JPH0395208A - Preparation of olefin polymer - Google Patents

Abstract

PURPOSE:To stably prepare an olefin polymer excellent in the transparency and crystallizability by polymerizing an olefin in the presence of a catalyst contg. a specific solid catalyst component contg. titanium. CONSTITUTION:A process for producing an olefin polymer by polymerizing an olefin in the presence of a catalyst comprising a titanium-contg. solid catalyst component, an organoaluminum compd., and, if required, an electron donor, wherein the titanium-contg. catalyst component is one which, in the course of its production, has undergone a polymn. treatment with a linear olefin and styrene in the presence of a reaction product of the organoaluminum compd. with water and has passed through subsequent process. For example, a solid product obtd. by reacting TiCl4 with the organoaluminum compd. or with a reaction product of the organoaluminum with the electron donor is subjected to the polymn. treatment with the linear olefin and styrene in multisteps, each at least once, in the presence of the reaction product of the organoaluminum compd. with water, and the treated product is reacted with the electron donor and an electron acceptor to give a TiCl3 compsn. which is used as the titanium- contg. catalyst component.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for producing an olefin polymer, and more particularly, to a method for producing an olefin polymer, which uses a specific titanium-containing solid catalyst component to produce an olefin polymer with excellent crystallinity and transparency. Concerning methods for producing polymers. (Prior art and its problems) Crystalline olefin polymers such as crystalline polypropylene are composed of transition metal compounds of groups ■ to ■ of the periodic table and organometallic compounds of metals of groups 1-III of the periodic table. It is well known that olefins can be obtained by polymerizing olefins using Ziegler-Natsuta catalysts, and among them, various titanium trichloride compositions, titanium, magnesium, halogens, and electron donors are used as transition metal compound catalyst components. Titanium-containing solid catalyst components, such as titanium-containing supported catalyst components, are widely used. Olefin polymers such as polybropylene obtained by the above method are superior in light weight, shapeability, mechanical strength, chemical stability, etc. compared to other plastics, and are also economically advantageous. Therefore, it is widely used in the production of various filIi-shaped products including films and sheets. However, when olefin polymers are shaped using conventional methods, the resulting molded products have problems such as not being as rigid as expected due to low crystallinity, and problems such as the molded products being translucent. Was. For this reason, attempts have been made to increase the crystallinity and improve the transparency of olefin polymers. 131.2H (hereinafter referred to as the prior invention) is proposed. The proposed composition has the effect of improving crystallinity to a certain degree, but since it uses a method of mixing syndiotactic polystyrene obtained by separate polymerization with polypropylene, syndiotactic polystyrene is separately obtained. Not only does this have the industrial disadvantage of requiring a manufacturing process, but the dispersibility of syndiotactic polystyrene into polypropylene is poor, resulting in insufficient nucleation and voids when made into a film. yA that will occur!
It had Il1. The present inventors have conducted extensive research into a method for producing highly crystalline olefin polymers that solves the problems faced by previous inventions. As a result, a titanium-containing solid catalyst component containing a syndiotactic styrene polymer block was discovered using a specific method, and olefins were polymerized using this titanium-containing solid catalyst component and a catalyst consisting of at least an organic alkalicum compound. The present inventors have discovered that the problems of the prior inventions described above can be solved by producing an olefin polymer using the same method as described above, leading to the present invention. As is clear from the above description, an object of the present invention is to provide a method for producing an olefin polymer with excellent crystallinity and transparency without industrial disadvantages. Another purpose is to provide an olefin polymer with excellent crystallinity and transparency. (Means for Solving Problem Ll) The present invention has the following features. (1) ■Titanium-containing solid catalyst component, ■Organoaluminum compound (A3), and, if necessary, ■Electron donor. In the method of producing an olefin polymer by polymerizing olefin using a catalyst consisting of (at), (1) a combination of an organoaluminum compound (A3) and water as a titanium-containing solid catalyst component during the production of the titanium-containing solid catalyst component; A method for producing an olefin polymer, characterized by using a titanium-containing solid catalyst component obtained by polymerization treatment with a straight-set olefin and styrene in the presence of a reaction product (A3) and further subsequent steps. (2) ) As a titanium-containing solid catalyst component, an organoaluminum compound (A4) or an organoaluminum compound (
A solid product (I!) obtained by reacting the reaction product (I) of A4) with an electron donor (B3) with titanium tetrachloride is reacted with an organic aluminum compound (A3) and water. In the presence of the product (A3), polymerization is carried out in multiple stages, one or more times each with a direct olefin and styrene, and then an electron donor (
83) and an electron acceptor. (3) As a titanium-containing solid catalyst component, a solid raw material (IV) obtained by contacting a liquefied magnesium compound with a precipitating agent, a halogen compound, an electron donor (B4), and a titanium compound (T+), Organoaluminum compound (A
2> and water In the presence of the raw material (A3), polymerization is carried out in multiple stages, one or more times each, with straight olefin and styrene.
A solid product (V) was obtained, and a halogen compound (T
2) is obtained by reacting the titanium-containing supported catalyst component (
The manufacturing method according to the above item 1 using V1). (0 organoaluminum compound (A-, the general formula is 81R'J
"p4s-ip*p・+ (wherein, Rl1R2 is a hydrocarbon group such as an alkyl group, cycloalkyl group, or aryl group*
or an alkoxy group, X represents a halogen, and ρ,
p'' represents an arbitrary number of O<p+p'≦3. ) The manufacturing method according to item 1 above, using an organoaluminum compound represented by: (5) Organoaluminum compound (A2)
The manufacturing method according to the above item 1 using trimethylaluminum. (6) In place of the titanium-containing solid catalyst component, a titanium-containing solid catalyst component and an organoaluminum compound (A1). The production method according to item 1 above, which uses a catalyst component which is preactivated by combining and, if necessary, an electron donor (B3) and reacting this with a small amount of solenoid. The structure of the present invention will be explained in detail below.

The titanium-containing solid catalyst component used in the production of the olefin polymer of the present invention may be directly quenched in the presence of a reaction product (A3) of the organoaluminum compound (A2) and water during the production of the titanium-containing solid catalyst component. A titanium-containing solid catalyst component obtained by polymerization using olefin and styrene and further subsequent steps is used. To specifically explain the method for producing such a titanium-containing solid catalyst component, for example, an organoaluminum compound (A4
) and the electron donor (82) to form a reaction product (1
), and a solid product (II) obtained by reacting this (1) with titanium tetrachloride, or a solid product obtained by reacting an organic aluminum compound (A4) with titanium tetrachloride. compound (II), an organoaluminum compound (
In the presence of the reaction product (A3) of A3) and water, the direct daughter olefin and styrene are each polymerized in multiple stages at least once, and further (by reacting an electron donor (aS) with an electron acceptor). The final titanium trichloride composition obtained (Ill
), the titanium-containing solid catalyst component is produced. In the present invention, "to polymerize" means to polymerize a direct olefin or styrene into a solid product (
11) or the direct polymerization of olefin or styrene by contacting with a solid product (!V) described below. This polymerization! A solid product (TI)
, or the solid raw material (rV) becomes coated with the polymer. The above-mentioned organic aluminium compound (A4) and an electron donor (
The reaction with B3) is carried out in the solvent (D1) at -20°C to 200°C.
℃, preferably -10℃ to 100℃ for 30 seconds to 5 hours. Organoaluminum compounds (A4), (B2), (
There is no restriction on the order of addition of DI), and the ratio of the amount of electron donor (B
z) 0.1 mol to 8 mol, preferably 1 to 4 mol, solvent 0.5 L to 5 L, preferably 0.5 L to 2 L. Thus, the reaction product (!) is obtained. Reaction product (I)
) can be used for the next reaction in the liquid state (sometimes referred to as reaction liquid (1)) after the reaction has completed without separation. Next, this reaction product (!) is reacted with titanium tetrachloride, or the organic aluminum compound (A4) and titanium tetrachloride are reacted to obtain a solid product (I1).
0°C to 2GQ°C, preferably 0°C to 100°C, S min to 1
Perform for 0 hours. Although it is preferable not to use a solvent, aliphatic or aromatic hydrocarbons can be used. Reaction product (1) or organoaluminum compound (A
4>, titanium tetrachloride, and the solvent may be mixed in any order. (■) or organoaluminum compound (A
4) It is preferable that the mixing of the entire amount of titanium tetrachloride and the solvent be completed within 5 hours, and the reaction will continue during the mixing. It is preferable to continue the reaction for another 5 hours after mixing the entire amount.

The amount of each used in the reaction is 1 mol of titanium tetrachloride, 0~3,000mJ2 of solvent, 1 mol of titanium tetrachloride,
) or the organoaluminum compound (A4) is the (1
) or ^If in organoaluminum compound (A4)
The ratio of the number of f atoms to the number of Ti atoms in titanium tetrachloride (A1/T0
is 0.05 to 10, preferably 0.06 to OJ. The thus obtained solid product (I1) is subjected to multistage polymerization treatment with a direct daughter olefin and styrene in the presence of a reaction product (A3) of an organoaluminum compound (A2) and water. As the polymerization treatment method, after the reaction between the reaction product (1) or the organoaluminum compound (A4) and titanium tetrachloride is completed, the liquid portion is separated and removed by filtration or decantation, and the obtained solid raw material is Things (11)
) is dissolved in a solvent, and then an organoaluminum compound (
After adding the reaction product (A3) of A3) and water, a method can be mentioned in which directly added olefin and styrene are added in multiple stages and polymerized. Note that the above polymerization treatment using straight chain olefin and styrene may be performed by polymerization treatment using styrene alone, but using straight chain olefin and styrene, first polymerization IA3l is performed with straight chain olefin, and then polymerization treatment is performed with ■styrene. This method is preferred from the viewpoint of polymerization operability when using the obtained titanium-containing solid catalyst component and the quality of the obtained olefin polymer. Furthermore, the polymerization treatment can be carried out by using linear olefin and styrene at least once each as described above.
It is also possible to perform the polymerization process two or more times, for example, by adding straight chain olefin after the styrene polymerization process. As for the reaction conditions for the polymerization treatment, solid raw material (L) is
1) The titanium atoms in the organic aluminum compound (A
The molar ratio of aluminum in the reaction product (A3) of 2) and water is 20:1 to 1:5×10', preferably 4:1.
~ 1:2 Atmospheric pressure (O kgf/clIl'G) ~ 10 kgf/cm"
Under the conditions of G, per 100g of solid product (■), 100a+J2~Sofl, 0.1g~ of straight olefin
100kg, and 0.01g of styrene A-100
kg, in the final titanium trichloride compound (■), the content of the direct-painted olefin polymer block is 0.1% to 49.5% by weight, and the content of the styrene polymer block is 0. Polymerize so that the weight of Ol is 49.5% by weight. The content of the styrene polymer block is 0.01% by weight
In Suemitsu, the effect of improving the crystallinity and transparency of the olefin polymer produced using the titanium-containing solid catalyst obtained was insufficient, and the improvement of the effect was not significant beyond the above range. , resulting in operational and economic disadvantages.

In addition, as mentioned above, it is preferable to use not only styrene but also a linear olefin in the polymerization treatment, and in this case,
The weight ratio of the straight-set olefin polymer block to the styrene polymer block is preferably 2/98 to 98/2, considering both the effect of improving driveability and the effect of improving the quality of the obtained olefin polymer. ．． In any of the above-mentioned polymerization treatments, after each stage of polymerization treatment using a straight-chain olefin or styrene is completed, the reaction mixture can be used as it is in the next stage of polymerization treatment. In addition, the coexisting solvent, unreacted linear olefin or styrene, and the reaction product (A3) of the organoaluminum compound (A2) and water are removed by filtration or decantation, and the solvent and the organoaluminum compound (A3) are removed again. A reaction product (A3) of A3) and water may be added and used in the next step of polymerization treatment with styrene or direct olefin.

The solvent used during the polymerization process is an aliphatic hydrocarbon, an alicyclic hydrocarbon, or an aromatic hydrocarbon.

After the reaction is completed, the liquid part is separated and removed by filtration or decantation, and then washing is repeated with a solvent.
The obtained solid product subjected to polymerization treatment (hereinafter sometimes referred to as solid product (II-A)) may be used in the next step while suspended in a solvent, or it may be further dried to form a solid product. You can take it out and use it as an object. The solid biosediment (II-A) is then reacted with an electron donor (B3) and an electron acceptor (F).

Although this reaction can be carried out without using a solvent, better results are obtained using an aliphatic hydrocarbon. The amount used is (Bs) O. lg to 1,000g, preferably 0.1g.
5g ~200g, (F) 0.1g ~1,00
0g, preferably 0.2g to 500g, solvent 0 to 3
, OOO+l . Preferably 100 ~ J, OOOmf
There is one.

As for the reaction method, ■solid raw material (11-A'
) is reacted with an electron donor (B3) and an electron acceptor (F) at the same time, ■ (u-A) is reacted with (F) and then (Bs) is reacted, ■ (II
- Method of reacting A) with (B3) and then reacting (F), ■ After reacting (B3) with (F), (T
There is a method of reacting I-A), but any method may be used.

The reaction conditions are 40°C to
It is desirable to react at 200°C, preferably 50°C to 100°C for 30 seconds to 5 hours.
If-A) and (B3) were reacted at 0°C to 50°C for 1
After reacting for minutes to 3 hours, it is reacted with (F) under the same conditions as in (1) and (2) above.

In addition, in method (■), (B3) and (F) are heated at 10°C to 1
After reacting at 00°C for 30 minutes to 2 hours, cooled to 40°C or lower, and adding (II-A''), the above
React under 12 conditions as in ②. After the reaction of the solid products (II-A), (B3), and (F) is completed, the liquid portion is removed by filtration or decantation, and then washing is repeated with a solvent.
A titanium trichloride combination compound (II!), which is a titanium-containing solid catalyst component used in the present invention, is obtained.

The organoaluminum compound (A4) used in the production of the titanium trichloride composite (II1) has the general formula 81R'pR"1xs-{p*p'+ <wherein, R',
R2 represents a hydrocarbon group such as an alkyl group, a cycloalkyl group, an aryl group, or an alkoxy group, X represents a halogen, and p. p' represents an arbitrary number of O<p+p'≦3. ) is used. Specific examples include trimethylaluminum, triethylaluminum, tri-n-probylaluminium, tri-n-butylaluminum, tri-i-butylaluminum, tri-n-hexylaluminum, tri-I-hexylaluminum, tri-2-methylbentylaluminum. ,
Trialkylaluminiums such as tri-n-octylaluminium and tri-n-decylaluminum, diethylaluminum monochloride, di-n-probylaluminium monochloride, di-l-butylaluminum monochloride, diethylaluminium monofluoride, diethyl dialkylaluminum monohalides such as al-aldium monobromide and diethylaluminium monoiodide; dialkylaluminum hydrides such as diethylaluminum hydride; alkylaluminium such as methylaluminum sesquichloride and ethylaluminum sesquichloride; Examples include sesquihalides, monoalkylaluminum dihalides such as ethylaluminum dichloride and 1-butylaluminum dichloride, and alkoxyalkylaluminums such as monoethoxydiethylaluminum and diethoxymonoethylaluminum can also be used. These organoaluminum compounds are 2f! It is also possible to mix and use more than one type.

During the polymerization treatment according to the present invention, a reaction product (A3) of an organic aluminum compound (A2) and water is used. Here, as the organic alkyl compound (A2), trialkylaluminum represented by the general formula AIR3, (wherein R3 represents an alkyl group having 1 to 8 carbon atoms), and the general formula R42^IX ( In the formula, R4 is a carbon number 1 to B
represents an alkyl group, and × represents a halogen. Examples include dialkylalkylaltanium monohalides represented by 〉. Specifically, trimethylalbinium, triethylaluminum, tri-n-propylaluminium, tri-l-propylaluminium, tri-n-butylaluminum, tri! -butylaluminum, tri-n-hexylaluminum, tri-n-octylaluminium, diethylaluminium monochloride, di-n-probylaluminum monochloride, di-1-butylaluminum monochloride, dietylaluminum monofluoride, Examples include diethylaluminum monobromide, diethylaluminum-based nicum monoiodide, and trimethylaluminum is particularly preferred. The product (A3) obtained by reacting the above organoaluminum compound (A2) with water is mainly produced by the following general formula [1
1 and an alkylalkyl-based noxane represented by the general formula [I1] or the general formula [I] or the general formula C n ]
is a halogenated aluminoxane in which R is partially substituted with a halogen atom such as chlorine or bromine, and the halogen content is 401% by weight or less, preferably 30% by weight or less. R (wherein; R is an alkyl group having 1 to 8 carbon atoms, and n is 1
~ is an integer of about 20. ) There are various methods for reacting the organoaluminum compound (A2) with water in this case, and the following method can be exemplified.

(1) Organoaluminum compound (A2) is added to a hydrocarbon medium suspension of a compound containing adsorbed water or a salt having crystal water, such as copper sulfate hydrate, aluminum sulfate hydrate, magnesium chloride hydrate, etc. Method of addition and reaction. (2) A method in which water is allowed to directly act on the organoaluminum compound (A2) in a solvent such as benzene, toluene, or ethyl ether. In the polymerization treatment according to the present invention, not only the reaction product (A3) of the above-mentioned organic aluminium compound (A2) and water can be used alone, but also this product (A3) and an unreacted organic aluminum compound can be used. It is also possible to use a mixture of (A2). As the electron donor used in the production of the titanium trichloride composite compound (III), which is the titanium-containing solid catalyst component used in the present invention, the following various ones can be used,
(B2), (BS) mainly uses ethers,
It is preferable to share other electron donors with ethers. Those used as electron donors are organic compounds having any of oxygen, nitrogen, sulfur, and phosphorus atoms, that is,
Ethers, alcohols, esters, aldehydes, fatty acids, ketones, nitriles, amines, atoms, urea or thioureas, isocyanates, azo compounds, phosphines, phosphites, phosphinites , hydrogen sulfide or thioethers, thioalcohols, silanols, and organosilicon compounds having a 51-0-(: bond. Specific examples include dimethyl ether, diethyl ether, di-n-probyl ether, di-n -butyl ether, di-l-arenyl ether, di-n-bentyl ether, di-n-hexyl ether, di-i-hexyl ether, di-n-octyl ether, di-l-octyl ether, di-n-dodecyl ether, diphenyl ether, ethylene Ethers such as glycol monoethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, methanol, ethanol, probanol,
Alcohols such as butanol, pentanol, hexanol, octanol, 2-ethylhexanol, allyl alcohol, benzyl alcohol, ethylene glycol, glycerin, phenols such as phenol, cresol, xylenol, ethylphenol, naphthol, methyl methacrylate, methyl formate , methyl acetate, methyl butyrate, ethyl acetate, vinyl acetate, n-probyl acetate, l-propyl acetate, butyl formate, aryl acetate, n-butyl acetate, octyl acetate, phenyl acetate, ethyl blobionate, methyl benzoate, Ethyl benzoate, brovyl benzoate, butyl benzoate, octyl benzoate, 2-ethylhexyl benzoate, methyl toluate, ethyl toluate,
Methyl anisate, ethyl anisate, probyl anisate,
Phenyl anisate, ethyl cinnamate, methyl naphthoate, ethyl naphthoate, brobyl naphthoate, butyl naphthoate, naphthoate al! Monocarboxylic acid esters such as 2-ethylhexyl and ethyl phenylacetate, aliphatic polycarboxylic acid esters such as diethyl succinate, diethyl methylmalonate, diethyl butylmalonate, dibutyl maleate, diethyl butylmaleate, monomethyl phthalate , dimethyl phthalate, diethyl phthalate, di-n-probyl phthalate, mono-n-butyl phthalate, di-n-butyl phthalate, di-l-butyl phthalate, di-n-heptyl phthalate, di-2-ethylhexyl phthalate ,
Aromatic polyesters such as di-n-octyl phthalate, diethyl isophthalate, diprobyl isophthalate, dibutyl isophthalate, di-2-ethylhexyl isophthalate, diethyl terephthalate, dibrobyl terephthalate, dibutyl terephthalate, di-l-butyl naphthalene dicarboxylate, etc. carboxylic acid esters, aldehydes such as acetaldehyde, brobionaldehyde, benzaldehyde, formic acid,
Carboxylic acids such as acetic acid, brobionic acid, butyric acid, oxalic acid, succinic acid, acrylic acid, maleic acid, valeric acid, benzoic acid,
Acid anhydrides such as benzoic anhydride, phthalic anhydride, and tetrahydrophthalic anhydride; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and benzofumione; nitrites such as acetonitrile and penzonitrile; methylamine, diethyl amine, and tributyl amine. Rin, triethanolamine, β(N,N-dimethylamino)ethanol, viridine, quinoline, α-vicolin, 2,4.6
-trimethylpyridine, 2,2,6.8-tetramethylbiveridine, 2,2,5.5-tetramethylpyrrolidine, N,N,N',N'-tetramethylethylenediamine, aniline, dimethylaniline, etc. Ayones, formamide, hexamethylphosphoric triamide, N,N,N'
, N', N''-pentamethyl-N'-β-dimethylaminomethyl phosphoric acid triamide, octamethylbirophosphoramide, etc., N,N,N''. Ureas such as N°-tetramethylurea, isocyanates such as phenyl isocyanate and tolylisocyanate, azo compounds such as azobenzene, phosphines such as ethylphosphine, triethylphosphine, tri-n-octylphosphine, triphenylphosphine, and triphenylphosphine oxide. phosphites such as dimethyl phosphite, di-n-octyl phosphite, triethyl phosphite, 1-tri-n-butyl phosphite, triphenyl phosphite, ethyl diethyl phosphinite, ethyl butyl phosphinite, fluorophosphite, etc. Phosphinites such as nyldiphenylphosphinite, thioethers such as diethylthioether, diphenylthioether, methylphenylthioether, thioalcohols such as ethylthioalcohol, n-probylthioalcohol, thiophenol, thiophenols, trimethylsilanol , silanols such as triethylsilanol, triphenylsilanol,
Trimethylmethoxysilane, dimethyldimethoxysilane, methylphenyldimethoxysilane, diphenyldimethoxysilane, methyltrimethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, trimethylethoxysilane, dimethyldiethoxysilane, diphenyldiethoxysilane, Methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane,
Examples include organic silicones having Si-0-C bonds such as butyltriethoxysilane, phenyltriethoxysilane, ethyltri-l-proboxysilane, and vinyltriacetoxysilane. These electron donors can also be used in combination.

The electron donor (B2) for obtaining the reaction product (1) and (B3) for reacting with the solid product (II-A) may be the same or different. Linear olefins used for polymerization include ethylene,
Propylene, Ptene-1, Pentene-1, Hexene-1
, octene-1 and the like are used, and ethylene and propylene are particularly preferably used. These direct olefins are used in amounts of 1 fi or more. The electron acceptors (F) used in the present invention are shown in the periodic table ■~■
It is represented by the halides of group elements. Specific examples include anhydrous aluminum chloride, silicon tetrachloride, stannous chloride, stannic chloride, titanium tetrachloride, zirconium tetrachloride,
Examples include phosphorus trichloride, phosphorus pentachloride, vanadium tetrachloride, and antimony pentachloride, and these can also be used in combination. The most preferred is titanium tetrachloride. The following solvents are used as the solvent (D1). Examples of aliphatic hydrocarbons include n-pentane, n-hexane, n-hebutane, n-octane, i-octane, etc.
Halogenated hydrocarbons such as carbon tetrachloride, chloroform, dichloroethane, trichlorethylene, and tetrachlorethylene can also be used instead of or together with aliphatic hydrocarbons. Examples of alicyclic hydrocarbons include cyclohexane, methylcyclohexane, cyclohexene, cyclohebutane, cyclobentane, and cyclopentene. ．． Aromatic compounds include aromatic hydrocarbons such as benzene, toluene, xylene, naphthalene, mesitylene, deerene, ethylbenzene, and isopropylbenzene, and halogens such as chlorobenzene, chlorotoluene, chloroxylene, chloroethylbenzene, dichlorobenzene, and bromobenzene. A monster is shown. In addition to the titanium trichloride composition (Kawa) obtained as described above, for example, a liquefied magnesium compound, a precipitating agent, a halogen compound, an electron donor (B4), and a titanium compound (TI) are used. The solid product (JV) obtained by contacting is subjected to multi-stage polymerization treatment with direct daughter ol/fin and styrene in the presence of a reaction product (A3) of an organoaluminum compound (A3) and water to form a solid product. The titanium-containing supported catalyst component (V1) obtained by obtaining the product (V) and reacting the solid product (V) with the halogenated titanium compound (T3) is also a titanium-containing solid catalyst component used in the present invention. It can be used as The method for producing the titanium-containing supported catalyst component (■) is shown below. In addition, "liquefaction" of a magnesium compound as used in the present invention refers to cases in which the magnesium compound itself becomes a liquid, as well as cases in which the magnesium compound itself becomes soluble in a solvent and forms an i8 liquid,
This also includes cases in which a compound is solubilized in a solvent and forms a solution as a result of reacting with other compounds or forming a complex. In addition, the solution may be completely dissolved or may contain colloidal or semi-dissolved substances. The magnesium compound to be liquefied may be any compound that can be liquefied as described above, such as magnesium dihalide, alkoxymagnesium halide, aryloxymagnesium halide, dialkoxymagnesium, diary roxymagnesium, magnesium oxyhalide, magnesium oxide, magnesium hydroxide, magnesium carboxylate,
In addition to dialkylmagnesium, alkylmagnesium halide, etc., metal magnesium can also be used.

Moreover, these magnesium compounds or metal magnesium may be a reaction product with an electron donor, a silicon compound, or an aluminum compound.

A known method is used to liquefy the magnesium compound. For example, if a magnesium compound is mixed with alcohol,
A method of liquefying with an aldehyde, alkyl or carboxylic acid (JP-A-56-811, etc.), a method of liquefying with an orthotitanate ester (JP-A-54-40.29, etc.)
3, etc., method of liquefying with phosphorus compound (Tokuma 1973)
8-19307, etc.), as well as methods combining these methods. Furthermore, for organomagnesium compounds having a C-Mg bond to which the above method cannot be applied, since they are soluble in ether, dioxane, pyridine, etc., they can be used as a solution of these or reacted with an organometallic compound. The general formula is 1.11g. R", R'.
(M is an aluminium, zinc, boron, or beryllium atom, R5 and R6 are hydrocarbon residues, L Qs'
, s>O, if v is the valence of the gutter, then r◆s”vp◆2q
There is a relationship between ) can be formed (JP-A-50-139,885, etc.), dissolved in a hydrocarbon solvent, and liquefied. Furthermore, when metallic magnesium is used, it can be liquefied with alcohol and ortho-titanate (such as JP-A-50-51587), or reacted with an alkyl halide in ether using the so-called Grignard reagent. Among the above methods of liquefying a magnesium compound, for example, when magnesium chloride is dissolved in a hydrocarbon solvent (D2) using a titanate ester and alcohol. In terms of magnesium chloride, 0.1 to 2 moles of titanate, 0.1 to 5 moles of alcohol, and 0.1j of solvent (D2).
Using Z~5j2, mix each component in any order of addition,
The suspension is heated with stirring at 40°C to 200°C, preferably 150°C on the 50°C axis.

The time required for the reaction and dissolution is 5 minutes to 7 hours, preferably 10 minutes to 5 hours.

As the titanate ester, orthotitanate ester represented by Ti (OR') 4 and R8→0-Ti
(OR") (OR'Q+-h-OR"). Here, R7, R8,
R9, RIG and R1 are an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 3N20 carbon atoms, and t
is a number from 2 to 20. Specifically, methyl orthotitanate, ethyl orthotitanate, n-probyl orthotitanate, ono[l-propyl totitanate, n-butyl orthotitanate, l-butyl orthotitanate, lmn-amyl orthotitanate, Orthotitanate esters such as 2-ethylhexyl orthotitanate, n-octyl orthotitanate, phenyl orthotitanate and cyclohexyl orthotitanate, methyl polytitanate, ethyl polytitanate, n-probyl polytitanate, Mi-propyl polytitanate, polytitanium acid n-
Polytitanate esters such as butyl, I-butyl polytitanate, n-amyl polytitanate, 2-ethylhexyl polytitanate, n-octyl polytitanate, phenyl polytitanate, and cyclohexyl polytitanate can be used. The amount of polytitanate to be used may be determined by converting it into orthotitanate and using the orthotitanate phase authority.

As alcohols it is possible to use aliphatic saturated and unsaturated alcohols. Specifically, methanol, ethanol, n-propanol,!・In addition to monohydric alcohols such as ibanol, n-butanol, bentanol, 17,゛sanol, octanol, 2-ethylhexanol, and furyl alcohol, ethylene glycol,
Polyhydric alcohols such as trimethylene glycol and glycerin can also be used. Among them, carbon number is 4~
1O aliphatic saturated alcohols are preferred. As the inert hydrocarbon solvent (02), the aforementioned titanium trichloride composition (
The same solvents as the solvent (J) used in producing In) can be used, but aliphatic hydrocarbons are particularly preferred.

A solid product (rV) is obtained by contacting the above liquefied magnesium compound with a precipitating agent (x3), a halogen compound (X3), an electron donor (B4) and a titanium compound (T1). Examples of the precipitation agent (X3) include halogenating agents such as halogens, halogenated hydrocarbons, halogen-containing silicon compounds, halogen-containing aluminum compounds, halogen-containing titanium compounds, halogen-containing zirconium compounds, and halogen-containing vanadium compounds. Further, when the liquefied magnesium compound is the above-mentioned organomagnesium compound, a compound having active hydrogen, such as an alcohol or a polysiloxane having an St-}1 bond, can also be used. These precipitating agents (X
+) is used in an amount of 0 per mole of magnesium compound.
．． Use 1 mole to SO mole. In addition, halogen compounds (×
Examples of 3) include halogens and halogen-containing compounds, and the same halogenating agents mentioned as examples of precipitating agents can be used. When a halogenating agent is used as a precipitating agent, New use of the halogen compound (x2) is not necessarily required. Halogen compounds (×
The amount of 2) used is 0.00% per mol of magnesium compound.
Use 1 mol to 50 mol. As the electron donor (B4), the above-mentioned (B2) and (
Those similar to B3) are used, preferably aromatic monocarboxylic acid esters, aromatic polyvalent carboxylic acid esters, alkoxysilanes, and particularly preferably aromatic polyvalent carboxylic acid esters. As these electron donors (B4), i fffi types or more are used, and the amount used is 0.01 mol to 1 mol of the magnesium compound.
It is S mole. The titanium compound (τ3) required for the preparation of the solid product (IV) has the general formula Tl (OR”) 4-u
Xu (wherein RI2 is an alkyl group, a cycloalkyl group,
or an aryl group, × represents a halogen, and U represents O<
Any number with u≦4. ), and the orthotitanate esters and polytitanates mentioned above for liquefaction of magnesium compounds are used. Specific examples of halogenated titanium compounds include titanium tetrachloride, titanium tetrabromide, methoxytitanium trichloride, ethoxytitanium trichloride, propoxytitanium trichloride, butoxytitanium trichloride, phenoxytitanium trichloride, and ethoxytitanium tribromide. , butoxytitanium tribromide, dimethoxytitanium dichloride,
Diethoxytitanium dichloride, diproboxytitanium dichloride,
Dibutoxytitanium dichloride, diphenoxytitanium dichloride,
Examples include diethoxytitanium dibromide, dibutoxytitanium dibromide, trimethoxytitanium chloride, triethoxytitanium chloride, tributoxytitanium chloride, triphenoxytitanium chloride, and the like.

Examples of the titanate ester and polytitanate include those mentioned above. One or more types of these titanium compounds (T1) are used, but when a halogenated titanium compound is used as the titanium compound (TI), since it has a halogen, the precipitating agent (T1) is used.
The use of x1) and halogen compound (x2) is optional.

Furthermore, even when a titanate ester is used during liquefaction of a magnesium compound, additional use of the titanium compound (T!) is optional. The amount of titanium compound (T1) used is 0.1 mol to 10 mol per mol of magnesium compound.
It is 0 mole. or more liquefied magnesium compounds,
A precipitating agent (x3), a halogen compound (x2), an electron donor (B4), and a titanium compound (T+) are brought into contact with each other under stirring to obtain a solid product (■). During the contact, an inert hydrocarbon solvent (D3) may be used, or each component may be diluted beforehand. Examples of the inert hydrocarbon solvent (Ds) to be used include those similar to the above-mentioned (D3). The amount used is O to 1 mole of magnesium compound.
S, OOOaj2. There are various methods of contact, for example, ■
Add (x0) to the liquefied magnesium compound to precipitate a solid, and add (x3), (B4), (TI) to the solid.
A method of making contact in any order. ■ A method of adding (Xl3) to a solution in which the liquefied magnesium compound and (B4) were brought into contact to precipitate a solid, and contacting the solid with (x3) and (T3) in any order. There is a method in which after bringing the magnesium compound and (TI) into contact, fX1) is added, and then (B4) and (x2) are brought into contact in any order.

The amount of each component to be used is within the above-mentioned range, but these components may be used all at once or in several stages. Furthermore, as mentioned above, if one component has an atom or group that also characterizes the other component, new use of the other component is not necessarily necessary. For example, when a titanate ester is used to liquefy a magnesium compound, (Ti) is used, but when a halogen-containing titanium compound is used as a precipitating agent (XI), (x3) and (
In T1), when a halogenating agent is used as the precipitating agent (X+), (x2) is the arbitrary usage power. The contact temperature of each component is -40°C to ◆180°C, preferably -20°C to ◆150°C, and the contact time is 5 minutes to 8 minutes per 1 step at a reaction pressure of atmospheric pressure to 10 kg/ca2G. The time is preferably 10 minutes to 6 hours. The solid product (rV) thus obtained was treated with an organoaluminum compound (A2
) and water in the presence of the reaction product (A3), polymerization is carried out in multiple stages using straight olefin and styrene. The polymerization treatment method includes, after completion of the reaction to obtain the solid product (TV),
After separating and removing the liquid portion by filtration or decantation, the obtained solid product (TV) is suspended in a solvent, and further a reaction product (A3) of the organoaluminum compound (A2) and water is added. , a method in which straight olefin and styrene are added in multiple stages and polymerized. The conditions for the multistage polymerization treatment using the direct daughter olefin and styrene are the same as those for the multistage polymerization treatment using the direct daughter olefin and styrene performed when obtaining the titanium trichloride composition (II1) described above, and The content of the linear olefin polymer block in the supported catalyst component (V1) is 0.1% to 49.5%! i amount % and the content of styrene polymer block (1.01 wt % to 49.
511% by weight, and the weight ratio of the straight-set olefin polymer block to the styrene polymer block was 27%.
Do this so that the ratio is 8 to 98/2. In addition, during the polymerization process, electron-donating compounds such as carboxylic acid esters such as ethyl benzoate, methyl toluate, and ethyl anisate, and organosilicon compounds such as phenyltriethoxysilane, diphenyldimethoxysilane, and methyltriethoxysilane are used. It is also possible for bodies to coexist. The amount used is solid raw material ([V)
Per 100g, O~5. It is about OOOg.

The organoaluminum compound (A2) used in the polymerization treatment
and water (A3L solvent (D4), and the linear olefin are the titanium trichloride compositions described above (
The same method as that used in the urination IA process used to obtain Il1) can be mentioned.

As described above, polyolefins and styrene
The solid product (V) is obtained by polymerization treatment and washing with the previously mentioned inert hydrocarbon solvent.

Subsequently, a halogenated titanium compound (
T2) to react to form the final titanium-containing supported catalyst component (
V1) is obtained. As the halogenated titanium compound (T2), the general formula Ti(O
R") A halogenated titanium compound is used, and although similar examples can be given, titanium tetrachloride is most preferred.

In the reaction between the solid product (V) and the halogenated titanium compound (T2), the magnesium compound 1 in the solid product (V)
Using 1 mole or more of the halogenated titanium compound (T3) per mole, reaction temperature of 20 ° C. to 200 ° C., reaction pressure of atmospheric pressure to lokg/cm'G, preferably for 5 minutes to 6 hours. Let react for 10 minutes to 5 hours. In addition, during the reaction, an inert hydrocarbon solvent (D3) and an electron donor (B1
), and specifically, the same inert solvents and electron donors as in (01) to (D4) and (B3) to (B4) described above are used.

These usage amounts are as follows: (Ds) is O ~ 5, OOOmJ2 per 100 g of solid product (V), and (B3) is per mole of magnesium compound in solid product (V).
is preferably in the range of 0 to 2 moles. After the reaction of the solid product (V) with the halogenated titanium compound (T2) and, if necessary, an electron donor, the solid is separated by filtration or decantation for several minutes and then washed with an inert hydrocarbon solvent to remove any unreacted material. By removing substances or by-products, the final titanium-containing supported catalyst component (■) is obtained. In the presence of (A3),
Multi-stage polymerization using straight olefin and styrene! The titanium-containing solid catalyst component obtained by the A process can be used in the same manner as known titanium catalyst components for producing olefin polymers such as polypropylene. The titanium-containing solid catalyst component is
It is used in olefin polymerization as a catalyst in combination with an organic aluminum compound (AI) and, if necessary, an electron donor (B3), or as a preactivated catalyst by further polymerizing a small amount of olefin.

In the polymerization of olefins, the organoaluminum compound (A
．． ) is the titanium trichloride composition (II+
The same organoaluminum compound as used in (A.) for obtaining ) can be used. Also, electron donor (83
) is preferably an organic acid ester, an organosilicon compound having an S+-0-C bond such as an alkoxysilane compound or an aryloxysilane compound, an ether, a ketone, an acid anhydride, an amine, or the like. Specifically, in addition to those exemplified as electron donors (B2) to (B4) used in producing the titanium-containing solid catalyst component described above, 2,2,6,6-tetramethylbiveridine, 2,2 , amines with large steric hindrance such as 5.5-tetramethylpyrrolidine, trimethylmethoxysilane,
Trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, methylphenyldimethoxysilane, diphenyldiethoxysilane, ethyltriethoxysilane, methyltrimethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane,
Examples include organosilicon compounds having a si-oc bond such as ethyltriethoxysilane, vinyltriethoxysilane, butyltriethoxysilane, phenyltriethoxysilane, ethyltril-propoxysilane, and vinyltriacetoxysilane.

The amount of each catalyst component used is the same as in the case of normal olefin polymerization, but specifically, 1 g of the titanium-containing solid catalyst component is used.
In contrast, organic aluminum compound (A+) 0.005
~500g, electron donor (B1) O ~200g. The olefins used for preactivation include ethylene, propylene, and pentene! , hexene-1, heptene-1, etc., linear monoolefins, 4-
These include branched monoolefins such as methyl-bentene-1,2-methyl-bentene-1.

These olefins may be the same as or different from the olefin to be polymerized, and two or more olefins may be used as a mixture. The type of polymerization of olefin using the above catalyst is not limited, and in addition to liquid phase polymerization such as slurry polymerization and bulk polymerization, gas phase polymerization can also be suitably carried out.

For slurry polymerization or bulk polymerization, a catalyst containing a titanium-containing solid catalyst component, an organoaluminum compound (A1), and, if necessary, an electron donor (B+) is sufficiently effective, but in the case of gas phase polymerization It is preferable to use one that has been preactivated by reacting with an olefin. When performing gas phase polymerization following slurry polymerization or bulk polymerization, even if the catalyst initially used is the former, it is the same as the latter catalyst because the olefin reaction has already occurred during gas phase polymerization. You can get excellent results. Preactivation is performed using brobane, butane, n-bentane, n-hexane, n-
It can be carried out in a hydrocarbon solvent such as hebutane, benzene, toluene, etc., it can also be carried out in a liquefied olefin such as liquefied propylene or liquefied butene-1, or in gaseous ethylene or brobylene. They may coexist.

During preactivation, polymer particles previously obtained by slurry polymerization, bulk polymerization, or gas phase polymerization can also be coexisting. The polymer may be the same as or different from the olefin polymer to be polymerized. The amount of coexisting polymer particles is in the range of 0 to 5,000 g per 1 g of the titanium-containing solid catalyst component. The solvent or olefin used in the preactivation can be removed by distillation under reduced pressure or filtration during or after the preactivation, and the solid product can be removed by distillation under reduced pressure or filtration.
A solvent may also be added to suspend the solution in an amount of not more than 8[IJ2]. As described above, the catalyst consisting of the combined titanium-containing solid catalyst component and the organo-alanium compound (A3) and, if necessary, the electron donor (B3), or the catalyst further preactivated with an olefin, is It is used in the production of olefin polymers. As mentioned above, the polymerization method for polymerizing olefins is as follows: ■ Hydrocarbon solvents such as n-bentane, n-hexane, n-hebutane, n-octane, benzene, or toluene. Slurry polymerization carried out in liquefied olefin monomers such as liquefied propylene and liquefied butene-1; 2) Gas phase polymerization in which olefins such as ethylene and brobylene are polymerized in the gas phase; There is a way to combine the above steps in stages.

In either case, the polymerization temperature is room temperature (20°C) to 200°C,
Polymerization pressure is normal pressure (O kg/cm"G) ~ 50 kg/
ca"G, and is usually carried out for about 5 minutes to 20 hours. The addition of an appropriate amount of hydrogen to control the molecular weight during polymerization is the same as in conventional polymerization methods. In addition, the olefin used for polymerization are ethylene, brobylene, butene-1
, linear monoolefins such as hexene-1 and octene-1, branched monoolefins such as 4-methylbentene-1,2-methylbentene-1, and diolefins such as butadiene, isoprene, and chlorobrene. In addition, not only can each of these be polymerized individually, but also in combination with other olefins, such as brobylene and ethylene, butene-1 and ethylene, propylene and butene-1, etc.
Combine as follows: brobylene, ethylene, butene-1
Copolymerization can also be carried out by combining three components as shown in
Further, block copolymerization can also be carried out by changing the type of olefin fed in multi-V1 polymerization.

[For production]

The olefin polymer obtained according to the method of the present invention using a titanium-containing solid catalyst component containing a straight chain olefin-grain block copolymer that has been cured by the multistage polymerization process according to the present invention is Molded articles manufactured using this olefin polymer contain a stereoregular styrene polymer block mainly composed of syndiotactic styrene polymer and partially isotactic styrene polymer, which has a nuclear effect. In particular, it has high crystallinity due to the nucleation effect of syndiotactic styrene polymer, and has high transparency. Furthermore, the linear olefin-styrene block copolymer produced by the multi-stage polymerization of straight-chain olefin-styrene according to the present invention has compatibility with the olefin polymer, so that the linear olefin-styrene block copolymer has compatibility with the olefin polymer. Since the dispersibility of the polymer block in the olefin polymer is highly improved, the nucleation effect of the styrene polymer block is significantly exhibited, and the crystals of pre-shaped products manufactured using the resulting olefin polymer are improved. It is estimated that this further improves the properties and transparency of the film, and significantly reduces the occurrence of voids in the film. [Example] The present invention will be described below with reference to Examples. Definitions of terms used in Examples and Comparative Examples and measurement methods are as follows. MFR: Melt flow rate JIS K 7210
According to condition 14 in Table 1. (Unit: g71
0 minutes) Internal haze: This is the haze inside the film excluding the influence of the surface.
The olefin polymer was formed into a film with a thickness of 150μ under the condition of 00kg/cm"G, and after coating both sides of the film with liquid paraffin, the haze was measured in accordance with JTS K7105. (Unit: 2%) Crystallization temperature : Measured using a differential scanning calorimeter at a cooling rate of 10°C/min. (Unit: 2°C) Flexural modulus:
Tetrakis[
Methylene-3-(3゜-1,5゜-di-t-butyl-4゜-hydroxyphenyl)probionate]methane 0.1
parts by weight, and 0.1 parts by weight of calcium stearate were mixed, and the mixture was granulated using an extrusion granulator with a screw diameter of 4h+i. Next, the granules were molded into JIS type test beads using an injection molding machine at a molten resin temperature of 230°C and a mold temperature of 50°C, and the humidity of the test beads was 50%.
, after being left indoors at a room temperature of 23°C for 72 hours, JIS K
The flexural modulus was measured in accordance with 72G3.
(Position: kgf/am”) Void: Granulate the olefin polymer in the same manner as in the previous section, extrude the resulting granules using a T-die film forming machine at a molten resin temperature of 250°C, A sheet with a thickness of 1 mm was prepared using a cooling roll at 20°C.The sheet was heated with hot air at 150°C for 70 seconds, and then stretched by a factor of 7 in the longitudinal and lateral directions using a biaxial stretching machine to obtain a sheet with a thickness of 2 mm.
A biaxially stretched film of 0μ was obtained. The film was examined under an optical microscope.
The number of poids having a diameter of 10 μm or more was measured by observing with a mirror, and less than 30 poids per 1 cm were marked as Q, and 30 or more were marked as X.

Example 1 (1) mI of the reaction product (A3) of the organoaluminium compound (A2) and water! After purging a stainless steel reactor with an internal volume of 301 cm with a stirrer with nitrogen, 37 kg of copper sulfate/S hydrate and dehydrated toluene at 50°C were charged, and after cooling to 1Ft, the internal temperature was 15°C.
500 mol of trimethylaluminum diluted with toluene Si was added to
Added over time. After the addition, the reaction was continued at 15°C for 48 hours, and then the solids were removed, and a portion of the toluene was distilled off under reduced pressure at room temperature to obtain 40ft of a toluene solution containing methylaluminoxane. (2) Preparation of titanium-containing solid catalyst component n-hexane 6j2, 5.0 mol of diethylaluminum monochloride (DEAC), and 12.0 mol of diisoamyl ether were mixed at 25°C for 5 minutes, and reacted at the same temperature for 15 minutes. A reaction solution (I) (molar ratio of diisoaryl ether/DEAC of 2.4) was obtained.

Put 40 moles of titanium tetrachloride into a reactor purged with nitrogen,
The mixture was heated to 35°C, and the entire amount of the reaction liquid (1) was added dropwise thereto over 180 minutes, and then kept at the same temperature for 60 minutes.
The temperature was raised to 0°C, the reaction was further carried out for 1 hour, and the mixture was cooled to room temperature.
The operation of removing the supernatant, adding 20J2 of n-hexane, and removing the supernatant by decantation was repeated four times to obtain a solid product (I!). The total amount of this (I1) is expressed as (
It was suspended in a toluene solution containing 400 moles of methylaluminoxane obtained in 1), and 420 Nj of ethylene was added at 30°C.
was added and polymerized for 1 hour at the same temperature:! 6J! I did. After the reaction time has passed, unreacted ethylene is removed and styrene 9.
5 kg was added and the mixture was treated at 40° C. for 2 hours. After the reaction was completed, the supernatant liquid was removed, toluene 3i was added, and the operation of removing with decantation was repeated four times to obtain a solid product ([118]) subjected to multistage polymerization treatment with ethylene-styrene.
I got it. The total amount of this solid product (n-A) was dissolved in n-hexane 9
3.5 kg of titanium tetrachloride was added to C in suspension in J2 at room temperature for about io minutes, and after reacting at 80°C for 30 minutes, diisoamyl ether 1. Itkg was added and reacted at 80°C for 1 hour. After the reaction was completed, the operation of removing the supernatant liquid was repeated five times, and then dried under reduced pressure to obtain a titanium trichloride composition (In), which was used as a titanium-containing solid catalyst component used in the present invention.

The content of the ethylene polymer block in the titanium trichloride composition (m) is 14.3% by weight, the content of the styrene polymer block is 14.31% by weight, and the titanium content is ta.
．． It was O @ amount%. (3) Preparation of preactivated catalyst component After purging a stainless steel reactor with inclined blades with an internal volume of 80J2 with nitrogen gas, 40J2 of n-hexane, 200g of diethylaluminium monochloride, and (2) as the titanium-containing solid catalyst component were added. The obtained titanium trichloride composite (II
I) After adding 45Qg at room temperature, the temperature inside the reactor was increased to 40Qg.
℃, add 800 g of propylene, and heat at 40℃ for 1 hour.
Pre-activation IA treatment was performed (titanium trichloride group sacrament (II)
I) Brobylene per Ig 1. Og reaction). After the reaction was completed, the mixture was washed with n-hexane, filtered, and dried to obtain a preactivated catalyst. [4] Production of olefin polymer L equipped with a stirrer with an internal volume of 150 J2 and nitrogen ra exchange
/D-4 stainless steel horizontal polymerizer with MFR 2.0
After adding 30 kg of polypropylene powder, the above (3)
n-hexane was added to the preactivated catalyst component obtained in ),
After making it into a 4.0% by weight suspension in n-hexane, the gloomy night was calculated as 5.6 milligram atoms/hr in terms of titanium atoms yA.
A 30% by weight hexane solution of diethylaluminum monochloride was continuously supplied at 4.7 g/hr as diethylaluminum monochloride. In addition, hydrogen was supplied so that the concentration in the gas phase of the polymerization reactor was maintained at 1.0% by volume, and brobylone was supplied so that the total pressure was maintained at 23 kg/ci'G, and the gas phase polymerization of brobylene was carried out for 70%. The test was carried out continuously for 160 hours at ℃.

During the polymerization, the polymer was continuously fed at a rate of 13.5 kg/hr so that the polymer retention level in the polymerization vessel was 45% by volume.
I extracted it. The extracted polymer was then heated at 95°C using nitrogen gas containing 0.2% by volume of brobylene oxide.
A contact treatment was carried out for 30 minutes to obtain polybrovinone. Comparative Example 1 (1) Preparation of titanium-containing solid catalyst component In (2) of Example 1, the solid product (ti) was prepared as a solid raw material (IT-A) without performing a multistage polymerization treatment with ethylene and styrene. A titanium trichloride compound was obtained in the same manner except that the equivalent material was used. (2) Preparation of pre-activated catalyst component In (3) of Example 1, titanium trichloride composite material (
A preactivated catalyst component was obtained in the same manner except that the titanium trichloride composition obtained in (1) above was used in place of II+).k. (3) Production of olefin polymer Propylene was polymerized in the same manner as in [4] of Example 1, except that the preactivated catalyst component obtained in (2) above was used as the preactivated catalyst component, and polypropylene was I got it.

Comparative Example 2 (1) A toluene solution of methylaluminoxane was obtained in the same manner as in Example 1 (1). (2) A titanium trichloride composition was obtained in the same manner as in (1) of Comparative Example 1. (3) Add 2 toluene to the reactor used in (3) of Example 1.
0J2, 100 moles of the toluene solution of methylalanoxane obtained in (1) above as aluminum atoms and 450 g of the titanium trichloride compound obtained in <<2>> above were introduced at room temperature. Next, 1.8 kg of styrene was added and heated to 35°C.
Preactivation treatment was carried out for 2 hours (0.2 g of styrene was reacted per 1 g of titanium trichloride composition). After the reaction was completed, the mixture was washed with toluene, filtered, and dried to obtain a preactivated catalyst component.

[4] Propylene was polymerized in the same manner as in [4] of Example 1, except that the preactivated catalyst component obtained in step 3 above was used as the preactivated catalyst component.
The polymerization of propylene had to be stopped 10 hours after the start of polymerization because the generated bulk polymer blocked the polymer extraction pipe. Comparative Example 3 Syndiotactic boris thousand rene obtained by polymerizing styrene using a catalyst consisting of cyclobentadienyl titanium trichloride and methylaluminoxane according to Example 1 described in JP-A-82-104,818. 1
．． 6 g was mixed with 10 kg of polybropylene obtained in Comparative Example 1 to obtain a polybropylene composition containing 160 ppm by weight of syndiotactic polystyrene. Comparative Example 4 and Example 2.3 In (2) &: of Example 1, the amounts of ethylene and styrene used in the polymerization treatment were changed to produce titanium trichloride compositions whose contents were as shown in the table. (Il1')
I got it. Thereafter, polypropylene was obtained in the same manner as in Example 1. Example 4 (1) Preparation of reaction product (A3) of organic aluminum compound (A2) and water A toluene solution of methylaluminoxane was obtained in the same manner as in Example 1 (2). (2) Preparation of titanium-containing solid catalyst component In a stainless steel reactor equipped with a stirrer, decane 31,
480 g of anhydrous magnesium chloride, 1.7 kg of n-butyl orthotitanate, and 1 liter of 2-ethyl-1-hexanol.
．． 95 kg were mixed and heated to 130°C for 1 hour while stirring to dissolve and form a uniform solution. The homogeneous solution was heated to 70°C.
Then, 180 g of diisobutyl phthalate was added with stirring, and after 1 hour, 5.2 kg of silicon tetrachloride was added dropwise over 2.5 hours to precipitate a solid, and the mixture was further heated to 70° C. for 1 hour. The solid was separated from the solution and washed with hexane to obtain a solid raw material (TV). After suspending the entire amount of the solid product (rV) in a toluene solution containing 140 mol of methylaluminoxane obtained in (1) above, ethylene III
t was added, and polymerization was carried out at 30°C for 1 hour. After the reaction time has passed, unreacted ethylene is removed and styrene 4.5
kg was added and polymerization was carried out at 35°C for 2 hours. After the reaction was completed, the supernatant liquid was removed by decantation and washed three times with 61 toluene to obtain a solid product (V).

The entire amount of the solid product (V) was added to 5f of 1,2-dichloroethane.
180 g of diisobutyl phthalate was added while stirring.
After reacting at 00°C for 2 hours, the liquid phase was removed by decantation at the same temperature, 1,2-dichloroethane 51 and titanium tetrachloride 51 were added again, and the mixture was heated to 100°C.
The mixture was stirred for 2 hours, washed with hexane, and dried to obtain a titanium-containing supported catalyst component (VT), which was used as a titanium-containing solid catalyst component used in the present invention.

The titanium-containing supported catalyst component (V1) has a nearly spherical particle shape, and the content of ethylene polymer blocks is
．． aii amount%, the content of styrene X combined block is 29
．． 4% by weight, and the titanium content was 1.8% by weight.

(3) Preparation of preactivated catalyst components After purging a stainless steel reactor with a stirrer with a volume of 30 ml with nitrogen gas, 2i n-hexane, 40 g of I-ethylaluminum, and the titanium obtained in (2) above were added. 200 g of co-supported catalyst content (V'[) was added. Subsequently, 30
Preactivation fi by supplying 190 NJ2 of ethylene at ℃
(1.0 g of ethylene reacted per 1 g of titanium-containing supported catalyst). After the reaction time had elapsed, unreacted ethylene was removed, washed with n-hexane, and further dried to obtain a preactivated catalyst component.

[4] Manufacture of olefin polymer L/D with 1 ton of nitrogen exchange and a stirrer with internal volume of 80 mm
・After charging 20 kg of VFR 2.0 Volibrovy 1/N powder into the horizontal polymerization vessel in step 3, add n-hexane to the preactivated catalyst component obtained in step (3) above. After making a suspension in n-hexane with a concentration of Oii%, the suspension was treated with 0.33 milligram atoms of ha in terms of titanium atoms, triethylaluminum at 7.5 g/hr, and diphenyldimethoxysilane. Continuously (supplied) from separate supply ports at a rate of 2.3 g/hr.

In addition, hydrogen was supplied so that the concentration in the gas phase of the polymerization reactor was maintained at 0.15% by volume, and propylene was supplied so that the total pressure was maintained at 23 kg/cm2G.
The test was carried out continuously for 120 hours at 0°C. During the polymerization, the polymer was continuously extracted at a rate of 10.0 kg/hr so that the polymer retention level in the polymerization vessel was 60% by volume. The extracted polymer was subjected to the same post-treatment as in [4] of Example 1 to obtain polypropylene. Comparative Example 5 Titanium-containing support was carried out in the same manner as in Example 4 (2) except that the multi-stage polymerization treatment with ethylene and styrene was omitted and the solid raw material (rV) was used as the solid product (V) equivalent. A type catalyst component was obtained.

Hereinafter, Example 4 will be carried out using the titanium-containing supported catalyst component.
(3). Brobylene was obtained in the same manner as [4]. Example 5 (1) A toluene solution of methylalkynoxane was obtained in the same manner as in Example 1 (1). (2) A reaction solution obtained by reacting n-hebutane at 4°C, 5.0 mol of diethylaluminum monochloride, 9.0 mol of diisoamyl ether, and 5.0 mol of di-n-butyl ether at 18°C for 30 minutes was After dropping into 27.5 moles of titanium chloride at 40℃ for 300 minutes, the water temperature was the same.
After reacting for 1.5 hours, the temperature was raised to 65°C, reacted for 1 hour, the supernatant liquid was removed, n-hexane 2i was added, and the operation was repeated 6 times to remove by decantation with soap and water. 1.8 kg of the solid product (I1) was suspended in the entire amount of the toluene solution of methylaluminoxane obtained in (1) above,
220 NIt of ethylene was added at 30°C, and 1
A time polymerization treatment was performed. After the reaction time has passed, unreacted ethylene is removed and styrene 1G. OKg was added and polymerization was carried out at 30°C for 2 hours.

After the reaction was completed, the supernatant was removed by decantation, and the operation of adding 201 toluene and removing by decantation was repeated twice, followed by washing with 2i n-hexane, and a solid product (TI) was subjected to multistage polymerization treatment. - A) was obtained. Subsequently, the solid product (II-A) was suspended in 7 L of n-hexitine, 1.8 kg of titanium tetrachloride and 1.8 kg of n-butyl ether were added, and the mixture was reacted at 60°C for 3 hours. After the reaction was completed, the supernatant was removed by decantation, and then
Adding n-hexane from No. 01, stirring for 5 minutes, standing still and removing the supernatant liquid was repeated three times, followed by drying under reduced pressure to obtain a titanium trichloride composite (II1). (3) In (3) of Example 1, the titanium trichloride compound (I) obtained in (2) above was used as the titanium-containing solid catalyst component.
A preactivated catalyst component was obtained in the form of a slurry in the same manner as above, except that I1) was used and that washing with n-hexane and drying were not performed after the reaction was completed. [4] Add the preactivated catalyst slurry obtained in (3) above to a nitrogen-substituted polymerization reactor equipped with a stirrer and a two-stage turbine blade with an internal volume of 1,501 cm at a rate of 13 square grams atoms/hr in terms of titanium atoms. ,
Diethylaluminium monochloride was continuously supplied at a molar ratio of 3.0 to titanium from the same pipe, and n-hexane was continuously supplied from a separate pipe at a rate of 21 kg/hr. Furthermore, hydrogen was supplied so that the concentration in the gas phase of the polymerization vessel was maintained at 1.5% by volume, and propylene was supplied so that the total pressure was maintained at 10 kg/cm"G, and the slurry polymerization of brobylene was carried out at 70 °C. It was conducted continuously for 120 hours.
During the polymerization, the polymer slurry was continuously drawn out from the polymerization vessel into a flash tank with an internal volume of 50 J2 so that the retention level of the polymer slurry in the polymerization vessel was 75% by volume. While reducing the pressure in the flash tank and removing unreacted hydrogen and propylene, methanol was added at 1 kg/hr.
It was supplied at 70°C and subjected to contact treatment. Subsequently, the slurry was centrifuged to separate the solvent and dried to obtain polypropylene at 10 kg/hr. Comparative Example 6 In (2) of Example 5, the solid product (U) was converted into the solid product (U) without the polymerization treatment with ethylene and styrene.
II-A) A titanium trichloride composition was obtained in the same manner except that the corresponding product was used. Thereafter, using the titanium trichloride composition, polybrobylene was obtained in the same manner as in Example 5 (3) and [4]. Example 6 (1) A toluene solution of methylaluminoxane was obtained in the same manner as in Example 1 (1).

(2) 1.7 kg of aluminum trichloride (anhydrous) and 0.6 kg of magnesium hydroxide were heated at 250°C in a vibrating mill.
When the reaction was carried out while being pulverized for a period of time, the reaction occurred with the generation of hydrogen chloride gas. After heating, it was cooled in a nitrogen stream to obtain a magnesium-containing solid. Decane at 6°C in a stainless steel reactor with a stirrer.
, 1.0 kg of magnesium-containing solid, 3.4 kg of n-butyl orthotitanate, and 3.9 kg of 2-ethyl-1-hexanol were mixed and heated to 130°C for 2 hours with stirring to dissolve and form a homogeneous solution. did. The solution was heated to 70°C, and 0.2 kg of ethyl p-toluate was added.
After reacting for an hour, 0.4 kg of diisobutyl phthalate was added, and after further reaction for 1 hour, silicon tetrachloride 10
kg was added dropwise over 2 hours and 30 minutes to precipitate a solid, and the mixture was further stirred at 70°C for 1 hour. The solid was separated from the solution and purified by washing with chitin to obtain a solid product (TV).

After suspending the entire amount of the solid product (rV) in a toluene solution containing 150 moles of methylaluminoxane obtained in (1) above, 145 g of diphenyldimethoxysilane was added, and then 120 Nj! of ethylene was added. was added and polymerization was carried out at 30°C for 1 hour. After the reaction time had elapsed, unreacted ethylene was removed, 4.7 kg of styrene was added, and polymerization was carried out at 35°C for 2 hours. After the reaction was completed, the supernatant liquid was removed, 20 liters of toluene was added, and the supernatant liquid was removed by decantation, which was repeated three times.Then, the solid product was washed with 20 ft of n-hexane and polymerized with ethylene and styrene. V) was obtained. The total amount of the solid product (V) was dissolved in 10% of 1,2-dichloroethane.
Add 0.4 kg of diisobutyl phthalate together with 10 λ of titanium tetrachloride diluted with 1, react at 100°C for 2 hours with stirring, remove the liquid phase by decantation at the same temperature, and add 1,2-dichloroethane again. toj2
, titanium tetrachloride lOJ2 was added, and while stirring 100
After reacting at ℃ for 2 hours, a solid portion was collected by hot filtration, washed with n-hexane, and dried to obtain a titanium-containing supported catalyst component ('/I). The titanium-containing supported catalyst component (
The ethylene polymer block content in V1) is 11.8!
i amount%, styrene polymer block content is 29.4! !
% by weight, and the titanium content was 2.01% by weight. (3) In (3) of Example 4, the titanium-supported catalyst component (V
A preactivated catalyst component was obtained in the same manner except that [) was used. [4] In [4] of Example 4, the preactivated catalyst component obtained in the above (3) is used as the preactivated catalyst component, and during the gas phase polymerization of propylene, the Propylene-ethylene copolymerization was carried out in the same manner except that ethylene was further supplied so that the concentration was maintained at 0.2% by volume to obtain a propylene-ethylene copolymer. Comparative Example 7 A titanium-containing supported type was prepared in the same manner as in (2) of Example 6, except that the polymerization treatment with ethylene and styrene was omitted and the solid product (IV) was made equivalent to the solid product (V). A catalyst component was obtained.

Thereafter, except for using the titanium-containing supported catalyst component as the titanium-containing solid catalyst component, (3) and [
4], a propylene-X tyrene copolymer was obtained. The titanium-containing solid catalyst component conditions and results of the above examples and comparative examples are shown in the table. [Effects of the Invention] The main effects of the present invention are that the olefin polymer, which has excellent transparency and crystallinity and does not generate voids even when made into a film, is stable without causing any manufacturing problems. This is what you can get by doing this. As is clear from the examples described above, the method of the present invention allows stable production over a long period of time without any manufacturing problems. In addition, the internal haze of the film produced using the obtained olefin polymer is 2.0%~
4.0%, which is about 9% to about 12% of the film produced using a conventional olefin polymer obtained using a known catalyst component that has not been subjected to the multistage polymerization treatment according to the present invention.
It has significantly higher transparency than . The crystallization temperature also increased by about 8°C to about 11°C, and as a result of the marked improvement in crystallinity, the flexural modulus also improved. (Example 1~
6. See Comparative Examples 1.5 to 7)

[Brief explanation of drawings]

FIG. 1 is a manufacturing process diagram (
flow sheet).

Claims (1)

[Scope of Claims] [1] (1) a titanium-containing solid catalyst component, (2) an organoaluminum compound (A_1), and, if necessary, (
3) In a method for producing an olefin polymer by polymerizing an olefin using a catalyst consisting of an electron donor (B_1), (1) an organoaluminum compound is added as a titanium-containing solid catalyst component during the production of the titanium-containing solid catalyst component; (A_2
) and water in the presence of a reaction product (A_3), a linear olefin and styrene are polymerized, and a titanium-containing solid catalyst component obtained by further subsequent steps is used. Production method. [2] As a titanium-containing solid catalyst component, an organoaluminum compound (A_4) or a reaction product of an organoaluminum compound (A_4) and an electron donor (B_2) (
A solid product obtained by reacting titanium tetrachloride with I) (
II) is polymerized in multiple stages with linear olefin and styrene at least once each in the presence of the reaction product (A_3) of the organoaluminum compound (A_2) and water, and then polymerized with the electron donor (B_3) and electron The manufacturing method according to claim 1, which uses titanium trichloride composition (III) obtained by reacting with a receptor. [3] As a titanium-containing solid catalyst component, a solid product (IV) obtained by contacting a liquefied magnesium compound with a precipitating agent, a halogen compound, an electron donor (B_4), and a titanium compound (T_1) is used as an organic Aluminum compounds (
In the presence of the reaction product (A_3) of A_2) and water, polymerization is performed in multiple stages, one or more times each with a linear olefin and styrene to obtain a solid product (V), and further a halogenated titanium compound (T_2) The manufacturing method according to claim 1, using the titanium-containing supported catalyst component (VI) obtained by reacting the titanium-containing supported catalyst component (VI). [4] As the organoaluminum compound (A_1), the general formula is AlR^1_pR^2_p'X_3_-_(_p_
+_p'_) (wherein R^1 and R^2 represent a hydrocarbon group such as an alkyl group, cycloalkyl group, or aryl group or an alkoxy group, X represents a halogen, and p and p' are 0
<p+p'≦3. ) The manufacturing method according to claim 1, using an organoaluminum compound represented by: [5] The manufacturing method according to claim 1, wherein trimethylaluminum is used as the organoaluminum compound (A_2). [6] Instead of the titanium-containing solid catalyst component, a titanium-containing solid catalyst component and an organoaluminum compound (A_1), and if necessary, an electron donor (B_1)
2. The manufacturing method according to claim 1, which uses a catalyst component which is preactivated by combining the above components and reacting this component with a small amount of olefin.