JPS62104813A - Production of polyolefin - Google Patents

Abstract

PURPOSE:To obtain the titled odorless highly stereoregular polymer by the use of a catalyst derived from combination of a solid product prepared by reaction between an Mg-compound, a titanic acid and an alcohol followed by treatment with Si- and Ti-compounds, etc., an organoaluminum compound and organosilicon compound. CONSTITUTION:The objective polymer can be obtained by (co)polymerization of alpha-olefin(s) by the use of a catalyst derived from combination of (A) a solid catalytic component prepared by reaction, in a hydrocarbon solvent, between (1) a magnesium halide of formula I (X is Cl or Br; R<1> is 1-20C alkyl, aryl, etc.; n is 0-2), (2) an orthotitanic acid ester of formula II (R<2> is 1-20C alkyl or aryl), etc. and (3) an alcohol to effect dissolution followed by reaction of a 2-24C monocarboxylic acid ester and a silicon halide of formula III (R<7> is 1-20C alkyl, aryl, etc.; l is 1-4), etc. to make a solid separate out followed by reaction of a titanium halide of formula IV (R<9> is 1-20C alkyl, aryl, etc.; q is 1-4), etc., (B) an organoaluminum compound and (C) an organosilicon compound having Si-O-C bond.

Description

[Detailed description of the invention] [Field of technology] The present invention relates to a method for producing polyolefins.

More specifically, the present invention relates to a method for producing an odorless polyolefin with high regioregularity, narrow molecular weight distribution, and using a new supported solid catalyst.

However, in the present invention, polyolefin refers to carbon a
In addition to Sino-German polymerization and copolymers of α-olefins with 3 or more carbon atoms, α-olefins with 3 or more carbon atoms and α-olefins with 2 carbon atoms
- A copolymer of olefins, in which the component ratio in the copolymer is 50% by weight or more.

[Conventional technology]

The present inventors have already reported in Japanese Patent Application No. 80-51507, Japanese Patent Application No. 80-51508, Japanese Patent Application No. 80-51509, and Japanese Patent Application No. 60-51510, etc. that environmental pollution caused by the odor of polyolefins and We proposed a method to solve the problem of poor workability.

However, the polyolefin obtained in the earlier application has the extraction stereoregularity (ESS) required by the Urato heptane extraction method.
Despite the high molecular weight, the infrared stereoregularity (IR-) determined by infrared spectroscopy was relatively low, and the molecular weight distribution was relatively wide. Therefore, there is a problem in that it may not be suitable for applications 1 that require polyolefins with high infrared stereoregularity and narrow molecular weight distribution, such as certain types of injection molding, film, or fiber applications. .

Furthermore, in JP-A-58-83008, a supported solid catalyst component containing an ester of a polyhydric carboxylic acid and/or a polyhydric hydroxy compound is combined with an organometallic compound component and S
A method of making polyolefins using a catalyst formed by combining with an organosilicon compound component having i-0 to C or Si-N-C bonds is disclosed. Although the prior application describes the stereoregularity of the extraction method, there is no description of the infrared stereoregularity, and there is no description of the fraction 7-1 distribution, so what kind of uses is the polyolefin produced? It is not easy to estimate.

In addition, in the earlier application, the presence of a liquid titanium compound is essential when forming a hydrocarbon solution of a magnesium compound or forming a solid product from the solution, and the liquid titanium compound is further added to the formed solid. There is a clear difference between the present method of producing the solid catalyst component in that it is not essential to react the titanium compound.

[Purpose of the invention]

The present inventors have completed the present invention as a result of intensive studies to solve the problems described in the previous application.

As is clear from the above description, the objects of the present invention are to provide a method that does not require the removal of residual catalyst in the polymer, has not only high stereoregularity in the extraction method, but also has high infrared stereoregularity upward, and has a high molecular weight. It is an object of the present invention to provide a method for producing a polyolefin having a narrow distribution, odorless, and a good particle shape.

[Structure and effects of the invention]

The present invention has the following main configuration (1).

(1) The solid product (II) produced through the reactions of steps I, II and III below is used as a solid catalyst component, and the solid catalyst component is combined with an organoaluminum compound component and S
A method for producing a polyolefin, comprising polymerizing an olefin using a catalyst obtained in combination with an organosilicon compound component having 1-0 to C bonds.

r, - General formula MgX++ (O11')2-71 TE Represented by Mg halide ~20 cycloalkyl group, n is a number from 0 to 2), general formula Ti(OR2)4
Orthotitanate ester and/or titanate ester represented by the general formula % formula % (wherein R2, R3, R4, R5 and port 6 are an alkyl group having 1 to 20 carbon atoms, an aryl group, or an aryl group having 3 to 20 carbon atoms) is a cycloalkyl group, m is 2-2
0) and a saturated or unsaturated monohydric or polyhydric alcohol with 1 to 2 carbon atoms @ are mixed in an inert hydrocarbon solvent and reacted and dissolved to obtain (component A).

■■, said ° (component A) is an aliphatic or aromatic monocarboxylic acid ester having 2 to 24 carbon atoms (hereinafter referred to as an organic acid ester) [d] and the general formula S+X@Rnie or S+Xp (Or+') 4-P (X is Cl or Br, R' and R11 are each an alkyl group having 1 to 20 carbon atoms, an aryl group, or a cycloalkyl group having s<3 to 20 carbon atoms, and p is 1 to 4 (component B) consisting of a silicon halide represented by Formula T iXq (OR
) 4-q (where, Titanium halide represented by
(O1r')4-t (where X is Cl or Br
, R'' and RI' are each an alkyl group having 1 to 20 carbon atoms, an aryl group, or a cycloalkyl group having 3 to 20 carbon atoms, S is a number of 1 to 3, and t is a number of 1 to 4). Consisting of vanadyl halide or vanadium halide ■ and aromatic polyhydric carboxylic acid ester ■ (
A reaction in which component C) is reacted to obtain a solid (hereinafter referred to as solid product (II)).

The configuration and effects of the present invention will be explained in detail below.

First, let's talk about stage construction.

(Component A) is obtained by mixing components (→, (O and Here, or Cl or Br, It' is an alkyl group having 1 to 20 carbon atoms, an aryl group, or a cycloalkyl group having 3 to 20 carbon atoms,
n is a number from 0 to 2. Specifically, they are magnesium cybaride, alkoxymagnesium halide, and magnesium dialkoxide.

More specifically, as the magnesium cybaride, magnesium chloride and anhydrous magnesium bromide can be used.

Examples of magnesium alkoxide include magnesium dimethoxide, magnesium jetoxide, magnesium alkoxide, magnesium alkoxide, magnesium di-2-ethylhexanoxide, magnesium dioctanoxide, magnesium diphenoxide, magnesium dicyclopropoxide, magnesium methoxyethoxide, and magnesium. Mention may be made of ethoxybutoxide, magnesium ethoxyphenoxide, and the like.

Examples of alkoxymagnesium halides include methoxymagnesium chloride, ethoxymagnesium chloride, propoxymagnesium chloride, 2-ethylhexanoxymagnesium chloride, phenoxymagnesium chloride, ethoxymagnesium bromide, phenoxymagnesium bromide, and octanoxymagnesium bromide. be able to.

Among these compounds, magnesium chloride, magnesium jetoxide, ethoxymagnesium chloride, and the like are preferred.

Ingredient (■) is a titanate ester. The titanate esters include orthotitanate kt-3 represented by Ti(OR")4 and 11Bfo-Ti(O1l') (
OR') is a polytitanate ester represented by kO-1. Kokote, n2, n3. R', R5oJ:
and n6 is a noalkyl group having 1 to 2 carbon atoms, an aryl group, or a cycloalkyl group having 3 to 20 carbon atoms, and 1m is 2 to 20 carbon atoms.
The number is 20.

Specifically, methyl orthotitanate, methyl orthotitanate, n-propyl orthotitanate, orthotitanate i
-propyl, n-butyl orthotitanate, dobutyl orthotitanate, n-7 mil orthotitanate, m2-ethylhexyl orthotitanate, n-octyl orthotitanate,
Sulfotitanate esters such as phenyl orthotitanate and cyclohexyl orthotitanate, polymethyl titanate, polyethyl titanate, n-propyl polytitanate, propyl polytitanate, n-butyl polytitanate, i-butyl polytitanate, polytitanate n-7 mil,
Polytitanate esters such as 2-ethylhexyl polytitanate, n-octyl polytitanate, polytitanium-ugly phenyl, and polytitanium-uglycyclohexyl can be used.

Ingredient ■ is alcohol. As alcohols it is possible to use aliphatic saturated and unsaturated alcohols.

Specifically, methyl alcohol, ethyl alcohol, n
-propyl alcohol, 1-propyl alcohol, n-
In addition to monohydric alcohols such as butyl alcohol, n-7myl alcohol, 1-amyl alcohol, n-henyl alcohol, n-octyl alcohol, 2-ethylhexyl alcohol, and allyl alcohol, ethylene glycol, trimethylene glycol, and glycerin Polyhydric alcohols such as can also be used. Among them, aliphatic saturated alcohols having a base number of 4 to 10 are preferred.

Inert hydrocarbon solvents used to dissolve the components (excellent, ■, and [e]) include pentane, hexane,
Aliphatic hydrocarbons such as heptane, nonane, decane and kerosene, aromatic hydrocarbons such as benzene, toluene and xylene, carbon tetrachloride, 1,2-dichloroethane,
Mention may be made of hydrocarbon halides such as l,x,2-trichloroethane, chlorobenzene and O-dichlorobenzene.

Among them, aliphatic hydrocarbons are preferred.

Specific methods for reacting and dissolving components +a'), t5) and (Φ in an inert hydrocarbon solvent include the following methods:
(Mixing Yu and @ in an inert hydrocarbon solvent in any order of addition, and heating the suspension while stirring; ■Heating components [b] and [c] in an inert hydrocarbon solvent while stirring; and add component ■ to the solution, ■component■
and ■ are heated with stirring in an inert hydrocarbon solvent,
Next, component [e] is added, or (1) components (2) and [e] are heated while stirring in an inert hydrocarbon solvent, and then component (2) is added.

Although any of the above methods can be employed, method (D) is preferred because it is extremely easy to operate.

Heating is necessary to dissolve components (1), [b] and [c] in the inert hydrocarbon solvent. The heating temperature is 40 to 200°C, preferably 50 to 150°C. The time required for the reaction and dissolution is 5 minutes to 7 hours, preferably 10 minutes to 5 hours.

The amount of component (2) to be used is 0.1 to 2 moles, preferably 0, when the former is an orthotitanate ester per mole of component 0.
．． 5 to 1.5 mol, similarly in the case of polytitanate ester, it is sufficient to use the equivalent amount of orthotitanate ester in terms of orthotitanate units. ~5 mol, preferably 0.
It is 5 to 4 moles.

As for the amount of ingredients (yu) and In addition to having to use silicon halide, solidification itself is difficult, and even after solidification, it is extremely difficult to control the particle shape.

Also, if the amount of component ■ and (ri) used is too small, component [a
] does not dissolve in the inert hydrocarbon solvent, the solid catalyst component is amorphous, and it is impossible to obtain a polymer with a spherical or nearly spherical particle shape. 0.1 to 5, preferably 0.
I watched 3-3 times.

Next, stage [I] will be described.

(Component B) consists of component [a] and (ri).

The ingredient is an organic acid ester. Examples of organic acid esters include methyl acetate, ethyl acetate, n-propyl acetate,
Aliphatic carboxylic acid esters such as propyl acid, n-butyl acetate, ethyl propionate, n-propyl propionate, i-butyl propionate, ethyl butyrate and phenyl acetate, methyl benzoate, ethyl benzoate, methyl toluate Aromatic carboxylic acid esters such as ethyl toluate, methyl anisate, ethyl anisate and phenyl anisate can be used.

Component 0 has the general formula SiX++11nee* or SiXp
It is a silicon halide represented by (O11')a-P. Here, X is Cl or Br, n' and n7 are an alkyl group having 1 to 20 carbon atoms, an aryl group or a cycloalkyl group having 3 to 20 carbon atoms, and 2 or P
is a number from 1 to 4. Specifically, SiXon2-
++ Silicon tetrachloride, silicon tetrabromide, ethyl silicon trichloride, propyl silicon dichloride, butyl silicon trichloride, phenyl silicon trichloride, cyclosilicon trichloride, ethyl silicon tribromide, diethyl dichloride Silicon, dibutyl silicon dichloride and triethyl silicon chloride, etc. 5j
Xp(OR')4-P, silicon tetrachloride, silicon tetrabromide, methoxy silicon trichloride, ethoxy silicon trichloride, propoxy silicon trichloride, butoxy silicon trichloride,
Phenoxy silicon trichloride, ethoxy silicon tribromide, dimethoxy silicon dichloride, jetoxy silicon dichloride, dibutoxy silicon dichloride, diphenoxy silicon dichloride, dimethoxy silicon tribromide, trimethoxy silicon chloride, triethoxy silicon chloride, etc. can be mentioned. It is also possible to use mixtures of the compounds mentioned above. Among them, silicon tetrachloride is preferred, and these components may be used after being diluted with the above-mentioned inert hydrocarbon solvent.

Next, the reaction between (component A) and (component B) will be described. (
The reaction of component A) and (component B) produces a solid product (I)
is obtained. This reaction can be done by adding (component B) to (component A), adding (component A) to (component B), or c) adding part of (component B) to (component A). , add to it the remaining ingredients of (component B) or make it (
This can be carried out by adding it to the remaining components of component B).

Specifically, for example, there are the following methods.

That is, component (2) is reacted with component A, and then component (2) is reacted to precipitate a solid product (L).

■ Components (Φ and [e] are reacted simultaneously to precipitate a solid product (I). ■ Component [e] is reacted to precipitate a solid, and then component ■ is reacted to precipitate a solid product (I). or a combination of two or more of ■■ to ■.Any method can be adopted.Even if component @ is mixed or reacted with (component A), solids will not precipitate. (Component A) or a mixture or reaction product of (Component A) and component (2) is a homogeneous solution.In order to precipitate a solid from these homogeneous solutions, component (2) is necessary. As for such addition method, ingredients@
is usually preferably added to (component A), but component
can be added to (component A) or (I & min A)
can also be added to component (■). Solid product (II
) is controlled by the particle shape of the solid product (I), so to control the particle shape, reaction of component ■ with (component A) or (component A) with a mixture or reactant of component @ is required. extremely important.

The usage ratios of (component A), component [d] and (2) are as follows. In other words, component 0 that constitutes (component A) as a raw material
With respect to 1 mol, the amount of component () used is 0.05 to 0.7 mol, preferably 0.1 to 0.8 mol, and the amount of component (2) used is 0.1 to 50 mol, preferably 1 ~20 moles. These components may be used all at once, or may be used in several stages.

The reaction temperature of (component A) and (component B) is -40 to (・1
The temperature is 80°C, preferably -20 to +150°C, and the reaction time is 5 minutes to 6 hours, preferably 10 minutes to 5 hours per step.
It's time. The solid product (I) precipitated by the reaction of (component A) with (d!t, min. B) may be subsequently reacted with (component C) in the next step, but the Washing with an activated hydrocarbon solvent is preferred because unreacted substances or by-products present in the solution may interfere with subsequent reactions. Thus, the next step m, which is spherical or near spherical, will be described.

(Component C) consists of ■ and/or (sec and ■).

Component (1) is a titanium halide represented by the general formula TiXq (Oft9)a-q. Here, X is C1 or B", 1B is an alkyl group having 1 to 20 carbon atoms, an aryl group, or a cycloalkyl group having 3 to 20 carbon atoms, and q is a number of 1 to 4. Specifically, , titanium tetrachloride, titanium tetrabromide, methoxytitanium trichloride, ethoxytitanium trichloride, propoxytitanium trichloride, butoxytitanium trichloride, hexoxytitanium trichloride, octoxytitanium trichloride,
Phenoxytitanium trichloride, cyclohexoxytitanium trichloride, ethoxytitanium tribromide, butoxytitanium tribromide, dimethoxytitanium dichloride, jetoxytitanium dichloride, dipropoxytitanium dichloride, dibutoxytitanium dichloride, dioctoxytitanium dichloride Oxytitanium, diphenoxytitanium dichloride, −
Dicyclohexoxytitanium chloride, jetoxytitanium tribromide, dibutoxytitanium tribromide.

Examples include trimethoxytitanium chloride, triethoxytitanium chloride, tributoxytitanium chloride, triphenoxytitanium chloride, triethoxytitanium bromide, and triphenoxytitanium bromide.

Titanium halides other than titanium tetrachloride or titanium tetrabromide can be produced by the reaction of titanium tetrahalides with orthotitanates, but in the reaction of step m, tetrahalides are used instead of those produced by the above reaction. Mixtures of titanium oxide and orthotitanate (v) can also be used.

As the orthotitanate ester, the same orthotitanate esters mentioned above can be used. Among these titanium halides, titanium tetrachloride is most preferred.

Component +, g) General formula VOXs (On' )3-s
Alternatively, it is vanadyl halide or vanadium halide represented by VXt (O moromi) 4-t. Here, X is Cl or Br, 11'' and rcl are an alkyl group having 1 to 20 carbon atoms, an aryl group, or
0 cycloalkyl group, S is 1-3, t is 1-4
is the number of Specifically, vanadyl trichloride, vanadyl tribromide, methoxyvanadyl dichloride, ethoxyvanadyl dichloride, butoxyvanadyl dichloride, phenoxyvanadyl dichloride, cyclohexoxyvanadyl dichloride, ethoxyvanadyl tribromide, dimethoxyvanadyl chloride, Jetoxyvanadyl chloride, diphenoxyvanadyl chloride, jetoxyvanadyl bromide, vanadium tetrachloride, vanadium tetrabromide, methoxyvanadium trichloride, ethoxyvanadium trichloride, butoxyvanadium trichloride, phenoxyvanadium trichloride,
Cyclohexoxyvanadium trichloride, ethoxyvanadium tribromide, dimethoxyvanadium dichloride, jetoxyvanadium dichloride, ethoxyvanadium dichloride, diphenoxyvanadium dichloride, jetoxyvanadium tribromide,
Examples include triethoxyvanadium chloride, triphenoxyvanadium chloride, and triethoxyvanadium bromide. Among these vanadyl halides or vanadium halides, vanadyl trichloride and vanadium tetrachloride are preferred.

Components (component ① can also be used as a mixture and/or reactant in the reaction with solid product (1) 5)
Ru. It can also be used after being diluted with the above-mentioned inert hydrocarbon solvent.

The ingredient is aromatic polycarboxylic acid ester. Examples of the aromatic polycarboxylic acid ester include benzene polycarboxylic acid ester and naphthalene polycarboxylic acid ester. As for benzene polyvalent carboxylic acid ester, monomethyl phthalate,
Dimethyl phthalate, monoethyl phthalate, diethyl phthalate, dipropyl phthalate, mono-n-butyl phthalate, di-n-butyl phthalate, monoisobutyl phthalate,
Diisobutyl phthalate, di-n-hexyl phthalate, di-2-ethylhexyl phthalate, di-n-octyl phthalate, didecyl phthalate, dibenzyl phthalate, diphenyl phthalate, diethyl isophthalate, dipropyl isophthalate, dibutyl isophthalate , isophthalic acid di-2
- Mono- and diesters of benzenedicarponic acids such as ethylhexyl, diethyl terephthalate, dipropyl terephthalate, dibutyl terephthalate, dioctyl terephthalate, dibenzyl terephthalate and diphenyl terephthalate, monobutyl hemimellate, dibutyl hemimellate, tributyl hemimellate , mono-, di- and triesters of benzenetricarboxylic acids, such as monoethyl trimeldate, dipropyl trimelide, tributyl trimelide, diethyl trimesate, tributyl trimesate and tri-2-ethylhexyl trimesate;
Mono, di, tri and tetraesters of benzenetetracarboxylic acids such as monomethyl brenidate, diethyl brenidate, tripropyl brenidate, tetrabutyl brenidate, diethyldibutyl brenidate, dibutyl merophanate, tetrabutyl pyromellitate and dimethyldipropyl biromellitate. mono-, di-, tri-, tetra-, penta- and hexaesters, etc., which are resistant to benzenepentacarboxylic acid and melito, can be used. Further, as the naphthalene polycarboxylic acid ester, mono-, di-, tri-, tetra-, and pentaesters of naphthalene dicarboxylic acid, naphthalene tricarboxylic acid, naphthalene tetracarboxylic acid, and naphthalene pentacarboxylic acid can be used.

Next, the reaction between solid product (I) and (component C) will be described. This m-th stage reaction is carried out by adding (component C) to the solid product (I) suspended in the above-mentioned inert hydrocarbon solvent, or adding the solid product (I) or its suspension to (component C). This can be done by adding a cloudy solution or the like.

Specifically, for example, there are the following methods. That is, ■solid product (■) in an inert hydrocarbon solvent;
Component (1) and/or (2) and component [e] are simultaneously added and reacted. ■After adding component (f) and/or (second) and component (+) into an inert hydrocarbon solvent, the solid product (1) is added and reacted. (3) Liquid component (■) and/or ( After adding the solid product (I) to the liquid component (2), add the component (second) and react; (An example is a method in which two or more of Xun (1) to (4) are combined.

The amount of component (1) or (2) to be used is 1-10% per mole of the magnesium compound that is the raw material for solid product (I).
0 mol, preferably 3 to 50 mol, and the amount used of the component (width) is 0.01 to 0.8 mol, preferably 0.03 to 0.
．． It is 7 moles. These components may be used all at once or in several stages.

The reaction temperature of solid product (I) and (component C) is 40-20
0°C, preferably 50-150°C, reaction time between 5 minutes and 6 minutes
After the reaction for a period of time, preferably 10 minutes to 5 hours, the solid is separated by filtration or decantation and washed with an inert hydrocarbon solvent to remove unreacted substances or by-products. A solid product (II) is thus obtained. The solvent used during cleaning is a liquid inert hydrocarbon. Specific examples include aliphatic saturated hydrocarbons such as hexane, heptane, octane, nonane, decane, and kerosene. During and after washing, the solid product (■) must coexist with at least 50% by weight of the liquid aliphatic saturated hydrocarbon mentioned above.

The washing method is particularly preferably a decantation method, and after washing, it is preferable that the solid product (II) coexists in an amount such that at least the solid product (II) is immersed in the liquid aliphatic hydrocarbon. ), the solid product (II
) does not exhibit sufficient catalytic performance even if it is subjected to polymerization after being combined with an organoaluminum compound, that is, the polymerization results are low in polymer yield and bulk specific gravity, and the shape of the polymer particles is poor.
Moreover, the stereoregularity is also low.The reason is not yet clear, but the solid product (II) during and after washing is stored in the coexistence of at least 50% by weight of liquid aliphatic saturated hydrocarbons, and It is important to subject it to polymerization.

Next, the polyolefin manufacturing method will be described. The solid product (U) can be used as a catalyst for polyolefin production by combining with an organoaluminum compound and an organosilicon compound component having Si-0 to C bonds as a solid catalyst component. can use a compound represented by AIXrR';-r. Here, X is C1, r is carbon number 1
~20 alkyl group, aryl group or 3 to 20 carbon atoms
is a cycloalkyl group, and r is a number from θ to 2. Specifically, triethylaluminum, tri-n-propylaluminum, tri-butylaluminum, tricyclohexylaluminum, tricyclohexylaluminum, dimethylaluminum chloride, diethylaluminum chloride, di-n-butylaluminum chloride, ethylaluminum sesquichloride, and ethylaluminum Examples include dichloride. Among them, triethylaluminum or a mixture of two types of organic aluminum compounds such as triethylaluminum and tri-1-butylaluminum, triethylaluminum and diethylaluminium chloride, and triethylaluminum and ethylaluminum sesquichloride, or triethylaluminum and tri-l-butylaluminum It is preferable to use a mixture of three types of organoaluminum compounds such as aluminum and ethylaluminum sesquichloride.

The organosilicon compound component has the general formula gsi(OnQ
) A compound represented by 4-u can be used.

Here, r and represent an alkyl group having 1 to 20 carbon atoms, an aryl group, or a cycloalkyl group having 3 to 20 carbon atoms, and U is a number of 0 to 3.

Specifically, methyl silicate, ethyl silicate, butyl silicate, methyltrimethoxysilane, methyltriethoxysilane, methyltriphenoxysilane, methyltribenzyloxysilane, methylethoxydimethoxysilane, methylphenoxydimethoxysilane, Methylmethoxyethoxyphenoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriphenoxysilane,
Ethyltribenzyloxysilane, ethyl ethoxydimethoxysilane, ethylmethoxyjethoxysilane, ethylphenoxydimethoxysilane, ethylmethoxyethoxyphenoxysilane, butyltrimethoxysilane, butyltriethoxysilane, benzyltrimethoxysilane, benzyltriethoxysilane, benzylphenoxy Dimethoxysilane, benzylmethoxyethoxyphenoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, cyclopropyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenylmethoxyjethoxysilane, phenylmethoxyethoxyphenoxysilane, dimethyldimethoxysilane , dimethyljethoxysilane, dimethyldiphenoxysilane, dimethyldibenzyloxysilane, dimethylmethoxyethoxysilane, dimethylmethoxyphenoxysilane, dimethylethoxyphenoxysilane, methylethyldimethoxysilane, methylethyldiphenoxysilane, methylphenyldimethoxysilane, methylphenyl Diethoxysilane, methylphenyldiphenoxysilane, ethylphenyldimethoxysilane, ethylphenyldiethoxysilane.

Phenylbenzyldimethoxysilane, methylcyclopropyldimethoxysilane, methylvinyldimethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, trimethylphenoxysilane, trimethylbenzyloxysilane, triethylmethoxysilane, triethylethoxysilane, triethylphenoxysilane, triphenylmethoxysilane, Tribenzylmethoxysilane, dimethylethylmethoxysilane, dimethylphenylmethoxysilane, diethylmethylmethoxysilane, diethylmethylphenoxysilane, diphenylmethylmethoxysilane, diphenylbenzylmethoxysilane, dimethylcyclopropylmethoxysilane, methylethylphenylmethoxysilane, methylethylphenyl Examples include phenoxysilane. Among these, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenylmethoxyjethoxysilane, benzyltrimethoxysilane, methylethyldimethoxysilane, methylphenyldimethoxysilane, Methylethoxysilane, methylphenyldiethoxysilane, methylbenzyldimethoxysilane, dimethyldimethoxysilane, diethyldimethoxysilane, diphenyldimethoxysilane, dimethyljethoxysilane, trimethylmethoxysilane, triethylmethoxysilane,
Trimethylethoxysilane is preferred.

The method for combining the solid product (II), the organoaluminum compound, and the organosilicon compound components is as follows: (i) feeding the solid product (n), the organoaluminum compound, and the organosilicon compound components together into a polymerization vessel independently; and the organosilicon compound component and the solid product (II) are separately fed to the polymerization reactor. ■Solid product (■).

A mixture of organoaluminum compound and organosilicon compound components is fed to a polymerization vessel. There are several modes, and any of these methods can be adopted. However, among them, ■ or ■ may be preferable.When combining three such as 0 or more, each component or any component may be substituted with an aliphatic compound such as butane, pentane, hexane, heptane, nonane, decane, and kerosene. It can also be used dissolved or suspended in a hydrocarbon. When mixing before supplying to the polymerization vessel as in (2) and (2), the temperature is -50 to +50°C, preferably -30 to +30°C, and the time is 5 minutes to 50 hours, preferably 10 minutes to 30 hours. .

The amount of the organoaluminum compound used is 10 to 1000 mol, preferably 50 to 500 mol, per 1 mol of titanium atoms contained in the solid product (■) as a solid catalyst component. The amount of the organosilicon compound to be used is 0.01 to 2 mol, preferably 0.01 to 2 mol, per 1 mol of the organoaluminum compound.
05 to 1 mole. When using a mixed organoaluminum compound or a mixed organosilicon compound, the total number of moles thereof may fall within the above range.

Solid product (II) as solid catalyst component according to the invention
, using a catalyst obtained by a combination of an organoaluminum compound and an organosilicon compound, α-
Polyolefins are produced using olefins. As the α-olefin having 3 or more carbon atoms, propylene, butene-1, pentene-1, hexene-1, octene-1, decene-1,4-methylpentene-1, 3-methylpentene-1, etc. are used. be able to. These α−
The polymerization of olefins includes not only homopolymerization but also copolymerization with one or more other α-olefins having 2 or more carbon atoms. In addition to the above-mentioned α-olefins having 3 or more carbon atoms, examples of α-olefins having 2 or more carbon atoms include ethylene, butadiene, isoprene, 1.4-
Mention may be made of pentadiene and methyl-1,4-hexadiene. The amount of these other α-olefins used is 50% by weight in the copolymer obtained by copolymerization.
Polymerization can be carried out in the liquid phase or in the gas phase. If the polymerization is carried out in the liquid phase, an inert hydrocarbon solvent such as hexane, heptane, nonane, decane or kerosene may be used as the polymerization medium, but the α-olefin itself may also be used as the reaction medium. can. When polymerization is carried out in the gas phase, no reaction medium is used in principle, but the catalyst or any of its components may be dissolved or suspended in the above-mentioned inert hydrocarbons. This is carried out by contacting the catalyst and the α-olefin in the process.

Polymerization temperature is 40-200°C, preferably 50-150°C
and the polymerization pressure is atmospheric pressure ~ 100 kg/crn'G
, preferably 5 to 50 kg/crrr2G, can be carried out in any of the batch, semi-continuous or continuous modes, but continuous polymerization is preferred industrially. It is also possible to carry out multistage polymerization with different numbers. The molecular weight of the polymer, in
In order to achieve this, it is effective to add a molecular adhesion regulator such as hydrogen to the polymerization system.

The production or storage of the solid catalyst components, preparation of the catalyst, and production of the polymer described above must be carried out under an atmosphere of an inert gas such as nitrogen or helium, but in some cases it may be carried out under an atmosphere of 70°C or under vacuum. It can be done under certain conditions.

The effects obtained by the present invention are as follows. The catalyst obtained by combining the solid catalyst component of the present invention with an organoaluminum compound component and an organosilicon compound component has extremely high polymerization activity and is effective in removing residual catalyst from the polymer. It's not necessary. This method eliminates the need for a polymer purification process, making it extremely economical. In addition, the stereoregularity of the polymer is extremely high, making it possible to omit the removal step of the 7-tactic polymer, making it economical. This is sufficiently clear from the stereoregularity. Moreover, the polyolefin of the present invention has a narrow molecular spear distribution,
Extremely suitable for injection molding, textiles and some types of films. Furthermore, the polymer obtained by the production method of the present invention is odorless, and during granulation, the gas discharged from the vent part of the granulator or the molten polymer at the outlet of the granulator has almost no odor due to the organosilicon compound component. That's true. This facilitates handling of the polymer during granulation and
Moreover, it is economical because it does not cause environmental pollution such as polluting the atmosphere.

Another advantage of the present invention is that the solid product (IT) has a spherical or near-spherical shape, and its average particle size can be controlled from about 5 to about fiOgm. Thus, the polymer obtained using the solid product (II) has a nearly spherical shape reflecting the shape of the solid product (II), and there is very little or no fine powder polymer with a particle size of less than 100 μm. Due to these features, it is possible to produce and transport polymers stably for a long period of time in liquid phase methods such as slurry polymerization and bulk polymerization, and gas phase polymerization methods, and the production process can be simplified compared to conventional methods. Among these, it is extremely advantageous for producing polymers by gas phase polymerization. Since the particle shape of the polymer is good, the fluidity is good, and even if it is a copolymer, there is little deterioration in the particle shape or decrease in bulk specific gravity, and the copolymer is easy to produce.

In Examples and Comparative Examples, the methods for measuring various properties that define the polymer are as follows.

(1) Me Jlz170~Rate (MFR t) t*
According to ASTM DI238(L).

(2) Polymer bulk density (abbreviated as BD) is ASTM
According to D1835.

(3) Extraction method stereoregularity (ESS) is the ratio of the extraction residue after extracting a polymer with boiling n-heptane (98°C) for 6 hours to the total amount before extraction.

(4) Infrared stereoregularity (IR-) refers to the absorbance ratio (A3B7/
A972), and the larger the value, the higher the stereoregularity.

(5) The presence or absence of odor of the polymer was determined by an odor sensory test after the polymer obtained by polymerization of α-olefin was left at 50° C. for 3 hours in a nitrogen stream.

(6) The molecular weight of the polymer is GPC-1 manufactured by Waters.
50C type gel permeation chromatography (
135° C.] to determine the number average molecular weight (˜) and the average I5 molecular value (ζ), and the ratio was used as an index of molecular weight distribution.

The present invention will be explained below with reference to Examples and Comparative Examples.

Example 1 (1) Preparation of solid catalyst component In a glass flask, 3 h of purified decane, 4.8 g of anhydrous magnesium chloride, and 1 n-butyl orthotitanate were added.
7 g and 19.5 g of 2-ethyl-1-hexanol were mixed and heated to 130°C for 1 hour while stirring to form a uniform solution. The solution was brought to room temperature and heated to 70'C for 1 hour after addition of 3.5 g of ethyl p-toluate, followed by 2.5 g of silicon tetrachloride with stirring.
The mixture was added dropwise over a period of time 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 purified hexane to yield solid product (I). The solid product (I)
The total amount was mixed with 50111 g of titanium tetrachloride dissolved in 50+41 l,2-dichloroethane, then 2.8 g of diisobutyl phthalate was added, and the mixture was reacted at 100°C for 2 hours with stirring, and then the liquid phase was formed at the same temperature. 1 part was removed by decantation, 50 mM of 1,2-dichloroethane and 50 ml of titanium tetrachloride were added, and 1
The mixture was stirred at 00° C. for 2 hours and washed with purified hexane to give a solid product (II). The solid product (H) was added with purified hexane without drying to form a solid product (II).
It was made into a suspension. Solid product (■) 3 in one sentence of the suspension
It was present in a proportion of 0g. The above-mentioned operations and similar operations in subsequent Examples and Comparative Examples were all performed under a nitrogen atmosphere.

The solid product (■) is spherical and its particle size distribution is narrow;
The 8 composition analysis results showed that the average particle size was 204 m, Ti 2
．． 3% by weight (hereinafter referred to as %), Cl 54.1%.

Kg 16.4%, Si 1.0%, P-ethyl toluate 1.8%, butoxy group 3.8%, ethylhexanoxy group 0.9% and diisobutyl phthalate 13.4%
Met.

(2) Production of polyolefin 2 mmol of triethylaluminum, 2 mmol of triethylaluminum,
After adding 0.3 mmol of diphenyldimethoxysilane, 15 g of solid product (■) and 0.71 g of hydrogen, 70
The mixture was heated for 2 hours while continuously introducing propylene so that the total pressure was 22 kg/crry'G. Thereafter, unreacted propylene was discharged to obtain 230 g of powdered polypropylene. 8 holes of the polypropylene are 0
．． 44, MFR5.4, the polymer particles had a nearly spherical shape and the particle size distribution was extremely narrow, and the amount of fine powder with a particle size of 1100p or less was 0.05 times 1% of the total. Also, E.S.
S is 98.0. IR-τ is 0.945. My/MN
was 5.0, no odor was observed in the odor sensory test, and it was not susceptible to grinding. The polymerization results are shown in the table below (
The same applies to the following Examples and Comparative Examples).

Comparative Examples 1 to 4 P-1 Ethyl toluate not used (Comparative Example 1), diisobutyl phthalate not used (Comparative Example 2), p-ethyl toluate 1.7 instead of diisobutyl phthalate
The procedure was the same as in Example 1, except that g was used (Comparative Example 3) and p-ethyl anisate was used instead of diphenyldimethoxysilane (Comparative Example 4).

Examples 2 to 5 Polytitanic acid n instead of orthotitanium flJn-butyl
- using 12 g of butyl (pentate) (Example 2),
Using 17.5 g of n-heptatool in place of 2-ethyl-1-hexanol (Example 3), using 567 g of magnesium jetoxide in place of anhydrous magnesium chloride (Example 4), and compacted magnesium monoethoxy A solid product (II) was prepared in the same manner as in Example 1, except that 5.3 g of the solid product (II) was used (Example 5), and a polyolefin was produced using the solid product (II).

The polyolefin had a nearly spherical particle shape, a narrow particle size distribution, and a fine powder amount of 0 to 0.07% by weight of the total, and was not susceptible to grinding.

Examples 6-16.

A solid product (II
) was prepared to produce a polyolefin.

Phthal chu monoisobutyl (Example 6), phthal mji n
-popyru (Example 7), di-2-xfhexyl phthalate (Example 8), diisobutyl isophthalate (Example 9), di-n-butyl isophthalate (Example 1O), diisobutyl terephthalate (Example 1O), Example 11), hemimelito-ugly tri-n-butyl (Example 12), diisopropyl trimelinate (Example 13), diethyl diisopropyl brenidate (Example 14), pyromellito-ugly tetra-n-butyl (Example 15) and dicarboxylic naphthalate di-n-butyl acid (Example te).

Example 17 Purification/nan 5hJl in a stainless steel flask
, 4.8 g of anhydrous magnesium chloride, 14.8 g of ethyl orthotitanate, and 16.3 g of n-year-old ethanol were mixed and heated to 110° C. for 2 cycles with stirring to form a homogeneous solution. The solution was brought to 70°C, and the temperature was 0. 3.2 g of ethyl fragrant was added and dissolved, and then 15 g of phenyl silicon trichloride was added dropwise over 2.5 hours to precipitate a solid.
The mixture was further stirred at 70°C for 1 hour. The solid was separated from the solution and washed with purified hexane to yield solid product (I).

The solid product (I) is mixed with 100 ml of titanium tetrachloride, followed by the addition of 2.2 g of di-n-butyl phthalate,
After reacting at 110°C for 1.5 hours with stirring,
At the same temperature, the liquid phase was removed and titanium tetrachloride 100 was added again.
The mixture was stirred at 100°C for 2 hours, and then washed with purified hexane to obtain a solid product (II). The solid product (II) was made into a purified hexane suspension without drying. . A proportion of 10 g of solid product (II) was present in 100 ml of the suspension.

The solid product (II) was spherical and had a narrow particle size distribution, with an average particle size of 18 m.From the composition analysis, Ti2.
7%, Cl55.8%,! IIg15.7%, Si
1.2%.

The contents were 1.0% ethyl benzoate, 3.1% ethoxy groups, 1.0% octoxy, 1.0%, and 14.1% di-n-butyl phthalate.

A polyolefin was prepared in the same manner as in Example 1, except that the solid product (II) of this example was used instead of the solid product (II) of Example 1, and phenyltriethoxysilane was used instead of diphenyldimethoxysilane. Manufactured.

Comparative Examples 5 to 7 Not using ethyl benzoate (Comparative Example 5), not using di-n-butyl phthalate (Comparative Example 6), and using ethyl p-anisate instead of phenyltriethoxysilane The same procedure as in Example 1 was carried out except for (Comparative Example 7).

Claims (7)

[Claims] (1) The solid product (II) produced through the reactions of the following steps I, II and III is used as a solid catalyst component, and the solid catalyst component is an organoaluminum compound component and an organosilicon compound component having a Si-O-C bond. A method for producing a polyolefin, which comprises polymerizing an olefin using a catalyst obtained in combination with. I, magnesium halide [a] represented by the general formula MgXn(OR^1)_2_-_n (where X is Cl
or Br, R^1 is an alkyl group having 1 to 20 carbon atoms, an aryl group, or a cycloalkyl group having 3 to 20 carbon atoms, and n is a number of 0 to 2), general formula Ti (OR^2)
Orthotitanate ester represented by _4 and/or general formula R^3-(O-Ti(OR^4) (OR^5))-_m
Polytitanate ester [b] represented by O-R^6 (
Here, R^2, R^3, R^4, R^5 and R^6 are an alkyl group having 1 to 20 carbon atoms, an aryl group or a cycloalkyl group having 3 to 20 carbon atoms, and m is 2. ~20) and a saturated or unsaturated monohydric or polyhydric alcohol [c] having 1 to 20 carbon atoms are mixed in an inert hydrocarbon solvent and reacted and dissolved to obtain (component A). , II, in the (component A), an aliphatic or aromatic monocarboxylic acid ester having 2 to 24 carbon atoms (hereinafter referred to as organic acid ester) [d] and the general formula SiX_lR^7_4_
−_l or SiX_p(OR^8)_4_-_p(
Here, X is Cl or Br, R^7 and R^8 are each an alkyl group having 1 to 20 carbon atoms, an aryl group, or a cycloalkyl group having 3 to 20 carbon atoms, and l and p are 1 to 4
(component B) consisting of silicon halide [e] represented by , general formula TiX_q(OR
^9)_4_-_q (Here, X is Cl or Br, R
^9 is an alkyl group having 1 to 20 carbon atoms, an aryl group, or a cycloalkyl group having 3 to 20 carbon atoms, and q is 1 to 4
titanium halide [f] represented by the number of ) and/or the general formula VOX_s(OR^1^0)_3_-
_s or VX_t(OR^1^1)_4_-_t(
Here, X is Cl or Br, R^1^0 and R^1
^1 is an alkyl group having 1 to 20 carbon atoms, an aryl group, or a cycloalkyl group having 3 to 20 carbon atoms, and S is 1 to 20 carbon atoms.
3, t is a number from 1 to 4) consisting of halogenated vanadyl or halogenated vanadium [g] and aromatic polyhydric carboxylic acid ester [h] (component C)
A reaction in which a solid (hereinafter referred to as solid product (II)) is obtained by reacting. (2) Constituent raw materials [a], [b] and [c of component A]
] in an inert hydrocarbon solvent at 50-150°C, 0-5 kg
The polyolefin manufacturing method according to claim 1, wherein the polyolefin is stirred or shaken and mixed for 10 minutes to 5 hours at a pressure of /cm^2G for reaction and dissolution. (3) 0.1 to 0.7 moles of [d] and 1 to 20 moles of [e] are mixed into (component A) per 1 mole of [a] that constitutes (component A) as a raw material. 0-130℃, 0-5
The polyolefin manufacturing method according to claim (1), wherein the reaction is carried out at kg/cm^2G for 10 minutes to 5 hours. (4) Wash the solid product (I) obtained by the reaction of (component A) and (component B) with an inert hydrocarbon solvent, and apply the constituent raw materials of the solid product (I) to the object to be washed. There is [a
] 3 to 50 moles per mole of (O and/or [
g] and 0.01 to 0.8 mol of [h] were mixed and heated at 50 to 150°C and 0 to 5 kg/cm^2G for 10 minutes to 5
A method for producing a polyolefin according to claim (1), in which the reaction is carried out over a period of time. (5) As the aromatic polycarboxylic acid ester, benzenedicarboxylic acid diester, benzenetricarboxylic acid diester and triester, benzenetetracarboxylic acid diester, triester and tetraester, and naphthalene dicarboxylic acid diester are used in claim 1 (1). ) The polyolefin manufacturing method described in item 1. (6) As an organosilicon compound having a Si-O-C bond, the general formula R^1^2_uSi(OR^1^3)_4_
-_u (Here, R^1^2 and R^1^3 are an alkyl group having 1 to 20 carbon atoms, an aryl group, or an aryl group having 3 to 2 carbon atoms.
0 cycloalkyl group, u is a number from 0 to 3)
2. The polyolefin manufacturing method according to claim 1, wherein 0.01 to 2 moles per gram atom of Al are used as the organoaluminum compound component in which the organosilicon compounds are simultaneously combined. (7) The polyolefin manufacturing method according to claim (1), in which the α-olefin is polymerized in a gas phase.