CN101357958B - Supported vanadium oxide non-metallocene catalyst for polyethylene and preparation method - Google Patents

Abstract

The invention provides a load-type non-metallocene polyethylene catalyzer in vanadium series, which comprises a magnesium chloride bearer, an aluminium alkyl compound and a non-metallocene complex in vanadium series having the formula (I), (II) or (III); vanadium accounts for 3.0 to 8.0 percent by mass in the catalyzer; magnesium accounts for 10 to 25.0 percent by mass; aluminium accounts for 0.5to 3.0 percent by mass. In the formulae (I) and (II), R1 is an alkyl selected from C1 to C6; R2 and R3 are an alkyl selected from H and C1 to C6, and an alkoxy or a nitryl selected from C1 to C6 respectively. In the formula (III), R4 and R5 are an alkyl selected from C1 to C12 and an aralkyl selected from C6 to C9 or a perfluoroalkyl selected from C1 to C12. In the formulae (I) to (III), X is a halogen and n is 1 or 2. The catalyzer is applied for polyreaction of Ethylene, which has high activity. The prepared polyethylene is in good particle shape and has high bulk density.

Description

A kind of supported vanadium series non-metallocene polyethylene catalyst and its preparation method

technical field

The invention relates to a supported vanadium-based non-metallocene polyethylene catalyst and a preparation method thereof, specifically, a vanadium-based metal active component loaded with acyl naphthol derivatives or β-diketone derivative ligands Polyethylene catalyst and preparation method thereof.

Background technique

After the typical transition metal compounds with cyclopentadiene and its derivatives as ligands, that is, metallocene catalysts, were successfully used in the industrial production of polyolefins, a transition metal compound containing heteroatoms such as oxygen and nitrogen in the ligand, That is, non-metallocene polyolefin catalysts have been developed rapidly.

Among these non-metallocene catalysts, there are more researches on catalysts centered on transition metals of Group IVB and Group VIII complexes, but relatively few studies on catalysts centered on transition metals of Group VB, and their ethylene polymerization Catalytic activity is mostly low.

Michael CWChan et al. (Chem.Commun., 1998, 1673~1674) reported the reaction of tert-butylimino vanacene complex (CpV(N- ^tBu )Cl ₂ ) with styrene-4-aminostyrene copolymer The latter formed supported imino vanadium complex catalyst. When the catalyst uses diethylaluminum chloride as a cocatalyst, its ethylene polymerization rate is more than ten times that of the unsupported catalyst, and the polymerization reaction is carried out under the conditions of Al/V molar ratio of 34, 50°C and 1.0 MPa for 1 hour, and the catalytic activity 7.72×10 ⁴ gPE·(molV) ^-1 ·hr ^-1 , the resulting polyethylene has a high molecular weight (M _w =1.9×10 ⁶ ), a molecular weight distribution (Mw/Mn) of 4.9, few branches, and 5000 carbon There are less than 1 branches.

Most of the supported vanadium catalysts disclosed in the patent are vanadium(III) acetylacetonate for ethylene-propylene copolymerization or VOCl ₃ , VCl ₄ , VCl ₃ and their complexes with tetrahydrofuran for olefin polymerization. As CN1133301A discloses a kind of supported catalyst for ethylene-propylene copolymerization. The catalyst is impregnated with silica gel with hydrocarbon solution of vanadium acetylacetonate, treated with diethylaluminum chloride after removing the solvent, and then dried. The catalyst is combined with diethylaluminum chloride as a cocatalyst, and organic matter containing chlorine, such as ethyl trichloroacetate, as an activator, and is used for ethylene-propylene copolymerization to obtain ethylene-propylene elastomer with low crystallinity and good shape.

Disclosed in US4579833 is a kind of preparation method that is used for the catalyst of the supported vanadium compound of ethylene homopolymerization or copolymerization, the used magnesium chloride support of this method is made by dialkylmagnesium, such as butyl octylmagnesium and tert-butyl chloride reaction, The electron donor diisoamyl ether is introduced during the reaction, and the active component vanadium compound used is VCl ₄ or VOCl ₃ . The valence state of the loaded vanadium compound is lower than the original four or five valence, that is, it exists in the reduced valence state. The catalyst can catalyze ethylene polymerization under the action of alkyl aluminum, such as tri-n-octyl aluminum co-catalyst, to obtain polyethylene products with uniform particle size distribution.

CN1887919A discloses an in-situ synthesized supported vanadium-based non-ocene polyolefin catalyst. The catalyst uses acyl naphthol chloride or β-diketone chloride as the active component, and the carrier is magnesium chloride. The carrier magnesium chloride is produced by the reaction of acyl naphthol chloride or dialkylmagnesium in the β-diketone solution with _VCl4 during the catalyst synthesis process, that is, the carrier magnesium chloride is produced while forming the vanadium complex. The catalyst is matched with a monochlorodiethylaluminum cocatalyst and is used for ethylene polymerization, but the catalytic activity is still low, and the molecular weight of the prepared polymer is also low.

CN00124667.4 discloses an ethylene polymerization catalyst prepared by loading the active component of a semi-metallocene catalyst containing a β-diketone derivative ligand on an inorganic chloride and its preparation method. The particle shape of the catalyst is not good, and there is a saturation value when the active component is loaded, resulting in a limited loading capacity, the prepared supported catalyst has a low titanium loading, the polymerization efficiency per unit mass of the catalyst is not high, and the obtained polymer has a low bulk density. , the shape is not good.

Contents of the invention

The purpose of the present invention is to provide a supported vanadium-based non-metallocene polyethylene catalyst and its preparation method. The catalyst has high catalytic activity and the particle shape of the obtained polymer is good.

The supported vanadium-based non-metallocene polyethylene catalyst provided by the invention comprises a magnesium chloride carrier, an alkyl aluminum compound and a vanadium-based non-metallocene complex having formula (I), (II) or (III), in which The vanadium content is 3.0-8.0% by mass, the magnesium content is 10-25.0% by mass, and the aluminum content is 0.5-3.0% by mass;

In the formulas (I) and (II), R ¹ is selected from C ₁ -C ₆ alkyl, R ² and R ³ are respectively selected from hydrogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ Alkoxy or nitro; in formula (III), R ⁴ and R ⁵ are respectively selected from C ₁ -C ₁₂ alkyl, C ₆ -C ₉ aralkyl or C ₁ -C ₁₂ perfluoroalkyl; In formulas (I) to (III), X is halogen, and n is 1 or 2.

The catalyst provided by the invention uses alcoholate and alkylaluminum to activate the carrier, and then supports the vanadium-based non-metallocene active components. The prepared catalyst has better fluidity and strength, and higher loading capacity of vanadium. The catalyst is used in ethylene polymerization, has good catalytic activity, good copolymerization performance and hydrogen adjustment sensitivity, and can obtain polymers with wide molecular weight distribution in the presence of hydrogen, and the molecular weight distribution of polymers can be adjusted by changing the amount of hydrogen. The obtained polymer particles have good morphology and high bulk density.

Detailed ways

The catalyst of the invention introduces vanadium-based non-metallocene active components and alkylaluminum into the magnesium chloride carrier, and the introduction of the alkylaluminum significantly improves the activity of the catalyst. The preparation of the catalyst of the present invention suspends magnesium chloride in an inert hydrocarbon solvent, activates it after contacting with Ti(OR) ₄ and ROH to obtain a magnesium chloride-alcohol carrier, and then treats the magnesium chloride-alcohol carrier with aluminum alkyl, and then The vanadium-based non-metallocene complex is supported to prepare a supported vanadium-based non-metallocene catalyst. The amount of alcohol used to activate magnesium chloride is less in the method, and the magnesium chloride is always in a solid state during the treatment process, so the carrier after activation can have a good shape, and the prepared supported catalyst also has a good particle shape. The bulk density of the polymer is thus significantly increased.

The structural formulas of the active components in the catalyst provided by the present invention are shown in formulas (I) to (III), wherein the ligands of (I) and (II) are derivatives of acyl naphthols, and R ¹ is preferably C ₁ to C ₃ alkyl, more preferably methyl; R ² and R ³ may be the same or different, and are groups on the naphthol benzene ring, preferably hydrogen, C ₁ to C ₃ alkoxy, or nitro, more preferably hydrogen.

The ligand of formula (III) is a derivative of β-diketone, wherein R ⁴ and R ⁵ are respectively preferably C ₁ -C ₃ alkyl, phenyl or C ₁ -C ₃ perfluoroalkyl, more Methyl or phenyl is preferred.

In the formulas (I) to (III), X is preferably chlorine.

Preferred formula (I) compound among the present invention has: (2-acetyl-1-naphthol)-vanadium trichloride, (4-methoxy-2-acetyl-1-naphthol)-trichloro Vanadium, (4-nitro-2-acetyl-1-naphthol)-vanadium trichloride, (8-methoxy-2-acetyl-1-naphthol)-vanadium trichloride, (8 -Nitro-2-acetyl-1-naphthol)-vanadium trichloride, bis(2-acetyl-1-naphthol)-vanadium dichloride, bis(4-methoxy-2-acetyl -1-naphthol)-vanadium dichloride, bis(4-nitro-2-acetyl-1-naphthol)-vanadium dichloride, bis(8-methoxy-2-acetyl-1- Naphthol)-vanadium dichloride or bis(8-nitro-2-acetyl-1-naphthol)-vanadium dichloride.

More preferred formula (II) compound has: (1-acetyl-2-naphthol)-vanadium trichloride, (4-methoxy-1-acetyl-2-naphthol)-vanadium trichloride, (4-Nitro-1-acetyl-2-naphthol)-vanadium trichloride, (8-methoxy-1-acetyl-2-naphthol)-vanadium trichloride, (8-nitro -1-acetyl-2-naphthol)-vanadium trichloride, bis(1-acetyl-2-naphthol)-vanadium dichloride, bis(4-methoxy-1-acetyl-2- Naphthol)-vanadium dichloride, bis(4-nitro-1-acetyl-2-naphthol)-vanadium dichloride, bis(8-methoxy-1-acetyl-2-naphthol) - vanadium dichloride or bis(8-nitro-1-acetyl-2-naphthol)-vanadium dichloride.

More preferred formula (III) compound has: (acetylacetone)-vanadium trichloride, (dibenzoylmethane)-vanadium trichloride, (hexafluoroacetylacetonate)-vanadium trichloride, two (acetylacetonate) - vanadium dichloride, bis(dibenzoylmethane)-vanadium dichloride or bis(hexafluoroacetylacetonate)-vanadium dichloride.

The compound of more preferred formula (I)～(III) has: (2-acetyl-1-naphthol)-vanadium trichloride, two (2-acetyl-1-naphthol)-vanadium dichloride , (1-acetyl-2-naphthol)-vanadium trichloride, bis(1-acetyl-2-naphthol)-vanadium dichloride, (dibenzoylmethane)-vanadium trichloride, di (Dibenzoylmethane)-vanadium dichloride, (acetylacetonate)-vanadium trichloride or bis(acetylacetonate)-vanadium dichloride.

In the catalyst of the present invention, the vanadium content is preferably 3.0-5.0 mass%, the magnesium content is preferably 10-20.0 mass%, and the aluminum content is preferably 0.8-2.0 mass%.

The preparation method of catalyst of the present invention comprises the steps:

(1) Suspend the magnesium chloride carrier in an inert hydrocarbon solvent, fully contact and react with Ti(OR) ₄ and C ₂ -C ₈ aliphatic alcohol at 30-80°C, and then dry the solid, the Ti(OR) ₄ The molar ratio to magnesium chloride is 0.01 to 0.2, the molar ratio of fatty alcohol to magnesium chloride is 0.1 to 1.0, and R in the formula Ti(OR) ₄ is selected from C ₁ to C ₇ alkyl groups;

(2) treating the dried carrier obtained in step (1) with an aluminum alkyl in the presence of an inert hydrocarbon solvent, and then drying, the molar ratio of the aluminum alkyl to magnesium chloride is 0.1 to 10;

(3) In the presence of a polar organic solvent, fully contact the carrier after step (2) drying with the vanadium-based non-metallocene complex having formula (I), (II) or (III), and collect the solid dry.

The step (1) of the method is the activation treatment step of the magnesium chloride carrier, suspending the magnesium chloride in an inert hydrocarbon, reacting with Ti(OR) ₄ and alcohol, preferably adding Ti(OR) ₄ to the magnesium chloride suspension to carry out Reaction, then add alcohol to carry out the reaction. The magnesium chloride can be new ecological magnesium chloride or anhydrous magnesium chloride. The Ti(OR) ₄ is preferably tetrabutoxytitanium, tetraethoxytitanium or tetrapropoxytitanium, and the molar ratio of Ti(OR) ₄ to magnesium chloride is preferably 0.01-0.1. The new eco-magnesium chloride is prepared by reacting Grignard reagent with halogenated alkane, and the preferred halogenated alkane is carbon tetrachloride.

(1) The suitable mass ratio of the inert hydrocarbon solvent described in the step and magnesium chloride is 5-100, preferably 5-20. The fatty alcohol is preferably ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, hexanol, heptanol, octanol or isooctyl alcohol.

The step (2) of the method of the present invention is to treat the carrier with an aluminum alkyl, and the aluminum alkyl is preferably diethylaluminum monochloride, triethylaluminum or triisobutylaluminum. The molar ratio of the alkylaluminum to magnesium chloride is preferably 0.1-3.0, and the temperature for treating the carrier with the alkylaluminum is -20-20°C, preferably -10-10°C.

The inert hydrocarbon solvent described in the method of the present invention is preferably a C ₅ -C ₁₀ alkane, more preferably hexane, decane, heptane or octane.

The step (3) of the method is to support the vanadium-based amphenocene complex, and the polar organic solvent is preferably toluene. The reaction temperature of the carrier and the vanadium-based non-acene complex is 10-50°C, preferably 20-40°C. During the loading process, the amount of the vanadium-based non-phenocene complex added should be such that the molar ratio of magnesium chloride to the vanadium-based non-phenocene complex is 5-500, preferably 5-50.

The preparation method of the vanadium series non-phenocene complex provided by the invention comprises the following steps:

(1) VX ₄ and acyl naphthol or β-diketone compound are dissolved with organic solvent respectively to make an organic solution of VX ₄ and acyl naphthol or β-diketone, X is a halogen in VX ₄ ,

(2) Drop the organic solution of acyl naphthol or β-diketone into the organic solution of VX ₄ at -78-0°C, fully react at 0-30°C, filter, wash, and dry the solid.

The above method (1) step is to prepare the ligand solution and the tetravalent vanadium halide solution for the reaction, the temperature of dissolving VX ₄ in the organic solvent is -78～0°C, and dissolving the acyl naphthol or β-diketone in the organic solvent The temperature of the solvent is 0 to 30°C. The structural formula of described acyl naphthol compound or β-diketone compound is as follows:

Wherein R ¹ , R ² and R ³ in formulas (1) and (2) are the same as formulas (I) and (II), and R ⁴ and R ⁵ in formula (3) are the same as formula (III).

The step (2) of the above method is to react the prepared two solutions according to a certain solute molar ratio, so as to prepare the vanadium-based amphenocene complex of the present invention. After the two solutions have reacted, the solid matter is washed and dried to obtain the catalyst. The dried solid matter can be washed or recrystallized to further improve the purity of the catalyst.

The organic solvent in the method and the solvent for washing or recrystallization are preferably C ₆ to C ₁₀ alkanes, halogenated alkanes, C ₆ to C ₈ aromatics or ethers, more preferably hexane, methylene chloride, toluene, ether or Tetrahydrofuran.

When intending to prepare single-ligand compounds, i.e. (I)～(III) when n is a compound of 1, the organic solvent used in (1) step is preferably _C6 ～ _C10 alkane, (2) step _VX4 and acyl The molar ratio of naphthol or β-diketone is 1-4:1, preferably 2:1. When it is desired to prepare a double-ligand compound, that is, a compound in which n is 2 in formulas (I) to (III), the organic solvent used in step (1) is preferably C ₆ -C ₈ aromatic hydrocarbons, ethers, C ₆ -C ₁₀ Alkane or haloalkane, (2) The molar ratio of step VX ₄ to acyl naphthol or β-diketone is 1:2.

The supported vanadium-based non-metallocene catalyst prepared by the invention is suitable for the homopolymerization of ethylene or the copolymerization of ethylene and α-olefin. During the polymerization, aluminoxane or alkylaluminum needs to be added as a cocatalyst, and the polymerization temperature is 10-100°C , preferably at 30-80°C, and at a pressure of 0.1-1.0 MPa. Polymerization can be carried out by bulk, slurry or gas phase fluidized bed processes. During the polymerization reaction, the molar ratio of aluminum in the cocatalyst to vanadium in the main catalyst, that is, the Al/V molar ratio, is 25-1000, preferably 100-500.

The cocatalyst aluminum alkyl is preferably triethylaluminum, triisobutylaluminum, diethylaluminum monochloride or mixtures thereof.

The present invention will be described in detail below by examples, but the present invention is not limited thereto.

Example 1

Preparation of new ecological magnesium chloride.

At 25°C, 20 ml of n-butyl ether and 0.49 g of iodine were added to 4.93 g of magnesium powder. The temperature was raised to 80° C., and 5.1 ml of n-chlorobutane was added to initiate the reaction, forming a suspended gray cloudy liquid. Then, a mixed solution of 20 milliliters of n-chlorobutane, 30 milliliters of butyl ether and 50 milliliters of heptane was added dropwise to the gray cloudy liquid, reacted for 30 minutes, and gradually cooled to 0°C. Filter to obtain iron gray filter cake and golden yellow filtrate. The obtained golden yellow filtrate is Grignard reagent.

40 ml of carbon tetrachloride was added dropwise to the above golden yellow filtrate at 0°C. After the dropwise addition was completed, the temperature was gradually raised to 80° C., and the reaction was carried out for 3 hours. Decrease to 25°C and let stand overnight. The temperature was raised to 80° C. again, filtered, and the filter cake was washed with 20 ml of butyl ether and 100 ml of hexane. The filter cake is dried under reduced pressure to obtain 14.68 grams of milky white fresh ecological magnesium chloride powder with good fluidity.

Example 2

Preparation of the supported catalyst of the present invention.

(1) Preparation of (2-acetyl-1-naphthol)-vanadium trichloride

At 0°C, 1.1117 g (5.77 mmol) of vanadium tetrachloride (produced by ACROS ORGANICS, USA) was dissolved in 144 ml of hexane to form an orange-yellow transparent solution. Another 0.5368 g (2.88 mmol) of 2-acetyl-1-naphthol (manufactured by ABCR, Germany) was dissolved in 72 ml of hexane at 25° C. to form a pale yellow transparent solution.

With stirring at 0°C, the hexane solution of 2-acetyl-1-naphthol was added dropwise to the hexane solution of vanadium tetrachloride for 80 minutes. The temperature was raised slowly to 25° C., and the stirring reaction was continued for 12 hours. Filter and wash the filter cake 9 times with 360 ml of hexane until the filtrate is colorless. The filter cake was dried under reduced pressure for 3 hours to obtain 0.6613 gram of dark green powdery solid catalyst A, which was (2-acetyl-1-naphthol) vanadium trichloride, and its elemental analysis measured value (calculated value) was as follows:

C: 42.36 mass % (42.08 mass %), H: 2.75 mass % (2.65 mass %).

(2) preparation of supported catalyst

(a) Take 40 milliliters of dry hexane, place in a nitrogen-purged three-necked flask, add 0.30 milliliters (8.8×10 ^-4 mol) of n-butoxytitanium under stirring, and then add 2.0 active magnesium chloride prepared in Example 1 g (2.1×10 ^-2 mol), suspend it in hexane, heat to 70°C, stir at this temperature for 30 minutes, then add 0.8 ml (8.7×10 ^-3 mol) of n-butanol dropwise, and stir to suspend liquid for 30 minutes, filtered, and the solid was washed three times with 30 ml of hexane, and dried at 30° C. for 2 hours to obtain a white powdery carrier a with good fluidity.

(b) Carrier a is placed in a three-necked flask purged with nitrogen, 40 ml of dry hexane is added, and 6.4 ml of a hexane solution of diethylaluminum chloride with a concentration of 1.0 mol/liter is added under stirring, and the reaction is carried out at 0°C. After 2 hours, filter, wash the solid with 30 ml of hexane three times, and dry at 30° C. for 2 hours to obtain the support b treated with alkylaluminum.

(c) Place 0.9 g of carrier b in a nitrogen-purged three-necked flask, add 87 mL of a 0.01 M toluene solution of (2-acetyl-1-naphthol)-vanadium trichloride, and stir at 20 ° C React for 8 hours, filter, and wash the filter cake three times with 60 mL of n-hexane. The filter cake was dried at 30° C. for 2 hours under reduced pressure to obtain 1.06 g of a dark green powder with good fluidity, which was a new ecological MgCl ₂ as carrier loading (2-acetyl-1-naphthol)-vanadium trichloride Catalyst A. The V content, the Mg content, and the Al content of Catalyst A were 3.46% by mass, 15.84% by mass, and 1.23% by mass, as measured by the plasma emission spectrometry (ICP), the same below.

Example 3

(1) Preparation of two (2-acetyl-1-naphthol)-vanadium dichloride

At 0°C, 0.7404 g (3.84 mmol) of vanadium tetrachloride was dissolved in 100 ml of toluene to form a dark brown solution. At 25°C, 1.4310 g (7.68 mmol) of 2-acetyl-1-naphthol was dissolved in 100 ml of toluene to form a pale yellow transparent solution.

At 0° C., the toluene solution of 2-acetyl-1-naphthol was added dropwise to the toluene solution of vanadium tetrachloride, and the dropping time was 90 minutes. Slowly raise the temperature to 25°C, continue stirring for 15 hours, then slowly raise the temperature to 30°C, and stir for 7 hours. Filter, wash the filter cake three times with 90 ml of toluene, and then wash with 30 ml of hexane. The filter cake was dried under reduced pressure for 3 hours to obtain 1.5846 grams of dark green powdery solid, which was two (2-acetyl-1-naphthol) vanadium dichloride, and its elemental analysis measured value (calculated value) was as follows:

C: 58.37% by mass (58.56% by mass), H: 3.75% by mass (3.68% by mass).

(2) preparation of supported catalyst

Prepare supported catalyst B by the method for example 2 (2) step, difference is that the active component that adds is two (2-acetyl-1-naphthol) vanadium dichlorides, obtains 1.2g light green solid powder, is Catalyst B supporting bis(2-acetyl-1-naphthol)-vanadium dichloride on nascent _MgCl2 . Catalyst B had a V content of 3.63% by mass, a Mg content of 14.51% by mass, and an Al content of 1.01% by mass.

Example 4

(1) Preparation of (1-acetyl-2-naphthol)-vanadium trichloride

At 0° C., 0.8560 g (4.44 mmol) of vanadium tetrachloride was dissolved in 110 ml of hexane to form an orange-yellow transparent solution. At 25°C, 0.4132 g (2.22 mmol) of 1-acetyl-2-naphthol (manufactured by ABCR, Germany) was dissolved in 55 ml of hexane to form a pale yellow transparent solution.

At 0° C., the hexane solution of 1-acetyl-2-naphthol was added dropwise to the hexane solution of vanadium tetrachloride for 60 minutes. The temperature was raised slowly to 25°C, and stirring was continued for 12 hours. Filter and wash the filter cake nine times with 360 ml of hexane until the filtrate is colorless. The filter cake was dried under reduced pressure for 3 hours to obtain 0.5168 grams of green powdery solid, which was (1-acetyl-2-naphthol) vanadium trichloride, and its elemental analysis measured value (calculated value) was as follows:

C: 42.27% by mass (42.08% by mass), H: 2.77% by mass (2.65% by mass).

(2) preparation of supported catalyst

Prepare supported catalyst C by the method for example 2 (2) steps, the difference is that the active component that adds is (1-acetyl-2-naphthol) vanadium trichloride, obtains 1.02g light green solid powder, is new Ecological MgCl ₂ as a catalyst C for supporting (1-acetyl-2-naphthol)-vanadium trichloride. Catalyst C had a V content of 3.43% by mass, a Mg content of 15.81% by mass, and an Al content of 1.31% by mass.

Example 5

(1) Preparation of two (1-acetyl-2-naphthol)-vanadium dichloride

At 0°C, 0.9014 g of vanadium tetrachloride (4.68 mmol) was dissolved in 120 ml of toluene to form a dark brown solution. At 20°C, 1.7425 g (9.36 mmol) of 1-acetyl-2-naphthol was dissolved in 120 ml of toluene to form a pale yellow transparent solution.

At 0°C, the toluene solution of 1-acetyl-2-naphthol was added dropwise to the toluene solution of vanadium tetrachloride, and the dropping time was 120 minutes. The temperature was slowly raised to 25°C, and stirring was continued for 16 hours. Filter, wash the filter cake three times with 90 ml of toluene, and then wash with 30 ml of hexane. The filter cake was dried under reduced pressure for 3 hours to obtain 1.8025 grams of dark green powdery solid, which was two (1-acetyl-2-naphthol) vanadium dichloride, and its elemental analysis measured value (calculated value) was as follows:

C: 58.14% by mass (58.56% by mass), H: 3.76% by mass (3.68% by mass).

(2) preparation of supported catalyst

Prepare supported catalyst D by the method for example 2 (2) steps, the difference is that the active component that adds is two (1-acetyl-2-naphthol) vanadium dichlorides, obtains 1.15g light green solid powder, is Neoecological MgCl ₂ is the catalyst D of bis(1-acetyl-2-naphthol)-vanadium dichloride supported on the carrier. The V content in the catalyst D was 3.67% by mass, the Mg content was 14.59% by mass, and the Al content was 1.08% by mass.

Example 6

(1) Preparation of (dibenzoylmethane)-vanadium trichloride

0.8311 g (4.31 mmol) of vanadium tetrachloride was dissolved in 108 ml of hexane at 0° C. to form an orange-yellow transparent solution. 0.4836 g (2.16 mmol) of dibenzoylmethane (manufactured by ACROSORGANICS, USA) was dissolved in 54 ml of hexane at 25° C. to form a colorless transparent solution.

At 0° C., the hexane solution of dibenzoylmethane was added dropwise to the hexane solution of vanadium tetrachloride for 40 minutes. The temperature was slowly raised to 25°C, and stirring was continued for 24 hours. Filter and wash the filter cake nine times with 270 ml of hexane until the filtrate is colorless. The filter cake was dried under reduced pressure for 3 hours to obtain 0.5613 grams of brown-green powdery solid, which was (dibenzoylmethane) vanadium trichloride, and its elemental analysis measured value (calculated value) was as follows:

C: 47.62% by mass (47.34% by mass), H: 3.07% by mass (2.91% by mass).

(2) preparation of supported catalyst

Prepare supported catalyst E by the method for example 2 (2) steps, the difference is that the active component that adds is (dibenzoylmethane) vanadium trichloride, obtains 1.25g light green solid powder, is with new ecology _MgCl as Catalyst E supporting (dibenzoylmethane)-vanadium trichloride. The V content in the catalyst E was 3.57% by mass, the Mg content was 16.12% by mass, and the Al content was 1.25% by mass.

Example 7

(1) Preparation of two (dibenzoylmethane)-vanadium dichlorides

At 0°C, 0.8218 g (4.26 mmol) of vanadium tetrachloride was dissolved in 110 ml of toluene to form a dark brown solution. At 25°C, 1.9122 g (8.53 mmol) of dibenzoylmethane was dissolved in 110 ml of toluene to form a colorless and transparent solution.

At 0°C, the toluene solution of dibenzoylmethane was added dropwise to the toluene solution of vanadium tetrachloride, and the dropping time was 90 minutes. Warm slowly to 25°C and continue stirring for 16 hours. Filter, wash the filter cake three times with 90 ml of toluene, and then wash with 30 ml of hexane. The filter cake was dried under reduced pressure for 3 hours to obtain 1.7202 grams of brown-green powdery solid, which was bis(dibenzoylmethane) vanadium dichloride, and its elemental analysis measured value (calculated value) was as follows:

C: 63.06% by mass (63.40% by mass), H: 3.98% by mass (3.90% by mass).

(2) preparation of supported catalyst

Prepare supported catalyst F by the method for example 2 (2) steps, the difference is that the active component that adds is two (dibenzoylmethane) vanadium dichlorides, obtains 1.15g light green solid powder, is new ecological _MgCl Catalyst F supported by bis(dibenzoylmethane)-vanadium dichloride. Catalyst F had a V content of 3.62% by mass, a Mg content of 14.69% by mass, and an Al content of 1.23% by mass.

Example 8

(1) Preparation of two (acetylacetone)-vanadium dichlorides

At 0° C., 0.6772 g (3.51 mmol) of vanadium tetrachloride was dissolved in 88 ml of hexane to form an orange-yellow transparent solution. At 25° C., 0.7028 g (7.02 mmol) of acetylacetone (manufactured by ALDRICH, USA) was dissolved in 88 ml of hexane to form a pale yellow transparent solution.

At 0° C., the hexane solution of acetylacetone was added dropwise to the hexane solution of vanadium tetrachloride for 80 minutes. The temperature was raised slowly to 25°C, and stirring was continued for 15 hours. Filter and wash the filter cake three times with 90 ml of hexane. The filter cake was dried under reduced pressure for 3 hours to obtain 0.8546 gram of dark green powdery solid, which was bis(acetylacetonate) vanadium dichloride, and its elemental analysis measured value (calculated value) was as follows:

C: 37.12% by mass (37.53% by mass), H: 4.52% by mass (4.41% by mass).

(2) preparation of supported catalyst

Prepare supported catalyst G by the _method for example 2 (2) steps, the difference is that the active component that adds is two (acetylacetonate) vanadium dichlorides, obtains 1.15g light green solid powder, is with new ecology MgCl as carrier Catalyst G supporting bis(acetylacetonate)-vanadium dichloride. The V content in the catalyst G was 3.76% by mass, the Mg content was 14.29% by mass, and the Al content was 1.13% by mass.

Example 9

Catalyst L is prepared by the method of example 2, and difference is that the hexane solution of triethylaluminum hexane solution of 1.0 mol/liter replaces the hexane solution of diethylaluminum chloride with 6.4 milliliters of concentrations and handles, and load active component ( 2-acetyl-1-naphthol)-vanadium trichloride to obtain 1.10 g of light green powdery solid, which is catalyst L. The V content in the catalyst L was 3.51% by mass, the Mg content was 15.42% by mass, and the Al content was 1.19% by mass.

Example 10

Catalyst Q is prepared by the method for example 2, and difference is that the hexane solution of diethylaluminum chloride of 1.0 mol/liter is used 12.8 milliliters of concentrations to handle carrier, load active component (2-acetyl-1-naphthalene After phenol)-vanadium trichloride, 1.19 grams of light green powdery solids were obtained, which was catalyst Q. The V content in the catalyst Q was 3.32% by mass, the Mg content was 15.27% by mass, and the Al content was 1.28% by mass.

Example 11

Two (dibenzoylmethane)-vanadium dichlorides prepared by example 7 are active components, and the catalyst is prepared by the method of example 2 (2) step, except that 1.5 milliliters (8.7 × 10 ^-3 mol) of isooctyl alcohol instead of n-butanol to treat the carrier, the V content in the prepared catalyst H was 3.56 mass%, the Mg content was 15.25 mass%, and the Al content was 1.35 mass%.

Example 12

Two (dibenzoylmethane)-vanadium dichloride prepared with example 7 is active component, prepares catalyst by the method for example 2 (2) step, difference is (a) step with anhydrous MgCl ₂ (Beijing (manufactured by Chemical Reagent Co., Ltd.) instead of MgCl ₂ of the new ecology, the content of V in the prepared catalyst I is 3.46 mass%, the content of Mg is 15.75 mass%, and the content of Al is 1.25 mass%.

Comparative example 1

Two (dibenzoylmethane)-vanadium dichloride prepared with example 7 is an active component, and the new ecology MgCl prepared by 0.9 gram example 1 is taken ₂ , directly make the carrier by the method of example 2 (2) step (c) Catalyst J was prepared by reacting with bis(dibenzoylmethane)-vanadium dichloride. The V content in Catalyst J was 3.16% by mass, and the Mg content was 16.46% by mass.

Comparative example 2

Prepare supported catalyst K by the method for comparative example 1, the difference is that the active component that uses is (2-acetyl-1-naphthol)-vanadium trichloride prepared by example 2, V content in the prepared catalyst K is 3.04% by mass, and the Mg content is 16.61% by mass.

Comparative example 3

Prepare supported catalyst M by the method for comparative example 1, the difference is that the active component used is the bis(acetylacetonate)-vanadium dichloride prepared in example 8, and the V content in the prepared catalyst M is 3.11% by mass, The Mg content was 16.52% by mass.

Examples 13-26

The following examples carry out normal pressure ethylene polymerization.

A 500 ml reaction flask equipped with a stirrer was replaced three times with nitrogen, then three times with ethylene, and ethylene was introduced until the pressure was 0.1 MPa. Add 200 ml of dry hexane, and raise the temperature to 25°C with stirring. Then use 20 ml of hexane to send 2.5×10 ^-5 moles of catalyst into the reaction bottle through the feeding tube, stir to make it evenly dispersed. Then add a hexane solution of diethylaluminum chloride with a concentration of 2.14M, so that the Al/V molar ratio is 100:1. React for 0.5 hours at 25°C, stop feeding ethylene, and then terminate the reaction with 10% ethanol hydrochloric acid solution . Filter the reaction solution, wash the polymerization product with ethanol, water and ethanol in sequence, and dry to obtain a polyethylene product. Catalyst and activity and polymer properties used in each example are shown in Table 1. The viscosity-average molecular weight Mη of the polymer in Table 1 was measured at 135° C. with decahydronaphthalene as a solvent with an Ubbelohde viscometer (model TAMSON TVB445), and the bulk density of polyethylene was measured with the ASTM-D-1895 method.

Examples 27-29

The following example uses the catalyst F of the present invention supporting bis(dibenzoylmethane)-vanadium dichloride to carry out the copolymerization reaction of ethylene and 1-hexene at normal pressure.

Homogeneous polymerization of ethylene was carried out as in Example 13, except that a certain amount of hexene was added before the hexane solution of diethylaluminum chloride. Catalyst used in each example, 1-hexene addition, catalytic activity and polymer properties are shown in Table 2.

Examples 30-35

The following examples carry out high pressure ethylene polymerization.

A 1-liter stainless steel reaction kettle equipped with a stirrer was replaced three times with nitrogen, and then three times with ethylene, and 400 milliliters of dry hexane was added successively, a hexane solution of diethylaluminum chloride with a concentration of 2.14M, and a cocatalyst The dosage should be such that the Al/V molar ratio is 100:1, stir to make it evenly dispersed. Use 100 ml of hexane to send 5.5×10 ^-5 moles of catalyst into the reaction kettle through the feeding tube, stir to make it evenly dispersed. Introduce hydrogen to 0.3MPa, raise the temperature to 70°C, and then inject ethylene until the pressure of the kettle is 0.9MPa, and polymerize at 80°C for 2 hours to obtain a polyethylene product. The catalyst used in each example, catalytic activity and polymer properties are shown in Table 3, and the molecular weight distribution ( _Mw / _Mn ) in Table 3 is measured by gel chromatography (GPC), and the melt flow rate (MFR _2.16 ) is measured in Chengde testing machine Measured on the XNR-400A melt flow rate instrument of the limited liability company, the FRR is MFR _21.6 /MFR _2.16 .

Table 1

instance number Catalyst number Reaction pressure, MPa Vanadium load, mass% Catalyst activity, 10⁵gPE·(molV)^-1·hr^－1] Mη(×10⁴) Bulk density, g/cm³ 13 A 0.1 3.46 3.86 312.3 0.22 14 B 0.1 3.63 4.24 292.3 0.24 15 C 0.1 3.43 3.71 323.6 0.21 16 D. 0.1 3.67 4.19 289.3 0.24 17 E. 0.1 3.57 6.96 247.4 0.25 18 f 0.1 3.62 7.76 232.2 0.26 19 G 0.1 3.76 2.74 369.7 0.21 20 L 0.1 3.51 2.82 295.6 0.19 twenty one Q 0.1 3.32 3.18 311.7 0.21 twenty two h 0.1 3.56 7.13 212.5 0.25 twenty three I 0.1 3.46 6.78 245.3 0.25

instance number Catalyst number Reaction pressure, MPa Vanadium load, mass% Catalyst activity, 10⁵gPE·(molV)^-1·hr^－1] Mη(×10⁴) Bulk density, g/cm³ twenty four J 0.1 3.16 5.57 264.5 0.23 25 K 0.1 3.04 2.14 289.4 0.20 26 m 0.1 3.11 2.38 310.2 0.20

Table 2

X _c in the table is the crystallinity of polymer

table 3

A in the table is catalyst activity, FRR is MFR21.6/MFR2.16

Claims (13)

1. a supported vanadium-based non-metallocene polyethylene catalyst, comprising a magnesium chloride carrier, an aluminum alkyl compound and a vanadium-based non-metallocene complex with formula (I), (II) or (III), in the catalyst The vanadium content is 3.0-8.0% by mass, the magnesium content is 10-25.0% by mass, and the aluminum content is 0.5-3.0% by mass;

In the formulas (I) and (II), R ¹ is selected from C ₁ -C ₆ alkyl, R ² and R ³ are respectively selected from hydrogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ Alkoxy or nitro; in formula (III), R ⁴ and R ⁵ are respectively selected from C ₁ -C ₁₂ alkyl, C ₆ -C ₉ aralkyl or C ₁ -C ₁₂ perfluoroalkyl; In formulas (I) to (III), X is halogen, and n is 1 or 2. 2. The catalyst according to claim 1, characterized in that R ¹ is selected from C ₁ -C ₃ alkyl, R ² and R ³ are respectively selected from hydrogen, C ₁ -C ₃ alkoxy or nitro, R ⁴ and R ⁵ are respectively selected from C ₁ -C ₃ alkyl, phenyl or C ₁ -C ₃ perfluoroalkyl, and X is chlorine. 3. The catalyst according to claim 1, characterized in that the vanadium content in the catalyst is 3.0-5.0 mass%, the magnesium content is 10-20.0 mass%, and the aluminum content is 0.8-2.0 mass%. 4. a preparation method of the described catalyst of claim 1, comprises the steps: (1) Suspend the magnesium chloride carrier in an inert hydrocarbon solvent, fully contact and react with Ti(OR) ₄ and C ₂ -C ₈ aliphatic alcohol at 30-80°C, and then dry the solid, the Ti(OR) ₄ The molar ratio to magnesium chloride is 0.01 to 0.2, the molar ratio of fatty alcohol to magnesium chloride is 0.1 to 1.0, and R in the formula Ti(OR) ₄ is selected from C ₁ to C ₇ alkyl groups; (2) treating the dried carrier obtained in step (1) with an aluminum alkyl in the presence of an inert hydrocarbon solvent, and then drying, the molar ratio of the aluminum alkyl to magnesium chloride is 0.1 to 10; (3) In the presence of a polar organic solvent, fully contact the carrier after step (2) drying with the vanadium-based non-metallocene complex having formula (I), (II) or (III), and collect the solid dry;

In the formulas (I) and (II), R ¹ is selected from C ₁ -C ₆ alkyl, R ² and R ³ are respectively selected from hydrogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ Alkoxy or nitro; in formula (III), R ⁴ and R ⁵ are respectively selected from C ₁ -C ₁₂ alkyl, C ₆ -C ₉ aralkyl or C ₁ -C ₁₂ perfluoroalkyl; In formulas (I) to (III), X is halogen, and n is 1 or 2. 5. according to the described method of claim 4, it is characterized in that described magnesium chloride is new ecology magnesium chloride or anhydrous magnesium chloride. 6. according to the described method of claim 4, it is characterized in that the mol ratio _of Ti(OR) described in step (1) and magnesium chloride is 0.01～0.1. 7. according to the described method of claim 4, it is characterized in that (1) step described Ti (OR) ₄ is tetrabutoxytitanium, tetraethoxytitanium or tetrapropoxytitanium 8. according to the described method of claim 4, it is characterized in that described inert hydrocarbon solvent is the alkane of C ₅ ～C ₁₀ , fatty alcohol is ethanol, propanol, isopropanol, butanol, isobutanol, pentanol , hexanol, heptanol, octanol or isooctyl alcohol. 9. The method according to claim 4, characterized in that the molar ratio of the alkylaluminum to magnesium chloride in step (2) is 0.1-3.0. 10. The method according to claim 4, characterized in that the aluminum alkyl described in step (2) is diethylaluminum chloride, triethylaluminum or triisobutylaluminum. 11. The method according to claim 4, characterized in that the temperature for treating the carrier with aluminum alkyl in step (2) is -20-20°C. 12. The method according to claim 4, characterized in that the polar organic solvent in step (3) is selected from toluene, and the reaction temperature between the carrier and the vanadium-based non-metallocene complex is 10-50°C. 13. The method according to claim 4, characterized in that in the step (3), the molar ratio of magnesium chloride to the vanadium-based non-metallocene complex is 5-500.