Catalyst for olefin polymerization and olefin polymerization method

Abstract

The invention belongs to the technical field of olefin polymerization catalysts, and relates to a catalyst for olefin polymerization and an olefin polymerization method. The catalyst comprises reaction products of the following components: 1) a solid catalyst component comprising titanium, magnesium, halogen and an internal electron donor compound; the internal electron donor comprises a carboxylic ester compound; 2) an aluminum alkyl compound; 3) compounding an external electron donor compound; the compound external electron donor comprises an ester compound and alkyl dialkoxy silane; the ester compound is selected from at least one of compounds shown in a formula (I); in the # imgabs0 # formula (I), R1 and R2 are respectively and independently selected from a straight chain or branched chain alkyl group, a cycloalkyl group, an alkaryl group, an aralkyl group, a condensed ring aryl group or an alkylene group; r3 is selected from straight chain or branched chain alkyl or cycloalkyl; r4 is selected from straight chain or branched chain alkyl, cycloalkyl, alkaryl, aralkyl or fused ring aryl. According to the catalyst system, the good comprehensive performance of the catalyst is maintained, and the hydrogen regulation sensitivity is improved.

Description

Technical Field

[0001] The present invention belongs to the technical field of olefin polymerization catalysts, and more specifically, relates to a catalyst for olefin polymerization and an olefin polymerization method. Background Art

[0002] In the prior art, it is well known that a catalyst containing a titanium compound supported on an active magnesium halide and an electron donor compound is used for homopolymerization or copolymerization of α-olefins. The catalyst system generally consists of three parts: (1) a main catalyst (solid catalyst), (2) a co-catalyst (usually an alkyl aluminum compound) and (3) an external electron donor compound added during polymerization.

[0003] The transition metal in the main catalyst is usually a compound of titanium, zirconium or vanadium, and these compounds are typically halides, halides, alkoxides, alcoholates, and halogen alcoholates of titanium, zirconium or vanadium. The transition metal compound can be represented by the following general formula: (R'O) n R" m MX p-m-n , wherein M is a transition metal of the 4th to 8th subgroup, preferably Ti, Zr or V, R' and R" are the same or different organic groups consisting of a main bond of 1 to 20 carbons, preferably an alkyl group, X is a halogen, preferably chlorine, p is 4 or 5, and n and m are integers between 0 and p. Preferably, the transition metal compound is a titanium compound, and in fact, titanium has been found to be a particularly good transition metal. Suitable titanium compounds include tetramethoxytitanium, tetraethoxytitanium, tetrapropoxytitanium, tetrabutoxytitanium and similar oxides, the corresponding titanium haloalcoholates in which 1 to 3 alkoxy groups are substituted by halogen, especially chlorine, and titanium halides, especially TiBr4 and TiC14, the most commonly used compound being TiCl4.

[0004] The cocatalyst is usually composed of an organic compound of a metal of the main group 1 to 3. Although aluminum compounds are often used, compounds of boron, zinc and alkali metals have also been used. The aluminum compound can be represented by the following formula: R n AlX 3-n , wherein R is an organic hydrocarbon group, preferably C1-C 20 alkyl, X is halogen, and n is an integer from 1 to 3. Different cocatalysts can be used simultaneously in various mixtures. The organic compound commonly used as a cocatalyst is trialkylaluminum, preferably triethylaluminum or triisobutylaluminum.

[0005] In addition, in order to enhance and improve the performance of the catalyst, the main catalyst also includes an internal electron donor compound that can provide electrons to improve the stereoselectivity and / or activity of the catalyst system. During the polymerization process, an external electron donor compound can also be added to improve the stereoselectivity of the final product, thereby further improving the final performance of the catalyst.

[0006] It is well known to those skilled in the art that one or more external electron donor compounds are used to control the stereoregularity and morphology of polymers during polymerization. In addition to affecting the stereoregularity of polymers, external electron donors often affect other aspects of the catalyst performance to varying degrees. Although many compounds are known to be external electron donors, different external electron donor compounds may produce different polymer properties for a specific catalyst. Selecting a suitable external electron donor can be particularly compatible with a specific catalyst, that is, finding a suitable external electron donor can significantly improve certain aspects of the performance of the polymer product, so it is very advantageous to find a group of external electron donors that can be used for a specific catalyst to give the polymer outstanding performance in certain aspects. Summary of the invention

[0007] The inventors unexpectedly discovered in their research work that when a solid catalyst component with a carboxylic acid ester compound as an internal electron donor is added with a specific structure ester compound and a hydrocarbon dihydrocarbyloxysilane as an external electron donor compound during olefin polymerization, its hydrogen regulation sensitivity is greatly improved under the same hydrogenation amount.

[0008] A first aspect of the present invention provides a catalyst for olefin polymerization, the catalyst comprising the reaction product of the following components:

[0009] 1) a solid catalyst component comprising titanium, magnesium, halogen and an internal electron donor compound; the internal electron donor comprises a carboxylate compound;

[0010] 2) Alkyl aluminum compounds;

[0011] 3) a compound external electron donor compound; the compound external electron donor comprises an ester compound and a hydrocarbyldihydrocarbyloxysilane;

[0012] The ester compound is selected from at least one of the compounds represented by formula (I);

[0013]

[0014] In formula (I), R 1 , R 2 Each independently selected from C1-C 20 Straight chain alkyl, C3-C 20 Branched alkyl, C3-C 20 Cycloalkyl, C7-C 20 Alkyl, C7-C 20 Aralkyl, C 10 -C 20 A fused aromatic group or a C2-C 20 The olefin group; R 3 Selected from C1-C20 Straight chain alkyl, C3-C 20 Branched alkyl or C3-C 20 Cycloalkyl; R 4 Selected from C1-C 20 Straight chain alkyl, C3-C 20 Branched alkyl, C3-C 20 Cycloalkyl, C7-C 20 Alkyl, C7-C 20 Aralkyl or C 10 -C 20 A fused ring aromatic group.

[0015] A second aspect of the present invention provides an olefin polymerization method, which comprises: contacting one or more olefins with the above-mentioned catalyst under olefin polymerization reaction conditions.

[0016] Compared with conventional external electron donors such as C-donor and D-donor, the composite external electron donor compound in the catalyst system of the present invention is combined with the solid catalyst component, and the hydrogen adjustment sensitivity of the catalyst is improved while maintaining good comprehensive performance of the catalyst.

[0017] Other features and advantages of the present invention will be described in detail in the following detailed description. DETAILED DESCRIPTION

[0018] The specific embodiments of the present invention are described in detail below. It should be understood that the specific embodiments described herein are only used to illustrate and explain the present invention, and are not used to limit the present invention.

[0019] A first aspect of the present invention provides a catalyst for olefin polymerization, the catalyst comprising the reaction product of the following components:

[0020] 1) a solid catalyst component comprising titanium, magnesium, halogen and an internal electron donor compound; the internal electron donor comprises a carboxylate compound;

[0021] 2) Alkyl aluminum compounds;

[0022] 3) a compound external electron donor compound; the compound external electron donor comprises an ester compound and a hydrocarbyldihydrocarbyloxysilane;

[0023] The ester compound is selected from at least one of the compounds represented by formula (I);

[0024]

[0025] In formula (I), R 1 , R 2 Each independently selected from C1-C 20Straight chain alkyl, C3-C 20 Branched alkyl, C3-C 20 Cycloalkyl, C7-C 20 Alkyl, C7-C 20 Aralkyl, C 10 -C 20 A fused aromatic group or a C2-C 20 The olefin group; R 3 Selected from C1-C 20 Straight chain alkyl, C3-C 20 Branched alkyl or C3-C 20 Cycloalkyl; R 4 Selected from C1-C 20 Straight chain alkyl, C3-C 20 Branched alkyl, C3-C 20 Cycloalkyl, C7-C 20 Alkyl, C7-C 20 Aralkyl or C 10 -C 20 A fused ring aromatic group.

[0026] According to the present invention, preferably, specific examples of the ester compound include, but are not limited to: 2-methoxybenzylidene dimethyl malonate, 3-methoxybenzylidene dimethyl malonate, 4-methoxybenzylidene dimethyl malonate, 2-ethoxybenzylidene dimethyl malonate, 3-ethoxybenzylidene dimethyl malonate, 4-ethoxybenzylidene dimethyl malonate, 2-propoxybenzylidene dimethyl malonate, 3-propoxybenzylidene dimethyl malonate, 4-propoxybenzylidene dimethyl malonate, 2-isopropoxybenzylidene dimethyl malonate, 3-isopropoxybenzylidene dimethyl malonate, 4-isopropoxybenzylidene dimethyl malonate, 2-butoxybenzylidene dimethyl malonate, 3-butoxybenzylidene dimethyl malonate. dimethyl 4-butoxybenzylidene malonate, dimethyl 2-isobutoxybenzylidene malonate, dimethyl 3-isobutoxybenzylidene malonate, dimethyl 4-isobutoxybenzylidene malonate, diethyl 2-methoxybenzylidene malonate, diethyl 3-methoxybenzylidene malonate, diethyl 4-methoxybenzylidene malonate, diethyl 2-ethoxybenzylidene malonate, diethyl 3-ethoxybenzylidene malonate, diethyl 4-ethoxybenzylidene malonate, diethyl 2-propoxybenzylidene malonate, diethyl 3-propoxybenzylidene malonate, diethyl 4-propoxybenzylidene malonate, diethyl 2-isopropoxybenzylidene malonate, diethyl 3-isopropoxybenzylidene malonate diethyl 4-isopropoxybenzylidene malonate, diethyl 2-butoxybenzylidene malonate, diethyl 3-butoxybenzylidene malonate, diethyl 4-butoxybenzylidene malonate, diethyl 2-isobutoxybenzylidene malonate, diethyl 3-isobutoxybenzylidene malonate, diethyl 4-isobutoxybenzylidene malonate, dipropyl 2-methoxybenzylidene malonate, dipropyl 3-methoxybenzylidene malonate, dipropyl 4-methoxybenzylidene malonate, dipropyl 2-ethoxybenzylidene malonate, dipropyl 3-ethoxybenzylidene malonate, dipropyl 4-ethoxybenzylidene malonate, dipropyl 2-propoxybenzylidene malonate, dipropyl 3-propoxybenzylidene malonate Esters, 4-propoxybenzylidene dipropyl malonate, 2-isopropoxybenzylidene dipropyl malonate, 3-isopropoxybenzylidene dipropyl malonate, 4-isopropoxybenzylidene dipropyl malonate, 2-butoxybenzylidene dipropyl malonate, 3-butoxybenzylidene dipropyl malonate, 4-butoxybenzylidene dipropyl malonate, 2-isobutoxybenzylidene dipropyl malonate, 3-isobutoxybenzylidene dipropyl malonate, 4-isobutoxybenzylidene dipropyl malonate, 2-methoxybenzylidene dimethyl succinate, 3-methoxybenzylidene dimethyl succinate, 4-methoxybenzylidene dimethyl succinate, 2-ethoxybenzylidene dimethyl succinate, 3-ethoxybenzylidene dimethyl succinate,4-ethoxybenzylidene succinate dimethyl ester, 2-propoxybenzylidene succinate dimethyl ester, 3-propoxybenzylidene succinate dimethyl ester, 4-propoxybenzylidene succinate dimethyl ester, 2-isopropoxybenzylidene succinate dimethyl ester, 3-isopropoxybenzylidene succinate dimethyl ester, 4-isopropoxybenzylidene succinate dimethyl ester, 2-butoxybenzylidene succinate dimethyl ester, 3-butoxybenzylidene succinate dimethyl ester, 4-butoxybenzylidene succinate dimethyl ester, 2-isobutoxybenzylidene succinate dimethyl ester, 3-isobutoxybenzylidene succinate dimethyl ester, 4-isobutoxybenzylidene succinate dimethyl ester Benzalkonium succinate dimethyl ester, 2-methoxybenzylidene succinate diethyl ester, 3-methoxybenzylidene succinate diethyl ester, 4-methoxybenzylidene succinate diethyl ester, 2-ethoxybenzylidene succinate diethyl ester, 3-ethoxybenzylidene succinate diethyl ester, 4-ethoxybenzylidene succinate diethyl ester, 2-propoxybenzylidene succinate diethyl ester, 3-propoxybenzylidene succinate diethyl ester, 4-propoxybenzylidene succinate diethyl ester, 2-isopropoxybenzylidene succinate diethyl ester, 3-isopropoxybenzylidene succinate diethyl ester, 4-isopropoxybenzylidene succinate diethyl ester diethyl ester, diethyl 2-butoxybenzylidene succinate, diethyl 3-butoxybenzylidene succinate, diethyl 4-butoxybenzylidene succinate, diethyl 2-isobutoxybenzylidene succinate, diethyl 3-isobutoxybenzylidene succinate, diethyl 4-isobutoxybenzylidene succinate, dipropyl 2-methoxybenzylidene succinate, dipropyl 3-methoxybenzylidene succinate, dipropyl 4-methoxybenzylidene succinate, dipropyl 2-ethoxybenzylidene succinate, dipropyl 3-ethoxybenzylidene succinate, dipropyl 4-ethoxybenzylidene succinate, dipropyl 2-methoxybenzylidene succinate, dipropyl 3-ethoxybenzylidene succinate, dipropyl 4-ethoxybenzylidene succinate, One or more of oxybenzylidene succinate dipropyl ester, 3-propoxybenzylidene succinate dipropyl ester, 4-propoxybenzylidene succinate dipropyl ester, 2-isopropoxybenzylidene succinate dipropyl ester, 3-isopropoxybenzylidene succinate dipropyl ester, 4-isopropoxybenzylidene succinate dipropyl ester, 2-butoxybenzylidene succinate dipropyl ester, 3-butoxybenzylidene succinate dipropyl ester, 4-butoxybenzylidene succinate dipropyl ester, 2-isobutoxybenzylidene succinate dipropyl ester, 3-isobutoxybenzylidene succinate dipropyl ester, 4-isobutoxybenzylidene succinate dipropyl ester, etc.

[0027] In the present invention, the ester compound can be prepared by conventional synthesis methods, or purchased by the general chemical product procurement method.

[0028] According to the present invention, preferably, the hydrocarbyldihydrocarbyloxysilane is selected from at least one of the compounds represented by formula (II);

[0029]

[0030] In formula (II), R1, R2, R3, and R4 are the same or different and are independently selected from C 1～ C 20 Straight chain alkyl, C3-C 20 Branched alkyl or C3-C 20 of a cycloalkyl group.

[0031] The hydrocarbyl dihydrocarbyloxysilane is selected from the group consisting of methylcyclohexyl dimethoxysilane, diisopropyl dimethoxysilane, diisobutyl dimethoxysilane, dicyclohexyl dimethoxysilane, dicyclopentyl dimethoxysilane, methylcyclohexyl diethoxysilane, diisopropyl diethoxysilane, diisobutyl diethoxysilane, dicyclohexyl diethoxysilane, dicyclopentyl diethoxysilane, methylcyclohexyl dipropoxysilane, diisopropyl dipropoxysilane, diisobutyl diethoxysilane, Butyldipropoxysilane, dicyclohexyldipropoxysilane, dicyclopentyldipropoxysilane, methylcyclohexyldibutoxysilane, diisopropyldibutoxysilane, diisobutyldibutoxysilane, dicyclohexyldibutoxysilane, dicyclopentyldibutoxysilane, etc.; preferably one of methylcyclohexyldimethoxysilane, dicyclopentyldimethoxysilane, diisopropyldimethoxysilane, diisobutyldimethoxysilane and dicyclohexyldimethoxysilane.

[0032] In the present invention, the hydrocarbyldihydrocarbyloxysilane can be prepared in a laboratory by a common synthesis method, or can be purchased on the market by a general chemical product procurement method.

[0033] In the present invention, the amount of the composite external electron donor compound ester is 0.001 to 1.0 mole per mole of the alkyl aluminum compound; the amount of the hydrocarbon dialkoxy silane is 0.001 to 1.0 mole per mole of the alkyl aluminum compound; the two can be added after mixing or added separately; the addition ratio of the ester to the hydrocarbon dialkoxy silane is 1:100 to 100:1 mole, preferably 1:50 to 50:1.

[0034] During the polymerization process, the external electron donor compound can be pre-contacted with the solid catalyst component for a period of time before being added, or can be mixed with the solid catalyst component for a short time before being added, or can be added at different stages of the polymerization.

[0035] The solid catalyst component of the present invention can be prepared according to conventional methods in the prior art. The solid catalyst component can be prepared by the following method:

[0036] Preferably, the steps include:

[0037] 1) mixing a titanium compound with a spherical magnesium halide alcoholate carrier at a temperature of -30°C to 0°C to obtain a carrier suspension;

[0038] 2) heating the carrier suspension to 80-130° C., adding an internal electron donor compound during the heating process, and reacting at a constant temperature for 0.2-2 hours to obtain a solid precipitate;

[0039] 3) washing and drying the solid precipitate to obtain the solid catalyst component;

[0040] Optionally, in step 3), the solid precipitate is treated with a titanium compound before washing. The treatment may be performed once or multiple times. The inert solvent used for washing may be selected from one or more of hexane, heptane, octane, decane and toluene.

[0041] In addition, in step 1), the mixing is optionally performed in the presence of an inert solvent.

[0042] Method 2: In an inert diluent, a magnesium compound, an organic epoxy compound, an organic phosphorus compound and an optional silane compound are contacted to form a uniform solution, and then the uniform solution is contacted with a titanium compound and an internal electron donor compound in the presence of a precipitation aid to obtain a solid catalyst component.

[0043] According to the present invention, preferably, the carboxylate is a monobasic or polybasic aliphatic carboxylate or an aromatic carboxylate compound. For example: benzoate, phthalate, malonate, succinate, glutarate, etc. Specifically, ethyl benzoate, diethyl phthalate, diisobutyl phthalate, di-n-butyl phthalate, diisooctyl phthalate, di-n-octyl phthalate, diethyl malonate, dibutyl malonate, diethyl 2,3-diisopropylsuccinate, diisobutyl 2,3-diisopropylsuccinate, di-n-butyl 2,3-diisopropylsuccinate, dimethyl 2,3-diisopropylsuccinate, diisooctyl 2,2-dimethylsuccinate. butyl ester, diisobutyl 2-ethyl-2-methylsuccinate, diethyl 2-ethyl-2-methylsuccinate, diethyl adipate, dibutyl adipate, diethyl sebacate, dibutyl sebacate, diethyl maleate, di-n-butyl maleate, diethyl naphthalene dicarboxylate, dibutyl naphthalene dicarboxylate, triethyl trimellitate, tributyl trimellitate, triethyl trimellitate, tributyl trimellitate, tetraethyl pyromellitate, tetrabutyl pyromellitate, etc.

[0044] In the solid catalyst component, the content of the internal electron donor compound is 0.01-5 moles per mole of magnesium.

[0045] The catalyst component (1) of the present invention can be prepared according to the preparation method of the solid catalyst disclosed in Chinese patent CN93102795.0 (method 1). The general formula of the magnesium halide alcoholate of the present invention is MgX2.m(R'OH).nE.qH2O, and the preferred ethanol compound of magnesium chloride is disclosed in Chinese patents CN1091748, CN00109216.2 and CN101050245, and all the relevant contents disclosed therein are incorporated herein by reference.

[0046] In the general formula MgX2.m(R'OH).qH2O, X is Cl, Br or I, preferably Cl; R' is Cl-C 12 Alkyl, C3-C 10 Cycloalkyl or C6-C 10 The aromatic group of the present invention; q is 0-2.

[0047] The specific preparation method of the magnesium halide alcoholate carrier is to mix anhydrous magnesium halide and low-carbon alcohol, and heat the reaction to generate a magnesium halide alcoholate melt at a reaction temperature of 90 to 140° C., and then put it into a cooled inert medium after high shearing in a dispersion medium to form spherical magnesium halide alcoholate particles, and then wash and dry to obtain a spherical carrier. High shearing can be obtained by conventional methods, such as high-speed stirring method (such as CN00109216.2), spray method (such as US6020279), high-gravity rotating bed (such as CN1580136A), and emulsifier method (CN1463990A). The dispersant system uses a hydrocarbon inert solvent, such as kerosene, white oil, silicone oil, paraffin oil, vaseline oil, etc. The cooling medium is selected from pentane, hexane, heptane, petroleum ether, raffinate oil, etc.

[0048] The synthesis method of the catalyst component (1) of the present invention is to suspend the above-obtained magnesium halide alcoholate in a precooled titanium compound or a mixture of a titanium compound and an inert solvent, such as hexane, heptane, octane, decane, toluene, etc., at a temperature of -30°C to 0°C, preferably -20°C to -10°C; then heat the above mixture to 80°C to 130°C, and add an electron donor compound during the heating process. Then, add the titanium compound for one or more times. Finally, wash with an inert solvent for multiple times to obtain a solid catalyst component.

[0049] The catalyst component (1) of the invention can also be prepared according to the preparation method of the solid catalyst disclosed in Chinese patents CN102464746A and CN1258684A (method 2).

[0050] The organic epoxy compound is selected from compounds such as oxides, glycidyl ethers and internal ethers of aliphatic olefins, dienes or halogenated aliphatic olefins or dienes with carbon atoms of 2 to 8, such as ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, methyl glycidyl ether, diglycidyl ether, tetrahydrofuran, etc.

[0051] The precipitation aid can be selected from at least one of organic anhydrides, organic acids, ethers and ketones, preferably at least one of acetic anhydride, phthalic anhydride, succinic anhydride, maleic anhydride, pyromellitic anhydride, acetic acid, propionic acid, butyric acid, acrylic acid, methacrylic acid, acetone, methyl ethyl ketone, benzophenone, methyl ether, ethyl ether, propyl ether, butyl ether and pentyl ether.

[0052] The amount of the organic epoxy compound used is 0.2-10 moles, and the amount of the precipitation aid used is 0.03-1 mole per mole of magnesium element.

[0053] According to the present invention, preferably, the general formula of the titanium compound is Ti(OR w ) 4-k X' k , where R w C1-C 20 Alkyl, X' is Cl, Br or I, and k is an integer of 0-4.

[0054] In the present invention, the titanium compound can be selected from titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, tetrabutoxytitanium, tetraethoxytitanium, monoethoxytitanium monochloride, diethoxytitanium dichloride, triethoxytitanium trichloride, titanium trichloride or a mixture thereof, preferably titanium tetrachloride.

[0055] In the present invention, the content of the titanium compound in the solid catalyst component is 0.5-150 moles per mole of magnesium.

[0056] Component (2) of the present invention is an alkyl aluminum compound, which has the general formula AlR"' n X 3-n , R"' is the same or different C 1-8 The alkyl group is 1≤n≤3, and one or more alkyl aluminums can be used in combination, preferably triethyl aluminum, triisobutyl aluminum, tri-n-butyl aluminum, tri-n-hexyl aluminum, alkyl aluminum chloride, Al(n-C6H 13 )3. Al(n-C8H 17 )3, AlEt2Cl, etc., generally the above-mentioned alkyl aluminum compounds are used with an Al / Ti molar ratio of 1 to 1000.

[0057] The component (2) alkylaluminum compound and the component (3) external electron donor compound may be contacted with the component (1) catalyst component either alone or as a mixture of the two components.

[0058] A second aspect of the present invention provides an olefin polymerization method, which comprises: contacting one or more olefins with the above-mentioned catalyst under olefin polymerization reaction conditions.

[0059] The above catalyst system is suitable for olefins CH2=CHR y , where R y The polymerization reaction is carried out by mixing a mixture of hydrogen or an alkyl or aryl group having 1 to 6 carbon atoms and, if necessary, a small amount of a diene.

[0060] The polymerization of olefins is carried out according to known methods, in the liquid phase of the liquid monomer or a solution of the monomer in an inert solvent, or in the gas phase, or by a combined polymerization process in the gas and liquid phase. The polymerization temperature is generally 0° C. to 150° C., preferably 60° C. to 100° C. The polymerization pressure is atmospheric pressure or higher.

[0061] The invention provides a catalyst system for olefin polymerization reaction. By using the catalyst system, the melting index of the polymer can be changed by adjusting the proportion of an external electron donor while the polymerization activity of the catalyst and the isotactic index of the polymer remain basically unchanged.

[0062] The present invention will be further described below in conjunction with embodiments, but the scope of the present invention is not limited to these embodiments.

[0063] Test Method

[0064] 1) The isotactic index of a polymer is determined by the n-heptane extraction method. According to GB / T 2412-2008, 2 g of a dried polymer sample is placed in an extractor and extracted with boiling n-heptane for 6 hours. The residue is dried to a constant weight. The ratio of the obtained polymer weight (g) to 2 is the isotactic index.

[0065] 2) Polymer melt index: measured according to GB3682-2000 at 230°C and 2.16 kg load.

[0066] Catalyst preparation

[0067] Preparation of Titanium-Containing Solid Catalyst Component A

[0068] In a 300 ml stirred glass reaction bottle fully replaced with high-purity nitrogen, add 100 ml of titanium tetrachloride, cool to -20 ° C, add spherical magnesium chloride alcoholate (preparation method see Chinese patent CN1330086A), slowly heat to 110 ° C in stages, add 3.9 mmol of dibutyl phthalate during the heating process, keep constant temperature at 110 ° C for 0.5 h, filter out the liquid, add titanium tetrachloride for two times, then wash with hexane five times, and obtain titanium-containing solid catalyst component A (main catalyst) after vacuum drying.

[0069] Preparation of Titanium-Containing Solid Catalyst Component B

[0070] In a reactor fully replaced with high-purity nitrogen, 4.8g of magnesium chloride, 95ml of toluene, 4ml of epichlorohydrin, 12.5ml of tributyl phosphate (TBP) and 2.0ml of tetraethoxysilane were added in sequence, and the temperature was raised to 50°C under stirring, and maintained for 2.5 hours. The solid was completely dissolved, and 1.4g of phthalic anhydride was added, and it was maintained for another hour. The solution was cooled to below -25°C, 56ml of TiCl4 was added dropwise within 1 hour, and the temperature was slowly raised to 80°C. Solids were gradually precipitated during the heating process, 2.7ml of diisobutyl phthalate was added, and the temperature was maintained at 80°C for 1 hour. After filtering, 70ml of toluene was added, and the solution was washed twice to obtain a solid precipitate. Then 60ml of toluene and 40ml of TiCl4 were added, the temperature was raised to 100°C, and the solution was treated for 2 hours. After the filtrate was removed, 60ml of toluene and 40ml of TiCl4 were added, the temperature was raised to 100°C, and the solution was treated for 2 hours. The filtrate was removed, and then 60ml of toluene and 40ml of TiCl4 were added, the temperature was raised to 100°C, and the solution was treated for 2 hours. The solution was then removed. 60 ml of toluene was added and washed three times in a boiling state, and then 60 ml of hexane was added and washed twice in a boiling state to obtain a solid catalyst component B (main catalyst).

[0071] Examples 1 to 7

[0072] In a 5-liter autoclave, nitrogen gas was used to purge at 70°C for 1 hour, and then the polymerization autoclave was replaced 3 times with gaseous propylene. Under nitrogen protection, 5 ml of triethylaluminum hexane solution (the concentration of triethylaluminum was 0.5 mmol / ml), 1 ml of hexane solution of external electron donors compounded with different ratios of 4-methoxybenzylidenemalonic acid dimethyl ester (DMPMBM) and methylcyclohexyldimethoxysilane (C-donor) (the concentration of external electron donors was 0.1 mmol / ml), 8 ml of anhydrous hexane and 8-12 mg of titanium-containing solid catalyst component A (main catalyst) were introduced. The autoclave was closed, and an appropriate amount of hydrogen and 1.0-1.2 kg of liquid propylene were introduced; the temperature in the autoclave was quickly raised to 70°C under stirring. After polymerization at 70°C for 1 hour, stirring was stopped, unpolymerized propylene monomers were removed, the polymer was collected, vacuum dried at 70°C for 2 hours, and the activity (AC) was calculated by weighing. The polymerization and test results are shown in Table 1.

[0073] Embodiments 8 to 10

[0074] The polymerization method is the same as that of Examples 1 to 7, except that the added external electron donor is changed to a hexane solution of a composite external electron donor of dimethyl 4-methoxybenzylidenemalonate (DMPMBM) and dicyclopentyldimethoxysilane (D-donor) in different ratios (the concentration of the external electron donor is 0.1 mmol / ml). The polymerization and test results are shown in Table 1.

[0075] Examples 11 to 17

[0076] The polymerization method was the same as in Examples 1 to 7, except that the added external electron donor was changed to a hexane solution of a composite external electron donor of 2-[(3-methoxyphenyl)methylene]-malonic acid 1,3-diethyl ester (MPMPDE) and methylcyclohexyldimethoxysilane (C-donor) in different ratios (the concentration of the external electron donor was 0.1 mmol / ml). The polymerization and test results are shown in Table 1.

[0077] Embodiments 18 to 20

[0078] The polymerization method was the same as in Examples 1 to 7, except that the added external electron donor was changed to a hexane solution of a composite external electron donor of 2-[(3-methoxyphenyl)methylene]-malonic acid 1,3-diethyl ester (MPMPDE) and dicyclopentyldimethoxysilane (D-donor) in different ratios (the concentration of the external electron donor was 0.1 mmol / ml). The polymerization and test results are shown in Table 1.

[0079] Examples 21 to 24

[0080] The polymerization method is the same as in Examples 1 to 7, except that the main catalyst added is changed to catalyst B. The polymerization and test results are shown in Table 1.

[0081] Embodiments 25 to 28

[0082] The polymerization method is the same as in Examples 11 to 17, except that the main catalyst added is changed to catalyst B. The polymerization and test results are shown in Table 1.

[0083] Comparative Examples 1 to 4

[0084] The polymerization method is the same as that of Examples 1 to 7, except that the added external electron donor is changed to 1 ml of a hexane solution of cyclohexylmethyldimethoxysilane (C-donor) or dicyclopentyldimethoxysilane (D-donor) (the concentration of C-donor or D-donor is 0.1 mmol / ml). The polymerization and test results are shown in Table 1.

[0085] Comparative Examples 5-6

[0086] The polymerization method is the same as that of Examples 1 to 7, except that the added external electron donor is changed to 1 ml of a hexane solution of 4-methoxybenzylidenemalonate (DMPMBM) or 2-[(3-methoxyphenyl)methylene]-malonic acid 1,3-diethyl ester (MPMPDE) (the concentration of DMPMBM or MPMPDE is 0.1 mmol / ml). The polymerization and test results are shown in Table 1.

[0087] Comparative Examples 7 to 8

[0088] The polymerization method is the same as that of Comparative Examples 1 to 4, except that the added catalyst is changed from A to B. The polymerization and test results are shown in Table 1.

[0089] Comparative Examples 9 to 10

[0090] The polymerization method is the same as that of Comparative Examples 5-6, except that the added catalyst is changed from A to B. The polymerization and test results are shown in Table 1.

[0091] Table 1

[0092]

[0093]

[0094]

[0095] in:

[0096] DMPMBM, dimethyl 4-methoxybenzylidenemalonate;

[0097] MPMPDE, 2-[(3-methoxyphenyl)methylene]-malonic acid 1,3-diethyl ester;

[0098] C-donor, cyclohexylmethyldimethoxysilane;

[0099] D-donor, dicyclopentyldimethoxysilane.

[0100] It can be seen from Table 1 that by using the external electron donor of the present invention and different main catalysts, a catalyst system with better hydrogen modulation sensitivity can be obtained.

[0101] The embodiments of the present invention have been described above, and the above description is exemplary, not exhaustive, and is not limited to the disclosed embodiments. Many modifications and changes will be apparent to those skilled in the art without departing from the scope and spirit of the described embodiments.

[0102] The endpoints and any values ​​of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

Claims

1. A catalyst for olefin polymerization, characterized in that The catalyst comprises the reaction product of: 1) a solid catalyst component comprising titanium, magnesium, halogen and an internal electron donor compound; the internal electron donor comprises a carboxylate compound; 2) Alkyl aluminum compounds; 3) a compound external electron donor compound; the compound external electron donor comprises an ester compound and a hydrocarbyldihydrocarbyloxysilane; The ester compound is selected from at least one of the compounds represented by formula (I); In formula (I), R 1 , R 2 Each independently selected from C1-C 20 Straight chain alkyl, C3-C 20 Branched alkyl, C3-C 20 Cycloalkyl, C7-C 20 Alkyl, C7-C 20 Aralkyl, C 10 -C 20 A fused aromatic group or a C2-C 20 The olefin group; R 3 Selected from C1-C 20 Straight chain alkyl, C3-C 20 Branched alkyl or C3-C 20 Cycloalkyl; R 4 Selected from C1-C 20 Straight chain alkyl, C3-C 20 Branched alkyl, C3-C 20 Cycloalkyl, C7-C 20 Alkyl, C7-C 20 Aralkyl or C 10 -C 20 A fused ring aromatic group.

2. The catalyst for olefin polymerization according to claim 1, wherein The ester compound is selected from the group consisting of 2-methoxybenzylidene dimethyl malonate, 3-methoxybenzylidene dimethyl malonate, 4-methoxybenzylidene dimethyl malonate, 2-ethoxybenzylidene dimethyl malonate, 3-ethoxybenzylidene dimethyl malonate, 4-ethoxybenzylidene dimethyl malonate, 2-propoxybenzylidene dimethyl malonate, 3-propoxybenzylidene dimethyl malonate, 4-propoxybenzylidene dimethyl malonate, 2-isopropoxybenzylidene dimethyl malonate, 3-isopropoxybenzylidene dimethyl malonate, 4-isopropoxybenzylidene dimethyl malonate, 2-butoxybenzylidene dimethyl malonate, 3-butoxybenzylidene dimethyl malonate, 4-butoxybenzylidene dimethyl malonate dimethyl 2-isobutoxybenzylidene malonate, dimethyl 3-isobutoxybenzylidene malonate, dimethyl 4-isobutoxybenzylidene malonate, diethyl 2-methoxybenzylidene malonate, diethyl 3-methoxybenzylidene malonate, diethyl 4-methoxybenzylidene malonate, diethyl 2-ethoxybenzylidene malonate, diethyl 3-ethoxybenzylidene malonate, diethyl 4-ethoxybenzylidene malonate, diethyl 2-propoxybenzylidene malonate, diethyl 3-propoxybenzylidene malonate, diethyl 4-propoxybenzylidene malonate, diethyl 2-isopropoxybenzylidene malonate, diethyl 3-isopropoxybenzylidene malonate, diethyl 4-isopropoxybenzylidene malonate diethyl ester, diethyl 2-butoxybenzylidene malonate, diethyl 3-butoxybenzylidene malonate, diethyl 4-butoxybenzylidene malonate, diethyl 2-isobutoxybenzylidene malonate, diethyl 3-isobutoxybenzylidene malonate, diethyl 4-isobutoxybenzylidene malonate, dipropyl 2-methoxybenzylidene malonate, dipropyl 3-methoxybenzylidene malonate, dipropyl 4-methoxybenzylidene malonate, dipropyl 2-ethoxybenzylidene malonate, dipropyl 3-ethoxybenzylidene malonate, dipropyl 4-ethoxybenzylidene malonate, dipropyl 2-propoxybenzylidene malonate, dipropyl 3-propoxybenzylidene malonate, dipropyl 4-propoxybenzylidene malonate , 2-isopropoxybenzylidene dipropyl malonate, 3-isopropoxybenzylidene dipropyl malonate, 4-isopropoxybenzylidene dipropyl malonate, 2-butoxybenzylidene dipropyl malonate, 3-butoxybenzylidene dipropyl malonate, 4-butoxybenzylidene dipropyl malonate, 2-isobutoxybenzylidene dipropyl malonate, 3-isobutoxybenzylidene dipropyl malonate, 4-isobutoxybenzylidene dipropyl malonate, 2-methoxybenzylidene dimethyl succinate, 3-methoxybenzylidene dimethyl succinate, 4-methoxybenzylidene dimethyl succinate, 2-ethoxybenzylidene dimethyl succinate, 3-ethoxybenzylidene dimethyl succinate, 4-ethoxybenzylidene dimethyl succinate,2-propoxybenzylidene succinate dimethyl ester, 3-propoxybenzylidene succinate dimethyl ester, 4-propoxybenzylidene succinate dimethyl ester, 2-isopropoxybenzylidene succinate dimethyl ester, 3-isopropoxybenzylidene succinate dimethyl ester, 4-isopropoxybenzylidene succinate dimethyl ester, 2-butoxybenzylidene succinate dimethyl ester, 3-butoxybenzylidene succinate dimethyl ester, 4-butoxybenzylidene succinate dimethyl ester, 2-isobutoxybenzylidene succinate dimethyl ester, 3-isobutoxybenzylidene succinate dimethyl ester, 4-isobutoxybenzylidene succinate dimethyl ester, 2-methoxybenzylidene succinate diethyl ester, 3-methoxybenzylidene succinate diethyl ester, 4-methoxybenzylidene succinate diethyl ester, 2-ethoxybenzylidene succinate diethyl ester, 3-ethoxybenzylidene succinate diethyl ester, 4-ethoxybenzylidene succinate diethyl ester, 2-propoxybenzylidene succinate diethyl ester, 3-propoxybenzylidene succinate diethyl ester, 4-propoxybenzylidene succinate diethyl ester, 2-isopropoxybenzylidene succinate diethyl ester, 3-isopropoxybenzylidene succinate diethyl ester, 4-isopropoxybenzylidene succinate diethyl ester, 2-butoxybenzylidene succinate diethyl ester 2-(2-(2-methoxybenzylidene)succinate, 2-(2-(2-methoxybenzylidene)succinate, 2-(2-(2-methoxybenzylidene)succinate, 2-(2-(2-methoxybenzylidene)succinate, 2-(2-(2-methoxybenzylidene)succinate, 2-(2-(2-methoxybenzylidene)succinate, 2-(2-(2-methoxybenzylidene)succinate, 2-(2-(2-methoxybenzylidene)succinate, 2-(2-(2-ethoxybenzylidene)succinate, 2-(2-ethoxybenzylidene)succinate, 2-(2-(2-ethoxybenzylidene)succinate, 2-(2-(2-ethoxybenzylidene)succinate, 2-(2-(2-meth ... At least one of dipropyl methylene succinate, dipropyl 3-propoxybenzylidene succinate, dipropyl 4-propoxybenzylidene succinate, dipropyl 2-isopropoxybenzylidene succinate, dipropyl 3-isopropoxybenzylidene succinate, dipropyl 4-isopropoxybenzylidene succinate, dipropyl 2-butoxybenzylidene succinate, dipropyl 3-butoxybenzylidene succinate, dipropyl 4-butoxybenzylidene succinate, dipropyl 2-isobutoxybenzylidene succinate, dipropyl 3-isobutoxybenzylidene succinate and dipropyl 4-isobutoxybenzylidene succinate.

3. The catalyst for olefin polymerization according to claim 1, wherein The hydrocarbyldihydrocarbyloxysilane is selected from at least one of the compounds represented by formula (II); In formula (II), R1, R2, R3, and R4 are the same or different and are independently selected from C 1～ C 20 Straight chain alkyl, C3-C 20 Branched alkyl or C3-C 20 Cycloalkyl; Preferably, the hydrocarbyldihydrocarbyloxysilane is selected from at least one of methylcyclohexyldimethoxysilane, diisopropyldimethoxysilane, diisobutyldimethoxysilane, dicyclohexyldimethoxysilane, dicyclopentyldimethoxysilane, methylcyclohexyldiethoxysilane, diisopropyldiethoxysilane, diisobutyldiethoxysilane, dicyclohexyldiethoxysilane, dicyclopentyldiethoxysilane, methylcyclohexyldipropoxysilane, diisopropyldipropoxysilane, diisobutyldipropoxysilane, dicyclohexyldipropoxysilane, dicyclopentyldipropoxysilane, methylcyclohexyldibutoxysilane, diisopropyldibutoxysilane, diisobutyldibutoxysilane, dicyclohexyldibutoxysilane and dicyclopentyldibutoxysilane; More preferably, the hydrocarbyldihydrocarbyloxysilane is methylcyclohexyldimethoxysilane and / or dicyclopentyldimethoxysilane.

4. The catalyst for olefin polymerization according to claim 1, wherein The amount of the ester compound is 0.001-1.0 mole per mole of aluminum in the alkyl aluminum compound, the amount of the hydrocarbyl dihydrocarbyloxysilane is 0.001-1.0 mole, and the molar ratio of the ester compound to the hydrocarbyl dihydrocarbyloxysilane is 1:100 to 100:1, preferably 1:50 to 50:

1.

5. The catalyst for olefin polymerization according to claim 1, wherein The solid catalyst component is prepared by the following method 1 or method 2: Method 1: a titanium compound, a magnesium compound and an internal electron donor compound are contacted and reacted to obtain a solid catalyst component; Preferably, the steps include: 1) mixing a titanium compound with a spherical magnesium halide alcoholate carrier at a temperature of -30°C to 0°C to obtain a carrier suspension; 2) heating the carrier suspension to 80-130° C., adding an internal electron donor compound during the heating process, and reacting at a constant temperature for 0.2-2 hours to obtain a solid precipitate; 3) washing and drying the solid precipitate to obtain the solid catalyst component; Method 2: In an inert diluent, a magnesium compound and an organic epoxy compound are contacted to form a uniform solution, and then in the presence of a precipitation aid, the uniform solution is contacted with a titanium compound and an internal electron donor compound to react to obtain a solid catalyst component.

6. The catalyst for olefin polymerization according to claim 1 or 5, wherein The carboxylate compound is a monovalent or polyvalent aliphatic carboxylate and / or an aromatic carboxylate compound; Preferably, the carboxylate compound is selected from at least one of benzoate, phthalate, malonate, succinate and glutarate; More preferably, the carboxylate compound is selected from ethyl benzoate, diethyl phthalate, diisobutyl phthalate, di-n-butyl phthalate, diisooctyl phthalate, di-n-octyl phthalate, diethyl malonate, dibutyl malonate, diethyl 2,3-diisopropylsuccinate, diisobutyl 2,3-diisopropylsuccinate, di-n-butyl 2,3-diisopropylsuccinate, dimethyl 2,3-diisopropylsuccinate, 2,2-dimethylsuccinate, dimethyl 2,3-diisopropylsuccinate, dimethyl 2,2-dimethylsuccinate, diethyl 2,3-diisopropylsuccinate, dibutyl 2,3-diisopropylsuccinate, dibutyl 2,3-diisopropylsuccinate, diethyl ...butyl 2,2-dimethylsuccinate, diethyl 2,3-diisopropylsuccinate, dibutyl 2,3-diisopropylsuccinate, dibutyl 2,3-diisopropylsuccinate, dibutyl 2,3-diisopropylsuccinate, dibutyl 2,2-dimethylsuccinate, dibutyl 2,2-diisopropylsuccinate, dibutyl 2,3-diisopropylsuccinate, dibutyl 2,3-diisopropylsuccinate, dibutyl 2,2-dimethylsuccinate, dibutyl 2,2-diisopropylsuccinate, dibutyl 2,3-diisopropylsuccinate, dibutyl 2,3-diisopropylsuccinate, dibutyl 2,2-di At least one of diisobutyl 2-ethyl-2-methylsuccinate, diisobutyl 2-ethyl-2-methylsuccinate, diethyl 2-ethyl-2-methylsuccinate, diethyl adipate, dibutyl adipate, diethyl sebacate, dibutyl sebacate, diethyl maleate, di-n-butyl maleate, diethyl naphthalene dicarboxylate, dibutyl naphthalene dicarboxylate, triethyl trimellitate, tributyl trimellitate, triethyl trimellitate, tributyl trimellitate, tetraethyl pyromellitate and tetrabutyl pyromellitate; In the solid catalyst component, the content of the internal electron donor compound is 0.01-5 moles per mole of magnesium.

7. The catalyst for olefin polymerization according to claim 1 or 5, wherein The general formula of the titanium compound is Ti(OR w ) 4-k X' k , where R w C1-C 20 alkyl, X' is Cl, Br or I, k is an integer of 0-4; preferably, the titanium compound is at least one selected from titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, titanium tetrabutoxide, titanium tetraethoxide, titanium triethoxide, titanium trichloride, titanium diethoxide, titanium trichloride and titanium trichloride, more preferably titanium tetrachloride; In the solid catalyst component, the content of the titanium compound is 0.5-150 moles per mole of magnesium.

8. The catalyst for olefin polymerization according to claim 5, wherein In method 1, the structural formula of the magnesium halide alcoholate is MgX2.m(R'OH).qH2O, wherein X is Cl, Br or I, preferably Cl; R' is C1-C 12 Alkyl, C3-C 10 Cycloalkyl or C6-C 10 The aromatic group of the present invention; q is 0-2.

9. The catalyst for olefin polymerization according to claim 5, wherein In method 2, the magnesium compound is selected from magnesium halides; The organic epoxy compound is selected from at least one of oxides, glycidyl ethers and internal ethers of aliphatic olefins, dienes or halogenated aliphatic olefins or dienes having 2 to 8 carbon atoms, preferably at least one of ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, methyl glycidyl ether, diglycidyl ether and tetrahydrofuran; The precipitation aid is selected from at least one of organic anhydrides, organic acids, ethers and ketones, preferably selected from at least one of acetic anhydride, phthalic anhydride, succinic anhydride, maleic anhydride, pyromellitic anhydride, acetic acid, propionic acid, butyric acid, acrylic acid, methacrylic acid, acetone, methyl ethyl ketone, benzophenone, methyl ether, ethyl ether, propyl ether, butyl ether and pentyl ether; Wherein, the amount of the organic epoxy compound used is 0.2-10 moles, and the amount of the precipitation aid used is 0.03-1 mole per mole of magnesium element.

10. The catalyst for olefin polymerization according to claim 1, wherein The general formula of the titanium compound is Ti(OR w ) 4-k X' k , where R w C1-C 20 alkyl, X' is Cl, Br or I, k is an integer of 0-4; preferably, the titanium compound is at least one selected from titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, titanium tetrabutoxide, titanium tetraethoxide, titanium triethoxide, titanium trichloride, titanium diethoxide, titanium trichloride and titanium trichloride, more preferably titanium tetrachloride; In the solid catalyst component, the content of the titanium compound is 0.5-150 moles per mole of magnesium.

11. The catalyst for olefin polymerization according to claim 1, wherein The general formula of the alkyl aluminum compound is AlR"' d X 1 3-d , where R'' is C l -C8 alkyl, X 1 is a halogen, 0<d≤3, when containing two or three R"'s, each R"' is the same or different; Preferably, the alkyl aluminum compound is triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, Al(n-C6H 13 )3. Al(n-C8H 17 )3 and AlEt2Cl at least one; The molar ratio of aluminum in the alkyl aluminum compound to titanium in the solid catalyst component is 1-1000:

1.

12. An olefin polymerization method, characterized in that: The method comprises: under olefin polymerization reaction conditions, contacting one or more olefins with the catalyst for olefin polymerization described in any one of claims 1 to 11; the general formula of the olefins is CH2=CH-R V , where R V is hydrogen or C1-C6 alkyl; the olefin is preferably propylene and / or ethylene, more preferably propylene; The olefin polymerization reaction conditions include: a polymerization temperature of 0-150° C., preferably 60-90° C., and a polymerization pressure of normal pressure or higher.

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