protection of anhydrous, oxygen and nitrogen, add 6.32 g (0.02 mol) of the metallocene compound 5 and stir to dissolve, and add 2.16g (0.01mol) of silicon compound 4 was kept at 5°C for 60 minutes, and then the temperature was raised to 50°C for 3 hours. After the reaction finishes, filter, wash 3 times at 40 ℃ with n-hexane, suction filter, obtain main catalyst Cat.7:

2) Ethylene copolymerization: under anhydrous and oxygen-free conditions, add 100mL toluene, 10mg main catalyst (Cat.7), 10mL MAO solution (1.5mol/L), and 5mL vinyl amino acid ester in a 250mL reaction flask in sequence. After exchanging air three times, keep ethylene polymerization at 80°C and 2atm for 1h, stop the reaction with ethanol solution containing 10% hydrochloric acid, filter, wash with ethanol three times, and dry the polymer in vacuum at 40°C for 24h.

Example 8

1) Preparation of the double metallocene catalyst: add 100mL of toluene to a dry reaction flask with a magnet under nitrogen protection, add 6.74g (0.02mol) of the metallocene compound 6 and stir to dissolve, add 2.16g (0.01mol) of compound 6 at 10°C ) silicon compound 4, kept at 10°C for 30 minutes, and then raised the temperature to 50°C for 3 hours. After the reaction finishes, filter, and wash 3 times at 40 ℃ with normal hexane, suction filtration, obtain main catalyst Cat.8:

2) Ethylene copolymerization: under anhydrous and oxygen-free conditions, in a 250mL reaction flask, add 100mL toluene, 10mg main catalyst (Cat.8), 7.8mL MAO solution (1.5mol/L), 5g 4-vinylbenzene formic acid. After exchanging air three times, keep the ethylene polymerization at 60°C and 3atm for 60min, stop the reaction with ethanol solution containing 10% hydrochloric acid, filter, wash with ethanol three times, and dry the polymer in vacuum at 40°C for 24h.

Example 9

1) Preparation of the double metallocene catalyst: Add 100 mL of toluene to a dry reaction flask with magnets under the protection of anhydrous, oxygen and nitrogen, add 4.33 g (0.02 mol) of the metallocene compound 7 and stir to dissolve, add at 10 °C 2.16 g (0.01 mol) of silicon compound 4 were kept at 10°C for 60 minutes, and then heated to 50°C for 3 hours. After the reaction finishes, filter, and wash 5 times at 40 ℃ with normal hexane, suction filtration, obtain main catalyst Cat.9:

2) Propylene copolymerization: under anhydrous and oxygen-free conditions, in a 250mL reaction flask, add 100mL toluene, 10mg main catalyst (Cat.9), 6.5mL MAO solution (1.5mol/L), and 25g 1-butene in sequence. After three air changes, keep the propylene polymerization at 130°C and 3atm for 30min, stop the reaction with ethanol solution containing 10% hydrochloric acid, filter, wash with ethanol three times, and dry the polymer in vacuum at 40°C for 24h.

Example 10

2) Preparation of the double metallocene catalyst: add 100mL of toluene to a dry reaction flask with a magnet under nitrogen protection, add 4.4g (0.02mol) of the metallocene compound 8 and stir to dissolve, add 2.16g (0.01mol) at 10°C ) silicon compound 4, kept at 10°C for 30 minutes, and then raised the temperature to 40°C for 4 hours. After the reaction finishes, filter, and wash 2 times at 40 ℃ with normal hexane, suction filtration, obtain main catalyst Cat.10:

3) Propylene copolymerization: under anhydrous and oxygen-free conditions, add 100mL toluene, 10mg main catalyst (Cat.10), 9.5mL MAO solution (1.5mol/L), and 15mL 1-hexene in sequence in a 250mL reaction flask. After three air changes, keep the propylene polymerization at 140°C and 2atm for 1h, terminate the reaction with ethanol solution containing 10% hydrochloric acid, filter, wash with ethanol three times, and dry the polymer in vacuum at 40°C for 24h.

Example 11

1) Preparation of the double metallocene catalyst: add 100mL of toluene to a dry reaction flask with a magnet under nitrogen protection, add 5.6g (0.02mol) of the metallocene compound 9 and stir to dissolve, add 2.16g (0.01mol) of compound 9 at 10°C ) silicon compound 5, kept at 10°C for 30 minutes, and then raised the temperature to 40°C for 4 hours. After the reaction finishes, filter, and wash 3 times at 40 ℃ with normal hexane, suction filtration, obtain main catalyst Cat.11:

2) Propylene copolymerization: under anhydrous and oxygen-free conditions, in a 250mL reaction flask, add 100mL toluene, 10mg main catalyst (Cat.11), 8.3mL MAO solution (1.5mol/L), and 15mL 1-octene in sequence. After three air changes, keep the propylene polymerization at 150°C and 3 atm for 1 hour, stop the reaction with ethanol solution containing 10% hydrochloric acid, filter, wash with ethanol three times, and dry the polymer in vacuum at 40°C for 24 hours.

Example 12

1) Preparation of the double metallocene catalyst: Add 100 mL of toluene to a dry reaction flask with magnets under the protection of anhydrous, oxygen and nitrogen, add 6.39 g (0.02 mol) of the metallocene compound 10 and stir to dissolve, and add 2.16 g (0.01 mol) of silicon compound 4 were kept at 10°C for 60 minutes, and then heated to 50°C for 3 hours. After the reaction finishes, filter, and wash 3 times at 40 ℃ with normal hexane, suction filtration, obtain main catalyst Cat.12:

2) Propylene copolymerization: under anhydrous and oxygen-free conditions, in a 250mL reaction flask, add 100mL toluene, 10mg main catalyst (Cat.12), 7.6mL MAO solution (1.5mol/L), 5mL 4-cyanobenzene vinyl. After three air changes, keep the propylene polymerization at 50°C and 2atm for 30min, stop the reaction with ethanol solution containing 10% hydrochloric acid, filter, wash with ethanol three times, and dry the polymer in vacuum at 40°C for 24h.

Example 13

1) Preparation of the double metallocene catalyst: Add 100 mL of toluene to a dry reaction flask with magnets under the protection of anhydrous, oxygen and nitrogen, add 9.62 g (0.02 mol) of the metallocene compound 11 and stir to dissolve, and add 2.16g (0.01mol) of silicon compound 4 was kept at 20°C for 1 hour, and then the temperature was raised to 50°C for 3 hours. After the reaction finishes, filter, and wash 3 times at 40 ℃ with normal hexane, suction filtration, obtain main catalyst Cat.13:

2) Propylene copolymerization: under anhydrous and oxygen-free conditions, in a 250mL reaction flask, add 100mL of toluene, 10mg of main catalyst (Cat.13), 5.6mL of MAO solution (1.5mol/L), and 15mL of methyl acrylate. After exchanging air three times, polymerize propylene and ethylene at 3 atm at 60°C for 1 hour, stop the reaction with ethanol solution containing 10% hydrochloric acid, filter, wash with ethanol three times, and dry the polymer in vacuum at 40°C for 24 hours.

Example 14

1) Preparation of the double metallocene catalyst: add 100mL of toluene to a dry reaction flask with a magnet under nitrogen protection, add 9.44g (0.02mol) of the metallocene compound 12 and stir to dissolve, add 2.16g (0.01mol) of compound 12 at 20°C ) silicon compound 4, kept at 20°C for 30 minutes, and then raised the temperature to 50°C for 3 hours. After the reaction finishes, filter, and wash 3 times at 40 ℃ with normal hexane, suction filtration, obtain main catalyst Cat.14:

2) Propylene copolymerization: under anhydrous and oxygen-free conditions, in a 250mL reaction flask, add 100mL of toluene, 10mg of main catalyst (Cat.14), 9.3mL of MAO solution (1.5mol/L), and 5mL of cyclopentene. After three times of gas exchange, keep at 120°C, 3atm propylene and 4atm ethylene to polymerize for 1h, stop the reaction with ethanol solution containing 10% hydrochloric acid, filter, wash with ethanol three times, and dry the polymer in vacuum at 40°C for 24h.

Example 15

1) Preparation of the double metallocene catalyst: Add 100 mL of toluene to a dry reaction flask with magnets under the protection of anhydrous, oxygen and nitrogen, add 5.46 g (0.02 mol) of the metallocene compound 13 and stir to dissolve, and add 2.26g (0.01mol) of silicon compound 6 was kept at 30°C for 1 hour, and then the temperature was raised to 50°C for 3 hours. After the reaction finishes, filter, and wash 2 times at 40 ℃ with normal hexane, suction filtration, obtain main catalyst Cat.15:

2) Propylene copolymerization: under anhydrous and oxygen-free conditions, in a 250mL reaction flask, add 100mL toluene, 10mg main catalyst (Cat.15), 8.5mL MAO solution (1.5mol/L), 8g 2-hydroxymethyl - 10-Vinyl-decyl alcohol. After three air changes, propylene and 2atm ethylene were polymerized at 80°C and 2atm for 1h, and the reaction was terminated with ethanol solution containing 10% hydrochloric acid, filtered, washed with ethanol three times, and the polymer was vacuum-dried at 40°C for 24h.

Example 16

1) Preparation of the double metallocene catalyst: Add 100 mL of toluene to a dry reaction flask with magnets under the protection of anhydrous, oxygen and nitrogen, add 7.30 g (0.02 mol) of the metallocene compound 14 and stir to dissolve, and add 2.26g (0.01mol) of silicon compound 6 was kept at 30°C for 1 hour, and then the temperature was raised to 50°C for 3 hours. After the reaction finishes, filter, and wash 2 times at 40 ℃ with hexanaphthene, suction filtration, obtain main catalyst Cat.16:

2) Propylene copolymerization: Under anhydrous and oxygen-free conditions, in a 250mL reaction flask, add 100mL toluene, 10mg main catalyst (Cat.16), 9.3mL MAO solution (1.5mol/L), 15mL 8-chloro-1- Octene. After three times of air exchange, keep at 120°C, 2atm propylene and 3atm ethylene for 30min, stop the reaction with ethanol solution containing 10% hydrochloric acid, filter, wash with ethanol three times, and dry the polymer in vacuum at 40°C for 24h.

Example 17

1) Preparation of the double metallocene catalyst: add 100mL of toluene to a dry reaction flask with a magnet under nitrogen protection, add 7.30g (0.02mol) of the metallocene compound 14 and stir to dissolve, add 2.26g (0.01mol) of compound 14 at 20°C ) silicon compound 6, kept at 30°C for 30 minutes, and then raised the temperature to 50°C for 3 hours. After the reaction finishes, filter, and wash 3 times at 40 ℃ with heptane, suction filtration, obtain main catalyst Cat.17:

2) Copolymerization of ethylene: under anhydrous and oxygen-free conditions, add 100mL toluene, 10mg main catalyst (Cat.17), 8.2mL MAO solution (1.5mol/L), and 15mL norbornene to a 250mL reaction flask in sequence. After exchanging air three times, keep at 100°C, 2atm ethylene and 3atm propylene to polymerize for 1h, stop the reaction with ethanol solution containing 10% hydrochloric acid, filter, wash with ethanol 3 times, and dry the polymer in vacuum at 40°C for 24h.

Example 18

1) Preparation of the double metallocene catalyst: Add 100 mL of toluene to a dry reaction flask with magnets under the protection of anhydrous, oxygen and nitrogen, add 4.78 g (0.02 mol) of the metallocene compound 15 and stir to dissolve, and add 2.26 g (0.01 mol) of silicon compound 6 was kept at 30°C for 1 hour; then the temperature was raised to 10°C for 3 hours. After the reaction finishes, filter, and wash 3 times at 40 ℃ with toluene, suction filtration, obtain main catalyst Cat.18:

2) Ethylene copolymerization: under anhydrous and oxygen-free conditions, in a 250mL reaction flask, add 100mL toluene, 10mg main catalyst (Cat.18), 7.8mL MAO solution (1.5mol/L), 5mL 10-enoic acid methyl ester, 20 mL 1-hexene. After exchanging air three times, keep at 170°C, 3atm ethylene and 3atm propylene to polymerize for 1h, stop the reaction with ethanol solution containing 10% hydrochloric acid, filter, wash with ethanol three times, and dry the polymer in vacuum at 40°C for 24h.

Example 19

1) Preparation of the double metallocene catalyst: add 100mL of toluene to a dry reaction flask with magnets under the protection of anhydrous, oxygen and nitrogen, add 4.78g (0.02mol) of the metallocene compound 15 and stir to dissolve, add at 20°C 4.14g of silicon compound 7 was kept at 20°C for 1 hour; then the temperature was raised to 40°C for 4 hours. After the reaction finishes, filter, and wash 3 times at 40 ℃ with toluene, suction filtration, obtain main catalyst Cat.19:

2) Copolymerization of ethylene: under anhydrous and oxygen-free conditions, add 100mL toluene, 10mg main catalyst (Cat.19), 8.8mL MAO solution (1.5mol/L), and 5mL isoprene to a 250mL reaction flask in sequence. After three times of gas exchange, keep at 130°C, 3atm ethylene and 4atm propylene to polymerize for 1h, stop the reaction with ethanol solution containing 10% hydrochloric acid, filter, wash with ethanol 3 times, and dry the polymer at 40°C for 24h in vacuum.

Example 20

1) Preparation of the double metallocene catalyst: Add 100 mL of toluene to a dry reaction flask with magnets under the protection of anhydrous, oxygen and nitrogen, add 0.02 mol of the metacene compound 16 and 0.02 mol of the metacene compound 17, stir to dissolve, 30 4.14 g of silicon compound 6 was added at ℃, and kept at 30°C for 1 hour; then the temperature was raised to 50°C for 4 hours. After the reaction finishes, filter, and wash 4 times at 30 ℃ with toluene, suction filtration, obtain main catalyst Cat.20:

2) Ethylene copolymerization: under anhydrous and oxygen-free conditions, add 100mL toluene, 10mg main catalyst (Cat.19), 8.8mL MAO solution (1.5mol/L), and 10mL styrene in sequence in a 250mL reaction flask. After three times of gas exchange, keep at 130°C, 3atm ethylene and 4atm propylene to polymerize for 1h, stop the reaction with ethanol solution containing 10% hydrochloric acid, filter, wash with ethanol 3 times, and dry the polymer at 40°C for 24h in vacuum.

The results of the polymerization reaction are shown in Table 1.

Table 1:

Claims (9)

1. bimetallic half cyclopentadienyl catalyst of silicon hydroxyl epoxide bridging, is made up of major catalyst and promoter；It is characterized in that, described The structure of major catalyst meet formula (1):

Formula (1)

In formula (1), R₁、R₁＇, R₂、R₂＇, R₃、R₃＇, R₄、R₄＇, R₅、R₅＇ is identical or different substituent group, independently earth's surface Show the heterocycle alkane of hydrogen, the alkyl of C1-C20, the cycloalkyl of C3-C20, the aryl of C6-C20, the halogenated aryl of C6-C20, C2-C20 The miscellaneous alkyl of virtue of base or C6-C20, wherein substituent R₁、R₂、R₃、R₄、R₅Or R₁＇, R₂＇, R₃＇, R₄＇, R₅＇ is closed into list each other Ring or condensed ring or do not close；M₁Or M₂It is identical or different transition metal atoms, is respectively selected from III B, IV B, VB, VIB or VIII In one；Wherein, X or X ' is identical or different halogen atom, selected from Cl, Br, F；Wherein, R₆Hydrocarbyl silyl for C1-C30 Or derivatives thereof, the siliceous cycloalkyl or derivatives thereof of C3-C30, the siliceous aryl or derivatives thereof of C6-C30, or C6-C30's Siliceous heterocyclic aryl or derivatives thereof.

Catalyst the most according to claim 1, it is characterised in that: described promoter is alkyl aluminum, aluminum alkoxide；Main Catalyst is 1:(100-5000 with the mol ratio of promoter).

3. the method preparing catalyst as claimed in claim 1, it is characterised in that the method meeting the major catalyst of formula (1), Comprise the following steps:

1) at 0 DEG C to 150 DEG C, the compound dissolution of formula (2) will be met or be scattered in organic solvent；

Formula (2)

Wherein, R₁、R₂、R₃、R₄、R₅It is identical or different substituent group, independently represents hydrogen atom, the alkyl of C1-C20, C3- The cycloalkyl of C20, the aryl of C6-C20, the halogenated aryl of C6-C20, the alkoxyl of C1-C20, the cycloalkyloxy of C3-C20 and The aryloxy group of C6-C20, wherein substituent R₁、R₂、R₃、R₄、R₅It is closed into monocycle or condensed ring each other or does not closes；

2) adding carbon number is the silicon-containing compound of C1 to C30, at-50 DEG C to 110 DEG C, reacts 0.5h-24h；Remove molten Be dried to obtain after agent and there is the compound meeting formula (1): wherein meet the compound of formula (2) and carbon number be C1 extremely The mol ratio of the silicon-containing compound of C30 is 1.8-2.5:1.

Method the most according to claim 3, it is characterised in that: described organic solvent be carbon number be the full of C5 to C30 With alkane, the saturated rings alkane of C5 to C30, the aromatic hydrocarbons of C6 to C30 or their mixed solvent.

Method the most according to claim 3, it is characterised in that: the compound meeting formula (2) is metallocene compound, bag Include mono-metallocene compound, dicyclopentadiene metallic compound, bridged combined metal compound or limit geometric type metallocene compound.

Method the most according to claim 3, it is characterised in that: silicon-containing compound is the siliceous dihydroxy fat of C1-C30 Hydrocarbon or derivatives thereof, the siliceous dihydroxy cycloalkane or derivatives thereof of C3-C30, the siliceous dihydroxy aromatic chemical combination of C6-C30 Thing or derivatives thereof, or the siliceous dihydroxy heterocyclic aromatic compound or derivatives thereof of C6-C30.

Major catalyst the most according to claim 1, it is characterised in that: the M in formula (1)₁Or M₂For Ti, Zr, Hf, Sc, Y, Nd, La, Sm, Ru, Rh, Fe, Co, Ni or Pd.

8. the application of the catalyst described in, it is characterised in that: catalysis nonpolar olefinic is all polymerized or combined polymerization；Wherein said is non- Polar olefin is the alkene of C2 C30.

Application the most according to claim 8, it is characterised in that described polymerizing condition is: polymerization temperature is 30 DEG C-200 DEG C, olefinic polymerization pressure is 0.1MPa-30MPa, and polymerization reaction time is 5min-300min.