CN1154372A - Alpha-olefin polymerization catalyst and process for producing alpha-olefin polymer - Google Patents

Abstract

The invention discloses an α-olefin polymerization catalyst, which comprises: (A) a solid catalyst component containing a trivalent titanium compound, the preparation method of which is described in detail in the specification; (B) an organoaluminum compound; and (C) an electronic Donor compound. In addition, a method for producing an α-olefin polymer by using the α-olefin polymerization catalyst is disclosed.

Description

α-olefin polymerization catalyst and method for producing α-olefin polymer

The present invention relates to an α-olefin polymerization catalyst and a method for producing α-olefin polymers. In particular, the present invention relates to an α-olefin polymerization catalyst capable of obtaining a highly stereoregular α-olefin polymer containing only a particularly small amount of residual catalyst and amorphous polymer, and having excellent mechanical properties and Processability, in the process of slurry polymerization, bulk polymerization, gas phase polymerization, etc., each solid catalyst and each titanium atom of the catalyst has very high catalytic activity, and it also involves the production of highly stereoregular Process for alpha-olefin polymers.

As a method for producing polymers of α-olefins such as propylene and 1-butene, it is known to use a so-called Ziegler-Natta type catalyst containing transition metal compounds and organometallic compounds of Groups 1, 2 and 13.

In the production of α-olefin polymers, in addition to highly stereoregular α-olefin polymers, amorphous polymers will also be generated as by-products, and highly stereoregular α-olefins have a high degree of industrial application. value. The value of this amorphous polymer in industrial applications is very low, and it has a great bad effect on the mechanical properties in the processing of α-olefin polymers into shaped articles, films, fibers, and other shaped articles. The formation of amorphous polymers results in a loss of monomers of the starting material and at the same time the necessity of equipment for removing the amorphous polymers is a particularly great disadvantage from an industrial point of view. There is therefore a need for a catalyst for the production of alpha-olefin polymers which forms little or no amorphous polymer.

In the obtained α-olefin polymer, a catalyst containing a transition metal compound and an organometallic compound may remain. Because these catalyst residues can cause various problems, such as affecting the stability and processability of α-olefin polymers. It is therefore necessary to have equipment to remove catalyst residues to stabilize the polymer. Because this defect can be improved by increasing the catalytic activity represented by the weight of the α-olefin polymer produced per unit weight of the catalyst, the above-mentioned equipment for removing catalyst residues is unnecessary, reducing the α-olefin polymerization. The production cost of the object is also possible.

It is known that the highly stereoregular and highly active polymerization of α-olefins can be achieved to a certain extent by using Ti-Mg composite solid catalysts, which are made of organic magnesium compounds in the presence of organic silicon compounds. It is obtained by reducing a tetravalent titanium compound and forming a magnesium-titanium eutectic mixture. In the polymerization, an organoaluminum compound is used as an accelerator, and an organosilicon compound is used as a third component. (Japanese Patents (Examined) Hei 3-43283(1991), Hei 1-319508(1989)).

In any case, non-extraction and non-deliming processes are at a possible level, however, further improvements are desired. In particular, it would be desirable to achieve a higher degree of stereospecific polymerization without sacrificing particle size distribution in order to produce high quality alpha-olefin polymers. Especially in the molding field, it is desired to produce polymers with high rigidity, and highly stereoregular polymers can directly obtain high rigidity, so catalysts with higher stereoregular polymerization performance are particularly desired. In practical applications, when using a solid catalyst such as the Ziegler-Natta type, the shape of the particles is particularly important in order to control the bulk density, particle size and fluidity of the polymer. With regard to improving the shape of the particles, in order to overcome this problem, attempts have been made to use a solid catalyst obtained by precipitating a titanium-magnesium compound on silica gel in ethylene polymerization (Japanese Patent (Unexamined) Showa 54-148098 (1979) and Showa 56-47407 (1981)).

It has been found that in the polymerization of polypropylene, particle properties can be greatly improved by using a solid catalyst in which a titanium-magnesium compound is impregnated on silica gel (Japanese Patent (Unexamined) Showa 62-256802 (1987)). Following this approach, a marked improvement in particle shape was indeed seen. However, the silica gel used as a carrier remains in the product, which can form fish eyes in film-forming applications, which is undesirable.

In Japanese Patent (Unexamined) Showa 63-289004, an α-olefin polymerization catalyst is proposed, which includes: (A) a solid catalyst component containing trivalent titanium, which is obtained by first using an ester compound, then using an ether compound and tetravalent titanium A mixture of titanium chlorides is obtained by treating a solid product by reducing Ti(OR ¹ ) _a X _4-a (R ¹ represents a hydrocarbon group with 1-20 carbon atoms, X represents a halogen atom, and a represents a number satisfying 0<a≤4), the organosilicon compound has a Si-O bond, and the porous polymer The microparticles have a pore diameter of 100-5000A° and a micropore volume of 0.1cc/g or more; (B) an organoaluminum compound; and (C) an electron-donor compound that significantly improves the shape of the obtained α-olefin polymer particles, It does not contain inorganic oxides that cause fisheye formation.

However, in these methods, it is necessary to further improve the activity of the catalyst and the stereoregularity of the produced α-olefin polymer.

An object of the present invention is to provide a catalyst for the polymerization of α-olefins with high stereoregularity, which has high bulk density, less fine powder, and does not contain, for example, silica gel, which would produce fish in film-making applications. Inorganic compounds of interest, said catalyst should have sufficiently high catalytic activity so that it is not necessary to remove catalyst residues and amorphous polymers, and also provide a method for producing high-quality alpha-olefin polymers with high stereoregularity method.

According to the present invention, a kind of α-olefin polymerization catalyst is provided, and it comprises: (A) the solid catalyst component that contains trivalent titanium, it is by first using ester compound, then with the mixture of ether compound and titanium tetrachloride or A mixture of ether compounds, titanium tetrachloride and ester compounds is obtained by treating a solid product by reducing Ti(OR ¹ ) with organomagnesium compounds in the presence of organosilicon compounds and porous polymer particles _a X _4-a (R ¹ represents a hydrocarbon group with 1-20 carbon atoms, X represents a halogen atom, and a represents a number satisfying 0<a≤4), the organosilicon compound has Si-O Bond, the pore size of the porous polymer particles is 100-5000 Å, the micropore volume is 0.1cc/g or more; (B) organoaluminum compound; and (C) electron donor compound, in addition to providing a A method for producing an alpha-olefin homopolymer or a copolymer of one alpha-olefin and another alpha-olefin using the catalyst.

By using the present catalyst, the aforementioned objects can be achieved, especially the highly stereoregular polymerization of α-olefins.

The present invention will be described in detail below.

Fig. 1 is a flowchart for easy understanding of the present invention. This flow diagram represents one embodiment of the invention.

(a) Titanium compounds

In the present invention, the titanium compound used to synthesize the solid catalyst component (A) has the general formula Ti(OR ¹ ) _a X _4-a (R ¹ represents a hydrocarbon group with 1-20 carbon atoms, and X represents a halogen atom , a represents a number satisfying 0<a≤4) represents. ^R includes alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, isopentyl, tert-amyl, hexyl, heptyl, octyl, Decyl, dodecyl, etc.; or aryl, such as phenyl, tolyl, xylyl, naphthyl, etc.; or alkenyl, such as propenyl, etc.; aralkyl, such as benzyl, etc., or the like things. Among them, an alkyl group having 2 to 18 carbon atoms, and an aryl group having 6 to 18 carbon atoms are preferred, and a linear alkyl group having 2 to 18 carbon atoms is particularly preferred. Titanium compounds with 2 or more different OR ¹ groups can be used.

The halogen atom represented by X may include chlorine, bromine or iodine, with chlorine giving better results.

In the titanium compound represented by the general formula Ti(OR ¹ ) _a X _4-n , a is a number satisfying 0<a≦4, preferably 2≦a≦4, particularly preferably a=4.

As a method of synthesizing the titanium compound represented by the general formula Ti(OR ¹ ) _a X _4-n , a known method can be utilized. For example, a method of reacting Ti(OR ¹ ) ₄ with TiX ₄ at a predetermined ratio, or a method of reacting TiX ₄ with a predetermined amount of alcohol (R ¹ OH) may be used. As the titanium compound, a dilute solution of its hydrocarbon compound or halogenated hydrocarbon compound can be used.

Examples of titanium compounds represented by the general formula Ti(OR ¹ ) _a X _4-n include: alkoxy titanium trihalide compounds such as methoxy titanium trichloride, ethoxy titanium trichloride, butoxy trihalide Titanium chloride, phenoxy titanium trichloride, ethoxy titanium tribromide, etc.; dialkoxy titanium dihalide compounds, such as dimethoxy titanium dichloride, diethoxy titanium dichloride, di Butoxytitanium dichloride, diphenoxytitanium dichloride, diethoxytitanium dibromide, etc.; trialkoxytitanium halide compounds, such as trimethoxytitanium chloride, triethoxychloride Titanium, tributoxytitanium chloride, triphenoxytitanium chloride, triethoxytitanium bromide, etc.; tetraalkoxytitanium compounds, such as tetramethoxytitanium, tetraethoxytitanium, tetrabutoxytitanium Titanium base, titanium tetraphenoxide, etc. (b) Organosilicon compounds containing Si-O bonds

Examples of organosilicon compounds containing Si-O bonds in their molecules used in the synthesis of the solid catalyst component of the present invention include compounds represented by the following general formula: Si(OR ² ) _m R ³ _4-m ; R ⁴ (R ⁵ ₂ SiO) _p SiR ⁶ ₃ ; and (R ⁷ ₂ SiO) _q wherein R ² is a hydrocarbon group with 1-20 carbon atoms, R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ are 1-20 carbon atoms or hydrogen atoms, m is a number satisfying 0<m≤4, p is an integer of 1-1000, and q is an integer of 2-1000. Examples of organosilicon compounds include tetramethoxysilane, dimethyldimethoxysilane, tetraethoxysilane, triethoxyethylsilane, diethoxydiethylsilane, ethoxytriethylsilane Silane, Tetraisopropoxysilane, Diisopropoxydiisopropylsilane, Tetrapropoxysilane, Dipropoxydipropylsilane, Tetrabutoxysilane, Dibutoxydibutylsilane, Dicyclopentyloxydiethylsilane, Diethoxydiphenylsilane, Cyclohexyloxytrimethylsilane, Phenoxytrimethylsilane, Tetraphenoxysilane, Triethoxyphenylsilane, Hexamethyldisiloxane, Hexaethyldisiloxane, Hexapropyldisiloxane, Octaethyltrisiloxane, Dimethicone, Diphenylpolysiloxane, Methyl Hydrogen polysiloxane, phenyl hydrogen polysiloxane, etc.

Among these organosilicon compounds, alkoxysilanes represented by Si(OR ² ) _m R ³ _4-m are preferred, and preferably 1≤m≤4, and tetraalkoxysilanes with m=4 are particularly preferred of. (C) Porous polymer particles

Examples of porous polymer particles used in component (A) of the present invention include porous polymer particles of polystyrene, polyacrylate, polymethacrylate, polyacrylonitrile, polyvinyl chloride, polyolefin and the like. Specific examples include polystyrene, styrene-divinylbenzene copolymer, styrene-N-N'-alkylene dimethylacrylamide copolymer, styrene-methyl dimethacrylate copolymer , polymethacrylate, polyethylacrylate, methacrylate-divinylbenzene copolymer, ethylacrylate-divinylbenzene copolymer, polymethylmethacrylate, methylmethacrylate - Copolymers of divinylbenzene, polyethylene glycol dimethyl methacrylate, polyacrylonitrile, acrylonitrile-divinylbenzene copolymers, polyvinyl chloride, polyvinylpyrrolidone (pyroridine), polyvinyl Pyridine, ethylvinylbenzene-divinylbenzene copolymer, polyethylene, ethylene-methyl acrylate copolymer, polypropylene, etc. Among these porous polymer particles, porous polymer particles such as polystyrene, polyvinyl chloride, polyolefin and polyacrylonitrile are preferably used, and polystyrene, styrene-divinylbenzene copolymer and polyacrylonitrile are further preferably used. Porous polymer particles of vinyl chloride. The average particle diameter of these polymer particles is preferably 5-1000μ, more preferably 10-600μ, most preferably 15-500μ. The volume of micropores with a pore diameter of 100-5000 Å is 0.1 cc/g or higher, preferably 0.2 cc/g or higher, particularly preferably 0.25 cc/g or higher. It is further preferred to use porous polymer microparticles from which adsorbed water has been removed. Specifically, it is vacuum-dried at about 80°C or higher, or the dried fine particles are treated with the aforementioned organometallic compound such as an organomagnesium compound at about 60°C or higher. (d) Ester compound

As the ester compound used in the present invention, monovalent or polyvalent carboxylate can be used, and examples thereof can include saturated aliphatic carboxylate, unsaturated aliphatic carboxylate, alicyclic carboxylate and aromatic carboxylate esters. Specific examples thereof include methyl acetate, ethyl acetate, phenyl acetate, methyl propionate, ethyl propionate, ethyl butyrate, ethyl valerate, methyl acrylate, ethyl acrylate, methyl methacrylate, Ethyl Benzoate, Butyl Benzoate, Methyl Toluate, Ethyl Toluate, Ethyl Methoxybenzoate, Diethyl Succinate, Dibutyl Succinate, Diethyl Malonate, Malonic Acid Dibutyl ester, dimethyl maleate, dibutyl maleate, itaconate diacetic acid, itaconate dibutyl ester, monoethyl phthalate, dimethyl phthalate, phthalate Methyl formate, diethyl phthalate, di-n-propyl phthalate, diisopropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, ortho Di-n-octyl phthalate, diphenyl phthalate, etc.

Among these ester compounds, unsaturated aliphatic carboxylic acids such as methacrylate and maleate, and phthalates are preferable, and phthalate diesters are particularly preferable. (e) Organomagnesium compounds

As the organomagnesium compound, any organomagnesium compound having a Mg-carbon bond in the molecule can be used in the present invention.

In particular, Grignard compounds represented by the general formula R ⁸ MgX (R ⁸ is a hydrocarbon group having 1 to 20 carbon atoms, X is a halogen atom) and Grignard compounds represented by the general formula R ⁹ R ¹⁰ Mg (R ⁹ and R ¹⁰ is a dialkyl magnesium compound or a diaryl magnesium compound represented by a hydrocarbon group having 1 to 20 carbon atoms).

R ⁸ , R ⁹ and R ¹⁰ may be the same or different, examples of which include alkyl, aryl, aralkyl and alkenyl groups with 1-20 carbon atoms, such as methyl, ethyl, propyl, isopropyl Base, butyl, sec-butyl, pentyl, isopentyl, hexyl, octyl, 2-ethylhexyl, phenyl, benzyl, etc.

Examples of Grignard compounds include methylmagnesium chloride, ethylmagnesium chloride, ethylmagnesium bromide, ethylmagnesium iodide, propylmagnesium chloride, propylmagnesium bromide, butylmagnesium chloride, butylmagnesium bromide, sec-butylmagnesium chloride , sec-butyl magnesium bromide, tert-butyl magnesium chloride, tert-butyl magnesium bromide, pentyl magnesium chloride, isopentyl magnesium chloride, hexyl magnesium chloride, phenyl magnesium chloride, phenyl magnesium bromide, etc., by the general formula R ⁹ R ¹⁰ Compounds represented by Mg include dimethylmagnesium, diethylmagnesium, dipropylmagnesium, diisopropylmagnesium, dibutylmagnesium, di-sec-butylmagnesium, di-tert-butylmagnesium, butyl-sec-butylmagnesium , Dipentyl magnesium, dihexyl magnesium, diphenyl magnesium, butyl ethyl magnesium, etc.

As a solvent for synthesizing the above organomagnesium compounds, ether solvents can be used, such as diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diisobutyl ether, dipentyl ether, diisoamyl ether ether, dihexyl ether, dioctyl ether, diphenyl ether, dibenzyl ether, phenetole, anisole, tetrahydrofuran, etc. Hydrocarbon solvents can be used, such as hexane, heptane, octane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, etc., and a mixed solvent of ether and hydrocarbon can also be used.

It is preferable to use the organomagnesium compound under the condition of an ether solution, and as the ether solution, an ether compound or a cyclic ether compound having 6 or more carbon atoms in the molecule is used. From the viewpoint of catalytic ability, it is preferable to use a Grignard compound represented by the general formula R ⁸ MgX as the ether solution. Also, a composite of the above-mentioned organomagnesium compound and a hydrocarbon-soluble organometallic compound may be used. As examples of these organometallic compounds, there are organic compounds of Li, Be, B, Al or Zn. (f) Ether compounds

As the ether compound used in the present invention, dialkyl ethers such as diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diisobutyl ether, diamyl ether, dialkyl ether, Isopentyl ether, di-neopentyl ether, dihexyl ether, dioctyl ether, methyl butyl ether, methyl isopentyl ether, ethyl isobutyl ether, etc. Among them, dibutyl ether and dipentyl ether are particularly preferable. (g) Synthesis of solid catalyst fraction

The solid catalyst component of the present invention is synthesized by first treating a solid product with an ester compound and then with a mixture of an ether compound and titanium tetrachloride or a mixture of an ether compound, titanium tetrachloride and an ester compound. The solid product is obtained by reducing the titanium compound with an organomagnesium compound in the presence of porous polymer particles, an organosilicon compound and an ester compound. All these synthetic reactions are carried out in an inert atmosphere such as nitrogen, argon, and the like.

The solid product is synthesized by reducing the titanium compound with an organomagnesium compound in the presence of porous polymer particles, organosilicon compound and ester compound. At this time, due to the reduction reaction, solids are deposited on the porous polymer particles. The solid product retains the shape of the porous polymer and preferably does not form fine particles.

As a method of reducing the titanium compound with the organomagnesium compound, either the organomagnesium compound is added to the mixture of the titanium compound, the organosilicon compound, the porous polymer particles and the ester compound, or conversely the titanium compound, the organosilicon compound, and the ester compound The mixture of compounds is added to the mixture of organomagnesium compound solution and porous polymer particles. From the viewpoint of catalyst activity, among these, a method in which an organomagnesium compound is added to a mixture of a titanium compound, an organosilicon compound porous polymer fine particles and an ester compound is preferable.

Titanium compounds, organosilicon compounds, porous polymer particles and ester compounds are preferably used in solutions or dilutions in appropriate solvents. These solvents include aliphatic hydrocarbons, such as hexane, heptane, octane, decane, etc.; aromatic hydrocarbons, such as toluene, xylene, etc.; alicyclic hydrocarbons, such as cyclohexane, methylcyclohexane, decalin, etc.; ether compounds , such as diethyl ether, dibutyl ether, diisoamyl ether, tetrahydrofuran, etc.

The reduction temperature is -50 to 70°C, preferably -30 to 50°C, particularly preferably -25 to 35°C. If the reduction temperature is too high, the catalytic activity will decrease.

The dropping time is not particularly limited, and may be about 30 minutes to 12 hours. After the reduction reaction is completed, a postreaction can be performed at 20-120°C.

The amount of the organosilicon compound is preferably 1-50, more preferably 3-30, particularly preferably 5-25 based on the atomic ratio (Si/Ti) of silicon atoms to titanium atoms in the titanium compound. The amount of the ester compound is based on the molar ratio of the ester compound to the titanium atom in the titanium compound (ester compound/Ti), preferably 0.05-10, more preferably 0.1-6, particularly preferably 0.2-3. In addition, for the amount of organomagnesium compound, based on the ratio (Ti+Si/Mg) of the total amount of silicon atoms and titanium atoms to magnesium atoms, it is preferably 0.1-10, more preferably 0.2-5.0, particularly preferably 0.2-2.0 . The amount of porous polymer used is preferably 20-95% by weight, more preferably 30-85% by weight, based on the weight of the solid product.

The solid product obtained by the reduction reaction is separated by solid-liquid separation and washed several times with inert hydrocarbon solvents such as hexane and heptane.

Next, the solid product obtained by the above-mentioned method is treated with an ester compound. The ester compound is preferably used at 0.1-50 mol, more preferably at 0.3-20 mol, particularly preferably at 0.5-10 mol, per mol of titanium atom in the solid product. The amount of the ester compound is preferably 0.01-1.0 mol, more preferably 0.03-0.5 mol, per mol of magnesium atoms in the solid product.

The treatment of the solid product with the ester compound can be carried out by any known method capable of contacting the solid product with the ester compound, such as a slurry method, or a mechanical grinding method using a ball mill, etc. However, when mechanical grinding is used, the solid catalyst component forms a large number of fine particles, and the particle size distribution becomes very wide, which is not preferable from an industrial point of view, but is beneficial to both in the presence of a diluent. contact is preferred.

As a diluent, aliphatic hydrocarbons, such as pentane, hexane, heptane, octane, etc., aromatic hydrocarbons, such as benzene, toluene, xylene, etc., alicyclic hydrocarbons, such as cyclohexane, cyclopentane, etc., halogenated Hydrocarbons, such as 1,2-dichloroethane, monochlorobenzene, etc. Among them, aromatic hydrocarbons and halogenated hydrocarbons are particularly preferable.

The amount of the diluent is preferably 0.1ml-1000ml, more preferably 1ml-100ml, per gram of solid product. The treatment temperature is preferably -50 to 150°C, more preferably 0 to 120°C. The treatment time is preferably 5 minutes or longer, further preferably 15 minutes to 3 hours. After the treatment is complete, the treated solid is allowed to stand, the solid is separated from the liquid phase, and then washed several times with an inert solvent to obtain the ester-treated solid. Then, the ester-treated solid is treated with a mixture of ether compound and titanium tetrachloride. This treatment is preferably carried out in a slurry state, and the solvent used for the slurry includes aliphatic hydrocarbons, such as pentane, hexane, heptane, octane, decane, etc., aromatic hydrocarbons, such as toluene, xylene, etc., alicyclic hydrocarbons, Such as cyclohexane, methylcyclohexane, decalin, etc., halogenated hydrocarbons, such as dichloroethane, trichloroethylene, monochlorobenzene, dichlorobenzene, trichlorobenzene, etc. Among them, halogenated hydrocarbons and aromatic hydrocarbons are particularly preferable.

The concentration of the slurry is preferably 0.05-0.7 g solid/ml-solvent, more preferably 0.1-0.5 g solid/ml-solvent. The reaction temperature is preferably 30-150°C, more preferably 40-135°C, particularly preferably 60-120°C. The reaction time is not particularly limited. Generally, however, about 30 minutes to 6 hours is preferred.

As a method of addition to solids treated with esters, ether compounds and titanium tetrachloride, either the ether compounds and titanium tetrachloride are added to the ester-treated solids or, conversely, the ester-treated The solid is added to a solution of the ether compound and titanium tetrachloride, both methods can be used. In the method of adding the ether compound and titanium tetrachloride to the ester-treated solid, adding the ether compound and then adding the titanium tetrachloride, or adding the ether compound and titanium tetrachloride at the same time, both methods are preferred, but the method of adding a previously prepared mixture of ether compound and titanium tetrachloride to the ester-treated solid is particularly preferred.

The reaction of the ester-treated solid with the ether compound and titanium tetrachloride may be repeated two or more times. From the viewpoint of catalyst activity and stereoregularity, the reaction with the mixture of ether compound and titanium tetrachloride is preferably repeated at least twice.

The amount of the ether compound used is preferably 0.1-100 mol, more preferably 0.5-50 mol, particularly preferably 1-20 mol, per mole of titanium atoms contained in the solid product. The amount of titanium tetrachloride used is preferably 1-1000 mol, more preferably 3-500 mol, particularly preferably 10-300 mol, per mole of titanium atoms contained in the solid product. The amount of titanium tetrachloride used is preferably 1-100 mol, more preferably 1.5-75 mol, particularly preferably 2-50 mol per mol of the ether compound.

The ester compound may coexist during the treatment of the ester-treated solid with the mixture of the ether compound and titanium tetrachloride. The amount of the ester compound used is preferably 30 mol or less, further preferably 15 mol or less, particularly preferably 5 mol or less, per mol of titanium atoms contained in the solid product.

The solid catalyst containing trivalent titanium compound obtained by the above method is subjected to solid-liquid separation, and then washed several times with an inert solvent such as hexane, heptane, etc., to be used for polymerization. From the viewpoint of catalytic activity and stereoregularity, after solid-liquid separation, the solid catalyst is preferably washed with a large amount of halogenated hydrocarbons such as monochlorobenzene or aromatic hydrocarbon solvents such as toluene at a temperature of 50-120 ° C. One or more times, then, washed several times with aliphatic hydrocarbon solvents, such as hexane, heptane, etc., before being used for polymerization. (h) Organoaluminum compound (B)

The organoaluminum compound used in the present invention has at least one Al-carbon bond in its molecule. Representative organoaluminum compounds are represented by the following general formula: R ¹¹ _γ AlY _3-γ and R ¹² R ¹³ Al-O-AlR ¹⁴ R ¹⁵ wherein R ¹¹ -R ¹⁵ represent hydrocarbon groups with 1-20 carbon atoms, Y represents halogen, hydrogen or alkoxy, and γ is a number satisfying 2≤γ≤3.

Examples of organoaluminum compounds include trialkylaluminum such as triethylaluminum, triisobutylaluminum, trihexylaluminum, etc.; dialkylaluminum hydrides such as diethylaluminum hydride, diisobutylaluminum hydride, etc.; Alkyl aluminum halides, such as diethylaluminum chloride, etc.; mixtures of trialkylaluminum and dialkylaluminum halides, such as mixtures of triethylaluminum and diethylaluminum chloride; alkylalumoxanes , such as tetraethyldialuminoxane, tetrabutyldialumoxane, etc.

Among these organoaluminum compounds, trialkylaluminum, mixtures of trialkylaluminum and dialkylaluminum halides and alkylaluminoxanes are preferred, particularly preferred are triethylaluminum, triisobutylaluminum, trialkylaluminum, Mixture of ethylaluminum and diethylaluminum chloride, tetraethyldialuminoxane.

For every mole of titanium atoms contained in the solid catalyst, the amount of the organoaluminum compound used can be selected from 0.5-1000 mol, and the particularly preferred range is 1-600 mol. (c) Electron donor compound (C)

The electron donor compound used for polymerization in the present invention can be an oxygen-containing electron donor, such as alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic or inorganic acids, ethers, amides (acid amides), anhydrides, etc. ; Nitrogen-containing electron donors, such as ammonia, amines, nitriles, isocyanates, etc.; and the like. Among them, inorganic acid esters and ethers are preferable.

A preferred inorganic acid ester is an organosilicon compound represented by the following general formula: R ¹⁶ _n Si(OR ¹⁷ ) _4-n , wherein R ¹⁶ is a hydrocarbon group with 1-20 carbon atoms or hydrogen, and R ¹⁷ is a - A hydrocarbon group of 20 carbon atoms, R ¹⁶ and R ¹⁷ may be different in the same molecule, and n is a number satisfying 0≤n<4. Examples include tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetraphenoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, butyltrimethoxysilane, isobutyl Trimethoxysilane, tert-butyltrimethoxysilane, isopropyltrimethoxysilane, cyclohexyltrimethoxysilane, phenyltrimethoxysilane, vinyltrimethoxysilane, dimethyldimethoxysilane Silane, diethyldimethoxysilane, dipropyldimethoxysilane, propylmethyldimethoxysilane, diisopropyldimethoxysilane, dibutyldimethoxysilane, di Isobutyldimethoxysilane, di-tert-butyldimethoxysilane, butylmethyldimethoxysilane, butylethyldimethoxysilane, tert-butylmethyldimethoxysilane, tert-butylethyl Dimethoxysilane, tert-butyl-n-propyldimethoxysilane, isobutylisopropyldimethoxysilane, tert-butylisopropyldimethoxysilane, tert-butyl-n-butyldimethoxysilane , tert-butylisobutyldimethoxysilane, tert-butyl-sec-butyldimethoxysilane, hexylmethyldimethoxysilane, hexylethyldimethoxysilane, dodecylmethyldimethoxysilane , Dicyclopentyldimethoxysilane, Cyclopentylmethyldimethoxysilane, Cyclopentylethyldimethoxysilane, Cyclopentylisopropyldimethoxysilane, Cyclopentyl Isobutyldimethoxysilane, cyclopentyl tert-butyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylethyldimethoxysilane, Cyclohexylisopropyldimethoxysilane, cyclohexylisobutyldimethoxysilane, cyclohexyltert-butyldimethoxysilane, cyclohexylcyclopentyldimethoxysilane, cyclohexylphenyldimethylsilane Oxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, phenylisopropyldimethoxysilane, phenylisobutyldimethoxysilane, phenyltert-butyl Dimethoxysilane, Phenylcyclopentyldimethoxysilane, Vinylmethyldimethoxysilane, Methyltriethoxysilane, Ethyltriethoxysilane, Butyltriethoxysilane , isobutyltriethoxysilane, tert-butyltriethoxysilane, isopropyltriethoxysilane, cyclohexyltriethoxysilane, phenyltriethoxysilane, vinyltriethoxy Silane, dimethyldiethoxysilane, diethyldiethoxysilane, dipropyldiethoxysilane, propylmethyldiethoxysilane, diisopropyldiethoxysilane, di Butyldiethoxysilane, diisobutyldiethoxysilane, di-tert-butyldiethoxysilane, butylmethyldiethoxysilane, butylethyldiethoxysilane, tert-butylmethyldiethoxysilane Ethoxysilane, Hexylmethyldiethoxysilane, Hexylethyldiethoxysilane, Dodecylmethyldiethoxysilane, Dicyclopentyldiethoxysilane, Dicyclohexyldiethoxysilane Oxysilane, cyclohexylmethyldiethoxysilane, cyclohexylethyldiethoxysilane, diphenyldiethoxysilane, phenylmethyldiethoxysilane, vinylmethyldiethoxysilane base silane, ethyl triisopropoxy silane, vinyl tributoxy silane, phenyl tri-tert-butoxy silane, 2-norbornane trimethoxy silane, 2-norbornane ) yltriethoxysilane, 2-norbornane (norbornane)ylmethyldimethoxysilane, trimethylphenoxysilane, methyltriaryloxysilane, and the like.

其中，R¹⁸-R²¹分别是直链的或支链的有1-20个碳原子的烷基、脂环基、芳基、烷芳基、或芳烷基，R¹⁸或R¹⁹可以是氢。其实例包括二乙基醚、二丙基醚、二异丙基醚、二丁基醚、二戊基醚、二异戊基醚、二新戊基醚、二己基醚、二辛基醚、甲基丁基醚、甲基异戊基醚、乙基异丁基醚、2，2-二异丁基-1，3-二甲氧基丙烷、2-异丙基-2-异戊基-1，3-二甲氧基丙烷、2，2-双(环己基甲基)-1，3-二甲氧基丙烷、2-异丙基-2-3，7-二甲基辛基-1，3-二甲氧基丙烷、2，2-二异丙基-1，3-二甲氧基丙烷、2-异丙基-2-环己基甲基-1，3-二甲氧基丙烷、2，2-二环己基-1，3-二甲氧基丙烷、2-异丙基-2-异丁基-1，3-二甲氧基丙烷、2，2-二异丙基-1，3-二甲氧基丙烷、2，2-二丙基-1，3-二甲氧基丙烷、2-异丙基-2-环己基-1，3-二甲氧基丙烷、2-异丙基-2-环戊基-1，3-二甲氧基丙烷、2，2-二环戊基-1，3-二甲氧基丙烷、2-庚基-2-戊基-1，3-二甲氧基丙烷等。Preferred are dialkyl ether and diether compounds represented by the general formula:

Wherein, R ¹⁸ -R ²¹ are linear or branched alkyl, alicyclic, aryl, alkaryl, or aralkyl groups with 1-20 carbon atoms respectively, and R ¹⁸ or R ¹⁹ can be hydrogen. Examples thereof include diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diamyl ether, diisoamyl ether, dineopentyl ether, dihexyl ether, dioctyl ether, Methyl butyl ether, methyl isoamyl ether, ethyl isobutyl ether, 2,2-diisobutyl-1,3-dimethoxypropane, 2-isopropyl-2-isoamyl -1,3-dimethoxypropane, 2,2-bis(cyclohexylmethyl)-1,3-dimethoxypropane, 2-isopropyl-2-3,7-dimethyloctyl -1,3-dimethoxypropane, 2,2-diisopropyl-1,3-dimethoxypropane, 2-isopropyl-2-cyclohexylmethyl-1,3-dimethoxy propane, 2,2-dicyclohexyl-1,3-dimethoxypropane, 2-isopropyl-2-isobutyl-1,3-dimethoxypropane, 2,2-diisopropyl 1,3-dimethoxypropane, 2,2-dipropyl-1,3-dimethoxypropane, 2-isopropyl-2-cyclohexyl-1,3-dimethoxypropane , 2-isopropyl-2-cyclopentyl-1,3-dimethoxypropane, 2,2-dicyclopentyl-1,3-dimethoxypropane, 2-heptyl-2-pentyl Base-1,3-dimethoxypropane, etc.

Among these electron donor compounds, organosilicon compounds represented by the general formula R ²² R ²³ Si(OR ²⁴ ) ₂ are preferable. (wherein ^R22 is a hydrocarbon group with 3-20 carbon atoms, and the carbon atom connected to Si is a secondary or tertiary carbon atom, examples of which include branched chain alkyl groups, such as isopropyl, sec-butyl, tert-butyl, tert- Pentyl, etc.; cycloalkyl, such as cyclopentyl, cyclohexyl, etc.; cycloalkenyl (cycloalkenyl), such as cyclopentenyl, etc.; aryl, such as phenyl, tolyl, etc. R ²³ is 1-20 Hydrocarbon groups of carbon atoms, examples of which include straight-chain alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, etc.; branched-chain alkyl groups such as isopropyl, sec-butyl, tert-butyl, tert-amyl Cycloalkyl, such as cyclopentyl, cyclohexyl, etc.; Cycloalkenyl, such as cyclopentenyl, etc.; Aryl, such as phenyl, tolyl, etc. R ²⁴ is a hydrocarbon group with 1-20 carbon atoms , preferred hydrocarbyl groups have 1-5 carbon atoms.)

Examples of organosilicon compounds used as electron donor compounds include diisopropyldimethoxysilane, diisobutyldimethoxysilane, di-tert-butyldimethoxysilane, tert-butylmethyldimethoxy Silane, tert-butylethyldimethoxysilane, tert-butyl-n-propyldimethoxysilane, isobutylisopropyldimethoxysilane, tert-butylisopropyldimethoxysilane, tert-butyl-n-butyl Dimethoxysilane, tert-butylisobutyldimethoxysilane, tert-butyl-sec-butyldimethoxysilane, dicyclopentyldimethoxysilane, cyclopentylisopropyldimethoxysilane, cyclo Amylisobutyldimethoxysilane, Cyclopentyltert-butyldimethoxysilane, Dicyclohexyldimethoxysilane, Cyclohexylmethyldimethoxysilane, Cyclohexylethyldimethoxysilane Silane, cyclohexylisopropyldimethoxysilane, cyclohexylisobutyldimethoxysilane, cyclohexyltert-butyldimethoxysilane, cyclohexylcyclopentyldimethoxysilane, cyclohexylphenyl Dimethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, phenylisopropyldimethoxysilane, phenylisobutyldimethoxysilane, phenyl tertiary Butyldimethoxysilane, phenylcyclopentyldimethoxysilane, diisopropyldiethoxysilane, diisobutyldiethoxysilane, di-tert-butyldiethoxysilane, tert Butylmethyldiethoxysilane, Dicyclopentyldiethoxysilane, Dicyclohexyldiethoxysilane, Cyclohexylmethyldiethoxysilane, Cyclohexylethyldiethoxysilane, Diphenyl Diethoxysilane, phenylmethyldiethoxysilane, 2-norbornylmethyldimethoxysilane, and the like. (j) Polymerization method of olefins

The α-olefin used in the present invention is an α-olefin having 3 or more carbon atoms, and examples thereof include linear monoolefins such as propylene, butene-1, pentene-1, hexene-1, heptene ene-1, octene-1, decene-1, etc.; branched monoolefins, such as 3-methylbutene-1, 3-methylpentene-1, 4-methylpentene-1, etc.; ethylene Cyclohexane etc. These α-olefins may be used alone or in combination of two or more. Among these α-olefins, it is preferable to carry out homopolymerization of propylene or butene-1, or to carry out copolymerization with mixed olefins containing propylene as the main component, especially preferably to carry out homopolymerization with propylene, or to use propylene as the main component for mixed olefins. Alkenes are copolymerized. In the copolymerization of the present invention, a mixture of ethylene and at least one α-olefin selected from the above α-olefins may be used. Also in the copolymerization, compounds having 2 or more unsaturated bonds, such as conjugated dienes and non-conjugated dienes, can be used. Hetero-block copolymerization involving two or more polymerization steps can be easily performed.

The method of feeding each catalyst fraction into the polymerization vessel is not particularly limited except that it is added in a dry state under an inert atmosphere such as nitrogen, argon, or the like.

The solid catalyst component (A), organoaluminum compound (B) and electron donor compound (C) may be added individually, or any two of them may be brought into contact and then added.

In the present invention, the olefin may be polymerized in the presence of the above-mentioned catalyst, but the below-mentioned prepolymerization may be carried out before the above-mentioned polymerization (main polymerization) is performed.

The prepolymerization is carried out by adding a small amount of olefin in the presence of the solid catalyst component (A) and the organoaluminum compound (B), preferably in a slurry state. As a solvent for slurrying, inert hydrocarbons such as propane, butane, isobutane, pentane, isopentane, hexane, heptane, octane, cyclohexane, benzene or toluene can be used. During slurry formation, some or all of the inert hydrocarbons may be replaced by liquid olefins.

In the prepolymerization, the amount of the organoaluminum compound used can be selected within a wide range of 0.5-700 mol, preferably 0.8-500 mol, more preferably 1-200 mol, per mole of titanium atoms in the solid catalyst component. The amount of prepolymerized olefin is 0.01-1000 g, preferably 0.05-500 g, particularly preferably 0.1-200 g, per 1 g of solid catalyst component.

In the prepolymerization, the concentration of the slurry is preferably 1-500 g of solid catalyst component/liter of solvent, particularly preferably 3-300 g of solid catalyst component/liter of solvent. The prepolymerization temperature is preferably -20 to 100°C, more preferably 0 to 80°C. The partial pressure of the olefin in the gas phase in the prepolymerization is preferably 0.01-20 kg/cm ² , particularly preferably 0.1-10 kg/cm ² , but this prepolymerization pressure and temperature are not applied to the liquid olefin. In addition, the prepolymerization time is not particularly limited, and 2 minutes to 15 hours is usually selected.

During the carrying out of prepolymerization, the addition of solid catalyst component (A), organoaluminum compound (B) and olefin can adopt the following method: or add after solid catalyst component (A) contacts with organoaluminum compound (B) olefin, or the organoaluminum compound (B) is added after the solid catalyst component (A) is contacted with the olefin.

The addition of the olefin may be carried out by either feeding the olefin to maintain the inherent pressure in the polymerization vessel, or feeding the entirety of the predetermined amount of the olefin at the beginning. To control the molecular weight of the polymer obtained, a chain transfer agent such as hydrogen may be added.

In addition, in the prepolymerization of a small amount of olefin in the presence of the solid catalyst component (A) and the organoaluminum compound (B), the electron donor compound (C) may coexist if necessary. The electron donor compounds used are part or all of the above-mentioned electron donor compounds (C). Relative to each mole of titanium atom contained in the solid catalyst component (A), its dosage is preferably 0.01-400mol, more preferably 0.02-200mol, particularly preferably 0.03-100mol; and relative to each mole of organoaluminum compound (B), its The amount used is preferably 0.003-5 mol, more preferably 0.005-3 mol, particularly preferably 0.01-2 mol.

The method of adding the electron donor compound (C) in the prepolymerization is not particularly limited. It can be added independently of the organoaluminum compound (B), as well as after being contacted with the organoaluminum compound (B). The olefin in the prepolymerization may be the same or different from the olefin used in the main polymerization.

After performing prepolymerization as described above, or without prepolymerization, the α- In the presence of an olefin polymerization catalyst, the main polymerization of α-olefin is carried out.

The amount of the organoaluminum compound used in the main polymerization can be selected from a wide range of 1 to 1000 mol relative to each mole of titanium atoms contained in the solid catalyst component (A), and the amount of the organic aluminum compound used in the main polymerization can be selected from a wide range of 1 to 1000 mol. The range of 5-600 mol per mole of titanium atoms is particularly preferred.

In this polymerization, the amount of the electron donor compound (C) is preferably 0.1-2000 mol, more preferably 0.3-1000 mol, particularly preferably 0.5-800 mol, relative to each mole of titanium atom contained in the solid catalyst component (A). Per mole of the organoaluminum compound (B), the amount used is preferably 0.001-5 mol, more preferably 0.005-3 mol, particularly preferably 0.01-1 mol.

The main polymerization can be performed at -30 to 300°C, preferably at 20 to 180°C. There is no particular limitation on the polymerization pressure. However, from the viewpoint of industry and economy, the pressure is preferably from normal pressure to 100 kg/cm ² , more preferably from 2 to 50 kg/cm ² . As the polymerization form, batch polymerization or continuous polymerization may be used. slurry polymerization or solution polymerization in the presence of an inert solvent such as propane, butane, isobutane, pentane, hexane, heptane, or octane, bulk polymerization using a liquid hydrocarbon at the polymerization temperature, and Media or gas phase polymerizations can also be employed.

In the main polymerization, a chain transfer agent such as hydrogen may be added to control the molecular weight of the produced polymer.

Example

The present invention will be described in detail with reference to the following examples and comparative examples, but the present invention is not particularly limited thereto. The evaluation methods of various material properties of the polymer in the examples are as follows: (1) xylene-soluble amount (hereinafter referred to as CXS) at 20°C

After 1 g of the polymerized powder was dissolved in 200 ml of boiling xylene, the resulting solution was slowly cooled to 50°C and then cooled to 20°C while stirring. After standing at 20° C. for 3 hours, the precipitated polymer was isolated by filtration. The xylene was evaporated in vacuo at 60°C, so that drying was obtained, and the polymer soluble in xylene at 20°C was recovered. (2) Intrinsic viscosity (hereinafter referred to as [η])

It is measured with tetralin at 135°C. (3) Bulk density

It is determined according to JiS K-6721-1966. The synthesis of embodiment 1 (a) solid catalyst component

After a 200ml flask with a stirrer and a funnel replaced the air with nitrogen, the copolymer of 8.2g styrene-divinylbenzene (the result of measuring with a porosimeter is: the micropores with a micropore diameter of 100-5000 Å The volume (dVp) is 1.14cc/g), 41ml of toluene, 0.17ml of diisobutyl phthalate, 0.45ml of tetrabutoxytitanium and 5.0ml of tetraethoxysilane were added to the flask and stirred at room temperature 2 hours. Then keep 5 DEG C in the flask, slowly drop the di-n-butyl ether solution (produced by YUKI GOSEI YAKUHIN Co., Ltd. of YUKI GOSEI YAKUHIN Co., Ltd., the concentration of n-butylmagnesium chloride of 11.6ml from funnel is 2.1mmol) /ml).

After the dropwise addition was completed, it was stirred at 5°C for 30 minutes at room temperature, and then further stirred at 35°C for 3 hours. After the resulting mixture was separated into solid and liquid, the resulting solid was repeatedly washed three times with 73 ml of toluene, and then 60 ml of toluene was added.

A portion of the solid product slurry was used as a sample for component analysis. The titanium atom was 0.41% by weight, the ethoxyl group was 9.3% by weight, and the butoxyl group was 0.6% by weight in the solid product. The slurry concentration was 0.19 g/ml. (b) Synthesis of ester-treated solids

After removing 21 ml of toluene supernatant from the slurry containing the solid product obtained in (a) above, the temperature of the slurry in the flask was raised to 95°C and stirred for 1 hour. Then 3.7 ml of diisobutyl phthalate was added, and the mixture was reacted at 95° C. for 30 minutes. After the reaction, the resulting reaction mixture was separated into solid and liquid. The resulting solid was washed twice with 73 ml of toluene. (c) Synthesis of solid catalyst components (activation treatment)

After washing in (b) above, 39ml of toluene, 0.29ml of diisobutyl phthalate, 0.33ml of di-n-butyl ether and 39ml of titanium tetrachloride were added to the flask, and reacted at 105°C for 3 hours. After the reaction was completed, the resulting mixture was subjected to solid-liquid separation at the same temperature. And the obtained solid was washed twice with 73 ml of toluene at the same temperature. Next, 39 ml of toluene, 0.29 ml of diisobutyl phthalate, 0.33 ml of di-n-butyl ether and 39 ml of titanium tetrachloride were added to the washed solid, and reacted at 105° C. for 1 hour. After the reaction was completed, the resulting mixture was subjected to solid-liquid separation at the same temperature, and the gained solid was washed three times with 73ml toluene at the same temperature, and then the gained solid was washed three times with 73ml hexane, and vacuum-dried to obtain 11.7g solid catalyst component .

In the above solid catalyst component, 0.35% by weight of titanium atom, 2.1% by weight of phthalate, and 0.1% by weight of ethoxyl group were contained, and no butoxyl group was detected. (d) Polymerization of propylene

A 3-liter stirred stainless steel reactor was replaced with argon, and 2.6 mmol of triethylaluminum, 0.26 mmol of cyclohexylethyldimethoxysilane, and 43.3 mg of the solid catalyst synthesized in (c) were added to the reactor Components, and add corresponding 0.33kg/cm ² partial pressure of hydrogen.

Next, 780 g of liquid propylene was added to the reactor, the temperature of the reactor was increased to 80° C., and the polymerization reaction was carried out at 80° C. for 1 hour. After the end of the polymerization, unreacted monomers were discharged. The produced polymer was vacuum-dried at 60° C. for 2 hours to obtain 282 g of polypropylene powder.

Therefore, the yield of polypropylene per gram of solid catalyst component (hereinafter abbreviated as pp/Cat) was 6,510 (g/g). At 20°C, the xylene-soluble fraction (CXS) of all products was 0.7 (wt%), the intrinsic viscosity [η] of the polymer was 1.82, and the bulk density was 0.47 (g/ml). The synthesis of comparative example 1 (a) solid catalyst component

After a 200ml flask with stirrer and funnel replaced the air with nitrogen, the copolymer of 8.2g styrene-divinylbenzene as in embodiment 1 (a), 41ml toluene, 0.45ml tetrabutoxytitanium and 5.0ml of tetraethoxysilane was added to the flask, and after washing three times with 73ml of toluene at a certain temperature, the obtained solid was washed three times with 73ml of hexane and dried in vacuum to obtain 11.7g of solid catalyst component.

The solid catalyst component contained 0.51% by weight of titanium atom, 3.3% by weight of phthalate, 0.2% by weight of ethoxy group and 0.01% by weight of butoxyl group. (d) Polymerization of propylene

Polymerization of propylene was carried out in the same manner as in Example 1(d) except that the solid catalyst component obtained in (c) above was used, and pp/Cat was 4,830 (g/g). CXS was 0.9 (wt%), [η] was 1.75, and bulk density was 0.48 (g/ml).

According to the present invention, there is provided an α-olefin polymerization catalyst having such high stereoregularity and catalytic activity that it is not necessary to remove catalyst residues and amorphous polymers, and has a high bulk density and little The fine particles do not contain inorganic oxides such as silica gel, which can form fish eyes in film-forming applications, and also provide a method for producing high-quality and high-stereoregular alpha-olefin polymers. and stirred at room temperature for 2 hours. Then keep 5 DEG C in the flask, slowly drop the di-n-butyl ether solution (produced by YUKI GOSEI YAKUHIN Co., Ltd. of YUKI GOSEI YAKUHIN Co., Ltd., the concentration of n-butylmagnesium chloride of 11.2ml from funnel is 2.1mmol) /ml). After the dropwise addition was completed, the resulting mixture was stirred at 5°C for 30 minutes at room temperature, and then further stirred at 35°C for 3 hours. A solid was obtained after solid-liquid separation of the resulting mixture, and the obtained solid was repeatedly washed three times with 73 ml of toluene, and 60 ml of toluene was added to the washed solid.

A part of the solid product slurry is used as a sample, and the component analysis is carried out to the slurry. In the solid product, the titanium atom is 0.44% (weight), the ethoxy group is 9.6% (weight), and the butoxyl group is 0.64% (weight). The concentration of the slurry is 0.19g/ml. (b) Synthesis of ester-treated solids

After removing 21 ml of toluene supernatant from the slurry containing the solid product obtained in (a) above, the temperature of the slurry in the flask was raised to 95°C and stirred for 1 hour. Then 3.1 ml of diisobutyl phthalate was added and reacted at 95°C for 30 minutes. After the reaction, the resulting reaction mixture was separated into solid and liquid. The resulting solid was washed twice with 73 ml of toluene. (c) Synthesis of solid catalyst components (activation treatment)

After washing in (b) above, 39ml of toluene, 0.29ml of diisobutyl phthalate, 0.33ml of di-n-butyl ether and 39ml of titanium tetrachloride were added to the flask, and reacted at 105°C for 3 hours. After the reaction was completed, the resulting mixture was subjected to solid-liquid separation at the same temperature. And the obtained solid was washed twice with 73 ml of toluene at the same temperature. Next, 39 ml of toluene, 0.29 ml of diisobutyl phthalate, 0.33 ml of di-n-butyl ether and 39 ml of titanium tetrachloride were added, and reacted at 105° C. for 1 hour. After the reaction was completed, the resulting mixture was subjected to solid-liquid separation at the same temperature, and the separated solids were separated at the same temperature.

Claims (23)

1. alpha-olefin polymerization catalyst, it contains:

(A) contain the solid catalytic ingredient of trivalent titanium compound, it obtains by handle a kind of solid phase prod with ester cpds, this solid phase prod is under the condition that has silicoorganic compound, porous polymer particle and ester cpds to exist, and reduces Ti (OR with organo-magnesium compound ¹) _aX _4-a(R ¹Represent the alkyl that 1-20 carbon atom arranged, X represents halogen atom, a represents it is a number that satisfies 0＜a≤4) obtain, described silicoorganic compound have the Si-O key, the aperture of described porous polymer particle is 100-5000 , micro pore volume is 0.1cc/g or bigger, then the solid of handling with ester with the mixture process of the mixture of ether compound and titanium tetrachloride or ether compound, titanium tetrachloride and ester cpds;

(B) organo-aluminium compound; With

(C) electronic donor compound capable.

2. according to the alpha-olefin polymerization catalyst of claim 1, it is characterized in that: the silicoorganic compound that contain the Si-O key in the molecule are selected from the group of being made up of the silicoorganic compound of following general formula representative: Si (OR ²) _mR ³ _4-mR ⁴(R ⁵ ₂SiO) _pSiR ⁶ ₃(R ⁷ ₂SiO) _qR wherein ²Be the alkyl that 1-20 carbon atom arranged, R ³, R ⁴, R ⁵, R ⁶, R ⁷Be alkyl or the hydrogen atom that 1-20 carbon atom arranged, m is a number that satisfies 0＜m≤4, and p is the integer of a 1-1000, and q is the integer of a 2-1000.

3. according to the alpha-olefin polymerization catalyst of claim 1, it is characterized in that: organo-magnesium compound is selected from the group of being made up of the organo-magnesium compound of following general formula representative: R ⁸MgX; And R ⁹R ¹⁰Mg is R wherein ⁸, R ⁹And R ¹⁰Be the alkyl that 1-20 carbon atom arranged, X is a halogen atom.

4. according to the alpha-olefin polymerization catalyst of claim 1, it is characterized in that: be used in the processing of reduction solid or and be selected from the group of forming by representative examples of saturated aliphatic carboxylic ester, unsaturated aliphatic carboxylicesters, alicyclic carboxylic ether and aromatic carboxylic acid esters as the ester cpds in ether compound, titanium tetrachloride and the ester cpds mixture.

5. according to the alpha-olefin polymerization catalyst of claim 1, it is characterized in that: ether compound is selected from the group of being made up of dialkyl ether, and wherein each alkyl has 2-10 carbon atom, and can be identical or different.

6. according to the alpha-olefin polymerization catalyst of claim 1, it is characterized in that: the diameter of polymer particles is 5-1000 μ.

7. according to the alpha-olefin polymerization catalyst of claim 1, it is characterized in that: in the processing of solid phase prod, each mole titanium atom in the relative solid phase prod, the consumption of ester cpds is 0.1-50mol, each mole magnesium atom in the relative solid phase prod, the consumption of ester cpds is 0.01-1.0mol.

8. according to the alpha-olefin polymerization catalyst of claim 1, it is characterized in that: electronic donor compound capable is selected from the group of being made up of alcohol, phenol, ketone, aldehyde, carboxylic acid, organic acid acetic, inorganic acid ester, ether, acid amides, acid anhydride, ammonia, amine, nitrile, isocyanic ester.

9. alpha-olefin polymerization catalyst according to Claim 8 is characterized in that: electronic donor compound capable is selected from by the inorganic acid ester with following general formula representative: R ¹⁶ _nSi (OR ¹⁷) _4-nWherein, R ¹⁶Be alkyl or the hydrogen that 1-20 carbon atom arranged, R ¹⁷Be the alkyl that 1-20 carbon atom arranged, R in a part ¹⁶, R ¹⁷Can be different, n is a number that satisfies 0≤n＜4, and ether is shown from generation to generation by following general formula: Wherein, R ¹⁸-R ²¹Be respectively the alkyl that 1-20 carbon atom arranged, alicyclic radical, aryl, alkaryl or aralkyl straight chain or side chain, R ¹⁸Or R ¹⁹Can be hydrogen.

10. method of producing alpha-olefinic polymer comprises with the alpha-olefin polymerization catalyst polymerization of Alpha-olefin that contains following component:

(A) contain the solid catalytic ingredient of trivalent titanium compound, it obtains by handle a kind of solid phase prod with ester cpds, this solid phase prod is under the condition that has silicoorganic compound, porous polymer particle and ester cpds to exist, and reduces Ti (OR with organo-magnesium compound ¹) _aX _4-a(R ¹Represent the alkyl that 1-20 carbon atom arranged, X represents halogen atom, a represents it is a number that satisfies 0＜a≤4) obtain, described silicoorganic compound have the Si-O key, the aperture of described porous polymer particle is 100-5000 , micro pore volume is 0.1cc/g or bigger, then the solid of handling with ester with the mixture process of the mixture of ether compound and titanium tetrachloride or ether compound, titanium tetrachloride and ester cpds;

(B) organo-aluminium compound; With

(C) electronic donor compound capable.

11. the method according to the production alpha-olefinic polymer of claim 10 is characterized in that: the silicoorganic compound that are used for reduction reaction are selected from the group of being made up of the silicoorganic compound of following general formula representative: Si (OR ²) _mR ³ _4-mR ⁴(R ⁵ ₂SiO) _pSiR ⁶ ₃(R ⁷ ₂SiO) _qR wherein ²Be the alkyl that 1-20 carbon atom arranged, R ³, R ⁴, R ⁵, R ⁶, R ⁷Be alkyl or the hydrogen atom that 1-20 carbon atom arranged, m is a number that satisfies 0＜m≤4, and p is the integer of a 1-1000, and q is the integer of a 2-1000.

12. according to the method for the production alpha-olefinic polymer of claim 10, it is characterized in that: organo-magnesium compound is selected from the group of being made up of the organo-magnesium compound of following general formula representative: R ⁸MgX; And R ⁹R ¹⁰Mg is R wherein ⁸, R ⁹And R ¹⁰Be the alkyl that 1-20 carbon atom arranged, X is a halogen atom.

13. the method according to the production alpha-olefinic polymer of claim 10 is characterized in that: wherein be used in the reduction solid handle in or be selected from the group of forming by representative examples of saturated aliphatic carboxylic ester, unsaturated aliphatic carboxylicesters, alicyclic carboxylic ether and aromatic carboxylic acid esters as the ester cpds in ether compound, titanium tetrachloride and the ester cpds mixture.

14. according to the method for the production alpha-olefinic polymer of claim 10, it is characterized in that: ether compound is selected from the group of being made up of dialkyl ether, wherein each alkyl has 2-10 carbon atom, and can be identical or different.

15. according to the method for the production alpha-olefinic polymer of claim 10, it is characterized in that: wherein the diameter of polymer particles is 5-1000 μ.

16. method according to the production alpha-olefinic polymer of claim 10, it is characterized in that: in the processing of solid phase prod, each mole titanium atom in the relative solid phase prod, the consumption of ester cpds is 0.1-50mol, each mole magnesium atom in the relative solid phase prod, the consumption of ester cpds is 0.01-1.0mol.

17. according to the method for the production alpha-olefinic polymer of claim 10, it is characterized in that: organo-aluminium compound is selected from the group of being made up of the organo-aluminium compound of following general formula representative: R ¹¹ _γAlY _3-γAnd R ¹²R ¹³Al-O-AlR ¹⁴R ¹⁵R wherein ¹¹-R ¹⁵Representative has the alkyl of 1-20 carbon atom, and Y represents halogen, hydrogen or alkoxyl group, and γ is a number that satisfies 2≤γ≤3.

18. the method according to the production alpha-olefinic polymer of claim 10 is characterized in that: each mole titanium atom that is contained in the solid catalyst relatively, the consumption of organo-aluminium compound is 0.5-1000mol.

19. according to the method for the production alpha-olefinic polymer of claim 10, it is characterized in that: electronic donor compound capable is selected from the group of being made up of alcohol, phenol, ketone, aldehyde, carboxylic acid, organic acid acetic, inorganic acid ester, ether, acid amides, acid anhydride, ammonia, amine, nitrile, isocyanic ester.

20. the method according to the production alpha-olefinic polymer of claim 19 is characterized in that: electronic donor compound capable is selected from by the inorganic acid ester with following general formula representative:

R ¹⁶ _nSi (OR ¹⁷) _4-nWherein, R ¹⁶Be alkyl or the hydrogen that 1-20 carbon atom arranged, R ¹⁷Be the alkyl that 1-20 carbon atom arranged, R in a part ¹⁶, R ¹⁷Can be different, n is a number that satisfies 0≤n＜4, and the ether of following general formula representative: Wherein, R ¹⁸-R ²¹Be respectively the alkyl that 1-20 carbon atom arranged, alicyclic radical, aryl, alkaryl or aralkyl straight chain or side chain, R ¹⁸Or R ¹⁹Can be hydrogen.

21. according to the method for the production alpha-olefinic polymer of claim 10, it is characterized in that: be contained in each mole titanium atom in the solid catalytic ingredient (A) relatively, the amount of electronic donor compound capable (C) is 0.1-1000mol.

22. the method according to the production alpha-olefinic polymer of claim 10 is characterized in that: carried out prepolymerization before alpha-olefine polymerizing.

23. according to the method for the production alpha-olefinic polymer of claim 10, it is characterized in that: polymerization is to carry out with the form of slurry polymerization, solution polymerization, mass polymerization or vapour phase polymerization.

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