JPS6389509A - Production of solid catalyst component for producing polyolefin - Google Patents

Abstract

PURPOSE:To obtain the title catalyst component excellent in heat stability, storage stability and grinding resistance, by allowing a specified Mg compound to support a titanium halide, etc. CONSTITUTION:A solid is obtained by prepolymerizing a 2C or higher alpha-olefin and a solid obtained by adding a mixture of a 2-24C aliphatic or aromatic monocarboxylic ester (D) with a silicon halide (E) of formula IV or V (wherein R<7-8> are each R<1>, and l and p are each 1-4) to a solution obtained by mixing a magnesium halide (A) of formula I (wherein X is Cl or Br, R<1> is a 1-20C alkyl, aryl or a 3-20C cycloalkyl and n is 0-2) with an ortho- and/or poly- titanic esters (B) of formulas II and III (wherein R<2-6> are each R<1> and m is 2-20) and a 1-20C (un)saturated alcohol (C) in an inert solvent in the presence of an organoaluminum compound. This solid is reacted with a titanium halide (F) of formula VI (wherein R<9> and R<1> and q is l) and/or a vanadyl halide of formula VII (wherein R<10> is R<1> and s is 1-3) or a vanadium halide (G) of formula VIII (wherein R<11> is R<1> and t is l).

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Technology] The present invention relates to a method for producing a solid catalyst component for producing polyolefins. More specifically, the catalyst component is a solid catalyst component for polyolefin production which has a magnesium compound as a main supporting material and a titanium halide or the like as a supported component, and has improved storage stability, thermal stability and attrition resistance. Regarding manufacturing methods.

[Technology of the prior application and its problems]

Previously, the present inventors disclosed in Japanese Patent Application No. 60-244500 a novel method for producing a solid catalyst component that provides an odorless olefin polymer with high monopolymerization activity, high stereoregularity, and narrow molecular weight distribution (hereinafter referred to as proposed a new catalyst manufacturing method.

However, the solid catalyst component obtained in the earlier application.

Although it is stable for a long period of time when stored at temperatures below 30°C, the catalyst performance tends to change when stored at temperatures above 40°C. Also, during large-scale production of solid catalyst components, it is susceptible to attrition in the production equipment, resulting in fine powder solids. A problem occurred in which catalyst components were generated.

The above-mentioned storage temperature of 30°C or lower means that the container containing the solid catalyst component needs to be kept semi-cold, and as an industrial catalyst agent, storage, transportation, or packaging costs require semi-cold storage. It will be more expensive than without it,
Even if it is kept in a semi-cold state, it is difficult to maintain a sufficiently long shelf life. In addition, if fine powder is generated during the production of the solid catalyst, it is difficult or uneconomical to separate and remove the fine powder, and if the component containing the fine powder is used to constitute an olefin polymerization catalyst and used for olefin polymerization. The formation rate of fine powder of the olefin polymer increases, leading to disadvantageous results regarding the post-production handling and quality uniformity of the polymer. It is a well-known fact to experts in this technical field that the morphology of olefin polymers obtained by

[Purpose of the invention]

The inventors were currently researching the above-mentioned problems, but
In the catalyst production method of the previous application, when the solid product (I) precipitated from the solution state is polymerized with a small amount of α-olefin having 2 or more carbon atoms in the coexistence of an organoaluminum compound, the final product obtained Even if the solid product is stored at a temperature significantly higher than normal temperature (hereinafter referred to as ultra-normal temperature), such as 40°C, its catalytic activity does not substantially decrease, and the solid catalyst component production The inventors have discovered the fact that the above-mentioned fine powder is hardly generated during handling or use (note: during preactivation or polymerization), and have arrived at the present invention. Incidentally, the pre-polymerization treatment is performed on the solid product (I), and is a so-called α-olefin treatment on the combination (catalyst) of the final solid carrying the titanium compound and the organoaluminum compound. It differs from pre-activation in its technical significance.

In addition, the solid product (I) has polymerization activity because it contains a polytitanate ester having a specific chemical structure. The object of the present invention is to solve the above-mentioned problems and provide a material with improved storage stability, thermal stability and attrition resistance.
An object of the present invention is to provide a method for producing a catalyst component for olefin polymerization that provides an odorless polyolefin with high polymerization activity, high stereoregularity, and a narrow molecular weight distribution.

[Structure and effects of the invention]

The present invention has the following configuration.

(1) In a method for producing a catalyst component for olefin polymerization in which titanium halide, vanadyl halide, or vanadium halide is supported on a carrier whose main component is an Mg compound precipitated from a solution state, 1. General formula MgX5 ( OR')2-71 Magnesium halide (a) (where X is Cl or Br, R' 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), an orthotitanium ester represented by the general formula Ti(OR'')4 and/or a general formula R3-f0-Ti(OR') (OR5) sleeve0-R
Polytitanate ester represented by & (here R2,
R1, R4, R5 and R6 are an alkyl group having 1 to 20 carbon atoms, an aryl group or a cycloalkyl group having 3 to 20 carbon atoms, m is a number of 2 to 20), and A saturated or unsaturated monohydric or polyhydric alcohol (2) is mixed in an inert hydrocarbon solvent and dissolved by reaction to obtain (r & min A); Aliphatic or aromatic monocarboxylic acid ester ■ and general formula Si
X cost claw - *i L < Ha5iXp (OR") < -P
@ (X is Cl or Or, R' and R@ 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 p is 1
A solid product (hereinafter referred to as solid product (1)) is precipitated by mixing and reacting (component B) consisting of a silicon halide (with a number of 1 to 4);
A solid product (I
I) is obtained, ■, the solid product (II) has the general formula TiX
q (OR')4-q (where X is Cl or Br
, R9 is an alkyl group having 1 to 2 carbon atoms, an aryl group, or a cycloalkyl group having 3 to 20 carbon atoms, and q is 1
~4) and/or titanium halide represented by the general formula VClXs (OR" h-8
< HA V is a number from 1 to 3, and t is a number from 1 to 4) (component C) consisting of vanadyl halide or vanadium halide represented by However, one or more of the steps ① and ③ above.

In component A or solid product Cl), (TI)
Alternatively, a method for producing a solid catalyst component for polyolefin production, which comprises mixing aromatic carboxylic acid ester (2) with (m) and reacting the mixture.

(2) 0.01 to 500 g per 1 g of solid product (I)
The method according to item (1) above, wherein the α-olefin is reacted.

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

Stage I will be described first.

(Component A) can be obtained by mixing components (1), (2) and (2) in an inert hydrocarbon and reacting and dissolving them. Component (2) is a magnesium halide represented by the general formula Mg(OR')2-n. Here, X is Cl or Or,
R' 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 0 to 20 carbon atoms.
The number is 2. Specifically, magnesium sybaride,
They are alkoxymagnesium halides and magnesium dialkoxides. 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 dialkoxide, magnesium diphenoxide, magnesium dicyclopropoxide, magnesium methoxyethoxide, and magnesium methoxyethoxy. and magnesium ethoxy phenoxide.

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. As the titanate ester, orthotitaph% expressed by Ti(OR2)4
-1-Stell and R3-fO-Ti(OR') (
OR') is a polytitanate ester represented by 0-n&. Here, R2, R3, R4, R5 and R
6 is an alkyl group having 1 to 20+7 carbon atoms, an aryl group, or a cycloalkyl group having 3 to 20 carbon atoms, and m is 2 to 20
The number is 20.

Specifically, methyl orthotitanate, ethyl orthotitanate, orthotitanium fi1jn-propyl, orthotitanium 1li-propyl, n-butyl orthotitanate, butyl orthotitanate, n-butyl orthotitanate, orthotitanium. 2-ethylhexyl acid, n- orthotitanate
Orthotitanate esters such as octyl, phenyl orthotitanate and cyclohexyl orthotitanate, methyl polytitanate, ethyl polytitanate, n polytitanate
-Propyl, i-propyl polytitanate, polytitanium f
Polytitanate esters such as llJn-butyl, i-butyl polytitanate, n-amyl polytitanate, 2-ethylhexyl polytitanate, n-octyl polytitanate, phenyl polytitanate, and cyclohexyl polytitanate 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, i-propyl alcohol, n-
Ethylene glycol as well as monohydric alcohols such as butyl alcohol, n-7myl alcohol, i-amyl alcohol, n-hexyl alcohol, n-octyl alcohol, 2-ethylhexyl alcohol and allyl alcohol.

Polyhydric alcohols such as trimethylene glycol and glycerin can also be used. Among them, carbon number is 4~
10 aliphatic saturated alcohols are preferred.

Inert hydrocarbon solvents used to dissolve components ■, ■ and 0 include aliphatic hydrocarbons such as pentane, hexane, heptane, nonane, decane and kerosene, aromatic hydrocarbons such as benzene, toluene and xylene. , carbon tetrachloride, 1,2-dichloroethane, 1,1
．． Mention may be made of hydrocarbon halides such as 21-lichloroethane, chlorobenzene and 0-dichlorobenzene.

Among them, aliphatic hydrocarbons are preferred.

Specific methods for reacting and dissolving components (1), @, and (2) in an inert hydrocarbon solvent include the following methods. That is, (1) components (2), (2), and (2) are mixed in an arbitrary order of addition in an inert hydrocarbon solvent, and the suspension is heated while stirring.

■Heating ingredients ■ and ■ in an inert hydrocarbon solvent with stirring, adding ingredients ■ to the solution, ■ ingredients ■ and ■
is heated with stirring in an inert hydrocarbon solvent, and then component (2) is added, or (2) component (2) and @ are heated in an inert hydrocarbon solvent while stirring, and then component (2) is added.

Although any of the above methods can be employed, method (2) is preferred because it is extremely easy to operate.

Heating is necessary to dissolve components (1), (2) and (2) in the inert hydrocarbon solvent. The heating temperature is 40
-200°C, preferably 50-150°C. The time required for the reaction and dissolution is 5 minutes to 7 hours, preferably 1 hour.
It is 0 minutes to 5 hours. The amount of component (■) to be used is 0.1 to 0.1 to 1 mole of component if the former is orthotitanium ugly ester.
2 moles, preferably 0.5 to 1.5 moles, and in the case of polytitanate esters, it is sufficient to use an amount equivalent to the orthotitanate ester in terms of orthotitanate units. The amount is 0.1 to 5 mol, preferably 0.5 to 4 mol.

Regarding the amount of components (■) and (2) used, it is easier to dissolve them when they are larger than the amount of component (■), but when (■) is dissolved in this way, an extremely large amount of halogenation is required to solidify (component A). In addition to having to use silicon, solidification itself is difficult, and even after solidification, it is extremely difficult to control the particle shape.

In addition, if the amounts of components (2) and (2) used are too small, component (2) will not dissolve in the inert hydrocarbon solvent, and the solid catalyst component will have an amorphous shape, making it impossible to obtain a polymer with a unispherical or nearly spherical particle shape. The amount of activated hydrocarbon solvent used is 0.1 to 5 fL, preferably 0.3 to 5 fL per mole of component 0.
There are 31.

Next, stage II will be described.

(Component B) consists of components (1) and (2).

Component (2) is an organic acid ester. Examples of organic acid esters include methyl acetate, ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, ethyl propionate,
n-propyl propionate, i-butyl propionate,
Using aliphatic carboxylic acid esters such as ethyl butyrate and phenyl acetate, aromatic carboxylic acid esters such as methyl benzoate, ethyl benzoate, methyl toluate, ethyl toluate, methyl anisate, ethyl anisate and phenyl anisate. Can be done.

Ingredient ■ is the general formula SiX or SiXp (
OR' ) 4-P is a silicon halide. Here, or Cl or Br, R' and R7 are an alkyl group having 1 to 20 carbon atoms, an aryl group having 3 to 20 carbon atoms, or
20 cycloalkyl groups, and or p is a number from 1 to 4. Specifically, as the 5iXeR knee cost, silicon tetrachloride, silicon tetrabromide, ethyl silicon trichloride, propyl silicon trichloride, butyl silicon trichloride, phenyl silicon trichloride, cyclohexyl silicon trichloride, ethyl silicon tribromide, 5iXp (OR'
) 4-P, silicon tetrachloride, silicon tetrabromide, methoxy silicon trichloride, silicon trichloride, propoxy silicon trichloride, butoxy silicon trichloride, phenoxy silicon trichloride, ethoxy silicon tribromide, dimethoxy silicon dichloride , dichlorosilicon dichloride, dibutoxysilicon dichloride, diphenoxysilicon dichloride, dimethoxysilicon tribromide, trimethoxysilicon chloride, triethoxysilicon chloride, and the like. 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 Cl)
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 A is reacted with component (2) and then component (2) is reacted to precipitate the solid product (I).

■A solid product (I) is obtained by simultaneously reacting components ■ and ■.
is precipitated. (1) A method in which component (2) is reacted to precipitate a solid and then component (2) is reacted to form a solid product (I), or a method in which two or more of any two or more of (2) to (2) are combined. Either method can be adopted.

Even when (component A) is mixed or reacted with component (2), no solid is precipitated.The mixture or reaction product of (component A) or (component A) and component (2) is a homogeneous solution. Component (2) is necessary to precipitate solids from these homogeneous solutions. As for the addition method related to the above-mentioned items 1 to 2, it is preferable to add component 2 to (component A), but component
), or (component A) can be added to component (2). Since the particle shape of the solid product (II) is controlled by the particle shape of the solid product (I), the particle shape can be controlled by a mixture or reaction of component (2) and (component A) or (component A) and component (2). Reactions with objects are extremely important.

The usage ratio of (component A) and components (1) and (2) is as follows. That is, for 01 mole of the component constituting (component A) as a raw material, the amount of component (2) used is 0.05 to 0.7 mole,
Preferably, the amount used is 0.1 to 0.6 mol, and the amount of component (1) used is 0.1 to 50 mol, preferably 1 to 20 mol.

These components may be used all at once or in several stages.

The reaction temperature of (component A) and (component B) is -40 to +18
The temperature is 0°C, preferably -20 to +150°C, and the reaction time is 5 minutes to 6 hours, preferably 10 minutes to 5 hours per step. The solid product (I) precipitated by the reaction of (component A) and (component B) may be subsequently subjected to the next step of the reaction, but it must be washed with the inert hydrocarbon solvent mentioned above. is preferred, thus obtaining a spherical or near-spherical solid product Cl).

Next, we will discuss stage (■).

In this step, the solid product (I) obtained in the previous step
- prepolymerization by contact with olefins to produce a solid product (I
The significance of the pre-polymerization treatment I) is as described above. In this case, a compound represented by AIXrle;-r, which will be described later, can be used as the organoaluminum compound and the material, which may or may not contain an inert hydrocarbon solvent. α- with 2 or more carbon atoms
As olefins, ethylene, fluoropylene, butene
1, pentene-1, hexene-1, octene-1,4-
In addition to methylpentene-1 and 3-methylpentene-1, mention may be made of butadiene, isoprene, 1,4-pentadiene, methyl-1,4-hexadiene, and the like. Inert hydrocarbon solvents may include hexane, heptane, nonane, decane and kerosene. As a method for prepolymerizing the solid product (I) by contacting it with an α-olefin, for example, ① Mixing the solid product (r) and an organoaluminum compound in an inert hydrocarbon solvent and then supplying the α-olefin. ■ Supplying the α-olefin after making the solid product (I) cloudy in an inert hydrocarbon solvent in which an organoaluminum compound is dissolved;
Alternatively, (2) the solid product (I) is added to an inert hydrocarbon solvent in which an organoaluminum compound and an α-olefin are dissolved, and if necessary, an α-olefin is further supplied.

Pre-polymerized polyolefin per 1 g of solid product Cl) is 0. QO1-1000 g, preferably 0.01-5
00g of α-olefin. The amount of organic aluminum used is 0.1 to 500 mol, preferably 0.5 to 100 mol, per 1 mol of titanium atoms contained in the solid product (1). The amount of inert hydrocarbon solvent to be used is from 0 to 1,000 ml per 1 g of solid product (I),
Preferably it is 5 to 500 Russian.

The temperature during pre-414 polymerization is -20 to +50°C, preferably 0 to 30°C, and the time is 1 minute to 5 hours, preferably 3 minutes to 3 hours. In the prepolymerization step, carboxylic esters such as ethyl benzoate, methyl toluate, and ethyl anisate, or silane compounds such as phenyltriethoxysilane, diphenyldimethoxysilane, and methyltriethoxysilane may be present. The amount used is 0 to 2 mol, preferably 0 to 0.5 mol, based on 1 mol of the organoaluminum compound. The solid product Cl) is coated with polyolefin.

Wash with the previously mentioned inert hydrocarbon solvent until no organoaluminum compound is detected in the filtrate.

A solid product (n) is thus obtained.

Next, we will discuss stage (■).

(Component C) consists of ■ and/or ■. Component (1) is a titanium halide represented by the general formula TiXq (OR')4-q. Here, X is Cl or Br, R'
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, Cyclohexytitanium chloride, ethoxytitanium tribromide, butoxytitanium tribromide, dimethoxytitanium dichloride, jetoxytitanium dichloride, dipropoxytitanium dichloride, dibutoxytitanium dichloride, dioctoxytitanium dichloride, dichloride Diphenoxy titanium, dicyclohexoxy titanium dichloride, jetoxy titanium tribromide, dibutoxy titanium tribromide, trimethoxy titanium chloride, triethoxy titanium chloride, tributoxy titanium chloride, triphenoxy titanium chloride, triethoxy bromide Examples include titanium and triphenoxytitanium bromide. Titanium halides other than titanium tetrachloride or titanium tetrabromide can be produced by the reaction of titanium tetrahalide and orthotitanate; Mixtures of titanium oxide and orthotitanate may 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.

Ingredient ■ has the general formula VOXs (OR”h-s or V
A vanadyl halide or a vanadium halide represented by
is an alkyl group, aryl group, or 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. Specifically, vanadyl trichloride, vanadyl tribromide, methoxyvanadyl dichloride, ethoxyvanadyl dichloride, butoxyvanadyl dichloride, phenoxyvanadyl dichloride, cyclohexoxyvanadyl dichloride, ethoxyvanadyl tribromide, dimethoxyvanadyl chloride, jetoxyvanadyl chloride,
Diphenoxyvanadyl chloride, solidified diphenoxyvanadyl,
Vanadium tetrachloride, vanadium tetrabromide, methoxyvanadium trichloride, ethoxyvanadium trichloride, butoxyvanadium trichloride, phenoxyvanadium trichloride, cyclohexoxyvanadium trichloride, ethoxyvanadium tribromide, dimethoxyvanadium dichloride, jetoxy dichloride Examples include vanadium, dibutoxyvanadium dichloride, diphenoxyvanadium dichloride, jetoxyvanadium tribromide, triethoxyvanadium chloride, triphenoxyvanadium chloride, and triethoxyvanadium bromide. Among these vanadyl halides or vanadium halides, vanadyl trichloride and vanadium tetrachloride are preferred.

Component (1) and component (2) can be used as a mixture and/or as a reactant in the reaction with the solid product (II''). They can also be used after being diluted with the above-mentioned inert hydrocarbon solvent.

Ingredient (2) is an aromatic polycarboxylic acid ester. Examples of the aromatic polycarboxylic acid ester include benzene polycarboxylic acid ester and naphthalene polycarboxylic acid ester. Specifically, benzene polycarboxylic acid esters include 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, di-2- isophthalate
Mono- and diesters of penzeldicarboxylic acids such as ethylhexyl, diethyl terephthalate, dipropyl terephthalate, dibutyl terephthalate, dioctyl terephthalate, dibenzyl terephthalate and diphenyl terephthalate, monobutyl hemimellate, dibutyl hemimellite, tributyl hemimellate, trimelide Mono-, di- and tri-esters of benzenetricarboxylic acids such as monoethyl acid, dipropyl trimellidate, tributyl trimellidate, diethyl trimesate, tributyl trimesate and tri-2-ethylhexyl trimesate, monomethyl brenide, diethyl brenide, tri-brenide resistant Mono-, di-, tri- and tetra-esters of benzenetetracarboxylic acids such as propyl, tetrabutyl brenidate, diethyldibutyl brenidate, diptyl merophanate, tetrabutyl pyromellitate and dimethyldipropyl pyromellitate, mono-, di-, tri- and tetraesters of benzenepentacarboxylic acid and mellitic acid. , di-, tri-, tetra-, penta- and hexaesters, etc. can be used. In addition, naphthalene polycarboxylic acid esters include naphthalene dicarboxylic acid, naphthalene tricarboxylic acid, naphthalene tetracarboxylic acid, and naphthalene pentacarboxylic acid,
Di, tri, tetra and pentaesters can be used.

Next, the reaction between the solid product (n) and (component C) will be described. This reaction in the second stage can be carried out by adding (s, part C) to the solid product (■) suspended in the previously mentioned inert hydrocarbon solvent, or by adding the solid product (n) or (component C) to the solid product (■). This can be carried out by adding a suspension solution thereof.

Specifically, for example, there are the following methods. That is, ■solid product (■) in an inert hydrocarbon solvent;
Components ■ and/or ■ and component ■ are simultaneously added and reacted. ■ After adding components Φ and/or ■ and component ■ to an inert hydrocarbon solvent, solid product (II) is added and reacted. ■ After adding the solid product (1'l) to liquid component (1) and/or (2), component (2) is added and reacted.

■Add component ■ to liquid component ■ and/or ■, then add solid product (■) and react, or ■■～■
A method that combines two or more of the following can be mentioned.

The amount of component (2) or (2) to be used is 1 to 1 mol per mole of the magnesium compound that is the constituent raw material of solid product (II).
00 mol, preferably 3 to 50 mol, and the amount of component (1) used 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 the solid product (IT) and (component C) is 40-2
00℃, preferably 50 to 150℃, reaction time is 5 minutes to
The time is 6 hours, preferably 10 minutes to 5 hours.

After the reaction, the solid is separated by separation or decantation and washed with an inert hydrocarbon solvent to remove unreacted substances or by-products. A solid product (m) 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. The solid product (m) can be dried and stored in the form of a powder, or can be stored as a suspension in the above-mentioned inert hydrocarbon solvent. In addition,
As mentioned above, the reaction in step V is carried out in one or more of steps 1 through 2, and is not an independent step.

Before using the solid product (m) to produce the polyolefin, it is also possible to further prepolymerize the solid product (II). Steps ■ except for using (III)
Prepolymerization can be carried out in the same manner as above. This prepolymerization treatment is distinguished from so-called "preactivation" in that the solid product (III) after treatment is not used directly for the formal polymerization of the olefin.

Next, the polyolefin manufacturing method will be described. The solid product (m) can be used as a catalyst for polyolefin production by combining an organoaluminum compound as a solid catalyst component and an organosilicon compound component having Sj, -0-C bonds. A compound represented by AIXrSho-r can be used. Here, X is C1, R″ is an alkyl group having 1 to 20 carbon atoms, an aryl group, or 3 to 2 carbon atoms.
0 cycloalkyl group, and r is a number of O to 2.

Specifically, triethylaluminum, tri-n-propylaluminum, tri-butylaluminum, tricyclopentylaluminium, tricyclohexylaluminum, dimethylaluminum chloride, diethylaluminum chloride, di-n-butylaluminum chloride, ethylaluminum sesquichloride, and ethylaluminum. Examples include dichloride.

Among them, triethylaluminum alone or triethylaluminum and treatybutylaluminum,
It is preferable to use a mixture of two types of organoaluminum compounds such as triethylaluminum and diethylaluminium chloride and triethylaluminum and ethylaluminum sesquichloride, or a mixture of three types of organoaluminum compounds such as triethylaluminum, treated butylaluminum and ethylaluminum sesquichloride. .

As the organosilicon compound component, general formula layer 5i (ORo
) A compound represented by 4-u can be used.

Here, f and r are 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, methyl Methoxyethoxyphenoxysilane, 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, trimethylphenoxy Silane, trimethylbenzyloxysilane, triethylmethoxydisilane, triethylethoxysilane.

Triethylphenoxysilane, triphenylmethoxysilane, tribenzylmethoxysilane, dimethylethylmethoxysilane, dimethylphenylmethoxysilane, diethylmethylmethoxysilane.

Examples include diethylmethylphenoxysilane, diphenylmethylmethoxysilane, diphenylbenzylmethoxysilane, dimethylcyclopropylmethoxysilane, methylethylphenylmethoxysilane, and methylethylphenylphenoxysilane. Among these,
Methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, phenyltriethoxysilane, phenylmethoxyjethoxysilane, benzyltrimethoxysilane, methylethyldimethoxysilane, methylphenyldimethoxysilane, methylethyljetoxysilane Toxysilane, methylphenyldiethoxysilane.

Preferred are methylbenzyldimethoxysilane, dimethyldimethoxysilane, diethyldimethoxysilane, diphenyldimethoxysilane, dimethyljethoxysilane, trimethylmethoxysilane, triethylmethoxysilane, and trimethylethoxysilane.

The method of combining the solid product (■), the organoaluminum compound, and the organosilicon compound component is as follows: ■The solid product (■), the organoaluminum compound, and the organosilicon compound component are fed independently to the polymerization vessel.■The organoaluminum compound and the organic silicon compound component and the solid product (m) are independently fed to the polymerization reactor, ■ the solid product (m
), a mixture of an organoaluminum compound and an organosilicon compound component is supplied to a polymerization vessel, and any of these methods can be adopted. However, among them, ■ or ■ may be preferable.When combining the champions such as 0 or more, each component or any component may be aliphatic carbonized such as butane, pentane, hexane, heptane, nonane, decane, and kerosene. It can also be used dissolved or suspended in hydrogen. 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 (m) 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 (■) as a solid catalyst component according to the present invention,
A polyolefin is produced using an α-olefin having 3 or more carbon atoms using a catalyst obtained by combining an organoaluminum compound and an organosilicon compound. Carbon number 3
The above α-olefins include propylene, butene-
1, pentene-1, hexene-1, octene-1, decene-1,4-methylpentene-1 and 3-methylpentene-1, etc. can be used. The polymerization of these α-olefins includes not only homopolymerization but also copolymerization with one or more other α-olefins having 2 or more carbon atoms. Examples of the α-olefin having 2 or more carbon atoms include ethylene, butadiene, isoprene, 1,4-pentadiene, and methyl-1,4-hexadiene in addition to the above-mentioned α-olefin having 3 or more carbon atoms. The amount of these other α-olefins used is such that the copolymer obtained by copolymerization contains less than 50% by weight. Hexapolymerization can be carried out in a liquid phase or a gas phase. If the polymerization is carried out in the liquid phase, an inert hydrocarbon solvent such as, for example, 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 with the α-olefin in the process.

Polymerization temperature is 40-200°C, preferably 50-150°C
The polymerization pressure is atmospheric pressure ~ 100 kg/cm'G
, preferably 5 to 50 kg/cg/g, 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 using different polymerization conditions. In order to control the molecular weight of the polymer, it is effective to add a molecular weight regulator such as hydrogen to the polymerization system.

The above-mentioned production or storage of solid catalyst components, preparation of catalysts, and production of polymers must be carried out under an atmosphere of an inert gas such as nitrogen or helium, but in some cases they may also be carried out under an atmosphere of monomers or under vacuum conditions. It can be carried out.

The effects obtained by the present invention are as follows.

The solid catalyst component for polyolefin production according to the present invention has excellent storage stability and thermal stability. It is extremely important in industry to be able to store things stably for long periods of time, regardless of the high or low outside temperatures. The preservation can be carried out either in powder form or in suspended form in an inert hydrocarbon solvent.

Furthermore, the solid catalyst component according to the present invention has excellent attrition resistance. The component is not susceptible to attrition during its use, ie, not only during the polyolefin production process, but also during the catalyst production process, which means that it prevents the formation of finely divided catalysts and thus prevents the formation of finely divided polymers. As a result, we were able to solve the entrainment problem that often occurs during the production of polyolefins in the gas phase polymerization process.

Another advantage of the present invention is that the polymerization activity is extremely high and there is no need to remove residual catalyst from the polymer. In addition, it is possible to produce a polyolefin that has high stereoregularity, a narrow molecular weight distribution, and is odorless.

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

Example 1 (1) Preparation of solid catalyst component In a glass flask, 730 m! ; L, anhydrous magnesium chloride 4.8 g, n-butyl orthotitanate 17 g and 2-ethyl-1-hexanol 19.5 g
were mixed and heated to 130° C. for 1 hour while stirring to dissolve and form a homogeneous solution. The solution was brought to room temperature and heated to 70° C. for 1 hour after adding 3.5 g of ethyl p-toluate, followed by stirring and adding 2.5 g of silicon tetrachloride.
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 hexane to obtain a solid product (1).

The Ti content of the solid product (1) is 3.0% by weight (hereinafter referred to as %).
The total amount of the solid product (I), which was described as 1.08-polymer/g
- Ethylene was introduced for 1 hour to give a solid product (I). A solid product (■) was obtained by washing with hexane until triethylaluminum was no longer detected in the filtrate.

The total amount of the solid product Cm) was dissolved in 50% of 1,2-dichloroethane.
Next, 2.8 g of diisobutyl phthalate was added, and the mixture was reacted at 100°C for 2 hours with stirring. The liquid phase was removed by decantation at the same temperature, and the mixture was heated again. , 50 mfL of 1,2-dichloroethane and 50 mf of titanium tetrachloride were added, stirred at 100°C for 2 hours, washed with hexane and dried to obtain a solid product (m). The solid product (m
) had a nearly spherical particle shape and contained 0.88% Ti and 61.0% polyethylene.

(2) Production of polyolefin A solid product (2 mmol of triethylaluminum, 0.3 mmol of diphenyldimethoxysilane,
After adding 38.6 mg of II) and 0.7 grams of hydrogen, 7
Polymerization was carried out for 2 hours while continuously introducing propylene at 0° C. so that the total pressure was 22 kg/am″GK. Thereafter, unreacted propylene was discharged to obtain 179 g of powdered polypropylene. Particles of the polypropylene The shape was close to spherical, MFR was 5.0, bulk density was 0.40, no odor was observed, N/MN was 4.8, and Urato heptane extraction residual rate (6 hours) was 98.0%.

(3) Friction resistance test In a nitrogen atmosphere, a magnet-driven circulation pump (
Using a magnetic pump MD-10 model manufactured by Iwaki Co., Ltd., a solution of 30 g of the solid product (m) suspended in 71 volumes of hexane was added at a flow rate of 1.1 cubic meters per minute and a temperature of 25°C.
After circulating for a period of time, a polyolefin was produced in the same manner as in Example 1 (2).

Examples 2-3 The solid product (m) obtained in Example 1 was heated under nitrogen atmosphere for 4 hours.
Stored at 0°C, after 3 months (Example 2) and after 6 months (
Example 3) A polyolefin was produced in the same manner as in Example 1 (2).

Example 4 When obtaining the solid product (IT) from the solid product (I) in Example 1 (1), the temperature was 15°C so that the polymer yield was tOg-polymer/g-solid product (1). The solid catalyst component was prepared, the polyolefin was produced (Example 4 (1)), and the attrition resistance test (Example 4 (2)) was conducted in the same manner except that ethylene was introduced for 3 hours.

Comparative Example 1 A solid product (Cl) obtained in the same manner as in Example 1 (1) was obtained in the same manner as in Example 1 except that the entire amount was converted into a solid product (Il) equivalent without prepolymerization treatment. Preparation of catalyst components, production of polyolefin (using 15 mg of solid product (m) equivalent, Comparative Example 1 (1)), and attrition resistance test (Comparative Example 1 (2)) were conducted.

Comparative Examples 2 to 3 The solid product (m) equivalent obtained in Comparative Example 1 was stored at 40°C under a nitrogen atmosphere, and after 3 months (Comparative Example 2) and 6 months (Comparative Example 3), Example In (2) of 1, the solid product (I) was substituted for 38.8 mg of the solid product (III).
II) A polyolefin was produced in the same manner except that 15 mg of the equivalent was used.

Example 5 Solid product (1) obtained in the same manner as in Example 1 (1)
Triethylaluminum E13 with Og cooled to 20°C
+a ol and phenyltriethoxysilane 10+u
sol in one volume of hexane, and propylene was introduced into the suspension at the same temperature with stirring for 1.5 hours so that the polymer yield was 1.0 g-polymer/g-solid product Cl). did. After washing with hexane to obtain a solid product (n), preparation of a solid catalyst component, production of polyolefin (Example 5 (1)), and attrition resistance test (Example 1) were carried out in the same manner as in Example 1. 5 (2)) was performed.

Example 6 In a stainless steel flask, 50 g of nonane, 4.8 g of anhydrous magnesium chloride, and 1 g of ethyl orthotitanate.
4.8 g of n-octatool and 18.3 g of n-octatool were mixed and heated to 110° C. for 2 hours with stirring to form a homogeneous solution. The solution was heated to 70°C, and 3.2 g of ethyl benzoate was added and dissolved, followed by 85 g of phenyl silicon trichloride.
．． It was added dropwise over 5 hours to precipitate the solid, and then heated to 70°C for 1 hour.
Stir for hours. The solid was separated from the solution and washed with hexane to yield solid product (I). T of solid product (1)
The i content was 2.5%. The total amount of the solid product Cl) was cooled to 15° C.
hexane 1 containing l and methyl toluate 3 intestinal layer o1
propylene was introduced into the suspension at the same temperature with stirring for 2.5 hours so that the polymer yield was 5.0 g of polymer/g of solid product (1).
Wash with hexane to obtain a solid product (II), mix the solid product (1 step) with 100 layers of titanium tetrachloride,
Subsequently, 2.2 g of di-n-butyl phthalate was added, and the mixture was allowed to react at 110°C for 1.5 hours with stirring. At the same temperature, the liquid phase was removed, and 100 layers of titanium tetrachloride were added again. The mixture was stirred at 100° C. for 2 hours, then washed with hexane and dried to give a solid product (III).

The solid product ([) has a particle shape close to spherical, and T
iO. 20% and 88.7% polypropylene. Polypropylene was produced in the same manner as in Example 1 using the solid product (III) (solid product (m)
Example 6 (7) (1)) Oyohi attrition resistance test (Example 6 (2)) was conducted using 133 mg. The polypropylene obtained in Example 6 (1) had a nearly spherical particle shape, a bulk density of 0.38, and an MFR of 4. ff
No odor was observed, x/x was 4.8, and the residual rate of boiling butane extraction was 97.7%.

Comparative Example 4 A solid product was produced in the same manner as in Example 6, except that the entire amount of solid product (I) obtained in the same manner as in Example 6 was used as an equivalent to solid product (II) (preliminary polymerization treatment was omitted). preparation of
Production of polyolefins (solid product (m) equivalent 15 m
g, Comparative Example 4 (1)) and abrasion resistance test (Comparative Example 4 (2)) were conducted.

Example 7 The solid product (III) obtained in Example 6 was stored at 40° C. under a nitrogen atmosphere, and after 6 months, a polyolefin was produced in the same manner as in Example 6.

Comparative Example 5 A polyolefin was produced in the same manner as in Example 7 (using 1 g of the solid product (III) equivalent at 15°C) except that the solid product (III) equivalent obtained in Comparative Example 4 was used. .

[Brief explanation of the drawing]

The figure is a flow sheet showing the steps involved in carrying out the method of the invention. that's all

Claims (2)

[Claims] (1) In a method for producing a catalyst component for olefin polymerization in which titanium halide, vanadyl halide, or vanadium halide is supported on a carrier whose main component is an Mg compound precipitated from a solution state, I, general formula MgX_n ( OR^1) Magnesium halide (a) represented by_2_-_n (where X is C
l or Br, R^1 is an alkyl group having 1 to 20 carbon atoms,
aryl group or cycloalkyl group having 3 to 20 carbon atoms, n is a number of 0 to 2), general formula Ti (OR^2
)_4 orthotitanate ester and/or general formula R^3-[O-Ti(OR^4)(OR^5)-_mO
- Polytitanate ester (b) represented by R^6 (here, R^2, R^3, R^4, R^5 and R^6 are alkyl groups having 1 to 20 carbon atoms, aryl groups, or carbon Number 3
~20 cycloalkyl group, m is a number from 2 to 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 react and dissolve (component A) to obtain (component A). (O
R^8)_4_-_p(d) (here, X is Cl or B
r, 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, l and p are numbers of 1 to 4). (Component B) consisting of silicon (e) is mixed and reacted to precipitate solid I (hereinafter referred to as solid product (I)); III. A solid product (II) is obtained by prepolymerization with an α-olefin having 2 or more carbon atoms, and IV, the solid product (
II), the general formula TiX_q(OR^g)_4_-_q(
Here, X is Cl or Br, R^g is a carbon number of 1 to 20
an alkyl group, an aryl group, or a cycloalkyl group having 3 to 20 carbon atoms, and q is a number of 1 to 4) and/or a titanium halide represented by the general formula VO
X_s(OR^1^0)_3_-_s or VX_t
(OR^1^1)_4_-_t (where,
A solid (hereinafter referred to as solid (referred to as product (III)); A method for producing a solid catalyst component for polyolefin production, which comprises mixing and reacting an acid ester (h). (2) 0.01 to 500 per 1 g of solid product (I)
Claim 1 (1) in which the α-olefin of g is reacted.
).