JPH0411603A - Production of propylene copolymer - Google Patents

Abstract

PURPOSE:To obtain the title copolymer excellent in the randomness of copolymerization and a constitutional distribution by copolymerizing propylene with a specified polymerizable monomer in the presence of a specified polymerization catalyst. CONSTITUTION:Propylene is copolymerized with at least one polymerizable monomer selected from among ethylene, a C4 or higher alpha-olefin and polyene (e.g. ethylene) in the presence of an olefin polymerization catalyst comprising a solid Ti catalyst component containing at least Mg, halogen and trivalent Ti and obtained by bringing a Ti complex compound obtained from TiCl3 and an electron donor (e.g. pyridine), an Mg halide compound (e.g. MgCl2) and an organometallic compound (e.g. ethylaluminum sesquichloride) into contact with each other; an organometallic compound (e.g. triethylaluminum); and an electron donor (e.g. ethyl benzoate) as an optional component.

Description

[Detailed Description of the Invention] The present invention relates to a method for producing a propylene copolymer using a specific olefin polymerization catalyst. The present invention relates to a method for producing a propylene copolymer.

Propylene-based copolymers are widely used as films and molded products with excellent heat sealability and transparency when the comonomer content is low, and when the comonomer content is high, the resistant It is used as an impact modifier or as a rubber product for the automobile industry, industrial rubber products, and electrical insulation rubber-coated fabrics.

In these applications, the use of propylene-based copolymers, which have excellent randomness and compositional distribution, can improve the blocking resistance of the film, prevent whitening of the film due to heat aging, and have excellent modification effects. characteristics are obtained.

Furthermore, when the comonomer in such a propylene copolymer is a polyene, rigidity, deep drawability, printability, adhesiveness, paintability, compatibility, etc. are also improved.

Therefore, it is desired to develop a method for producing propylene copolymers that is convenient in terms of randomness and has excellent composition distribution.

Anisato L11 Clothes of the Invention This invention has been made in view of the prior art as described above, and aims to provide a method for producing a propylene copolymer that is convenient in terms of randomness and has excellent compositional distribution.

In the method for producing a propylene copolymer according to the present invention, [A] [I] a titanium complex compound obtained from titanium trichloride and an electron donor (a), [n] a halogen-containing magnesium compound and [III] a solid titanium catalyst component containing at least magnesium, halogen, and trivalent titanium obtained by contacting an organometallic compound, [B] an organometallic compound, and optionally [C] an electron donor. In the presence of an olefin polymerization catalyst formed from (1
) Propylene is copolymerized with (ii) at least one polymerizable monomer selected from the group consisting of ethylene, a-olefins having 4 or more carbon atoms, and polyenes.

According to the method for producing a propylene copolymer according to the present invention (
i', it is possible to produce a propylene copolymer with convenient randomness and excellent compositional distribution.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The method for producing a propylene copolymer according to the present invention will be specifically described below.

FIG. 1 shows an explanatory diagram of the preparation process of the olefin polymerization catalyst according to the present invention.

The olefin polymerization catalyst according to the present invention is formed from [A] a solid titanium catalyst component, [B] an organometallic compound, and optionally [C] an electron donor.

[A] The solid titanium catalyst component as described above includes [I] a titanium complex compound obtained from titanium trichloride and an electron donor (a), [n] a halogen-containing magnesium compound, and [III] an organometallic compound. The gourd obtained by contacting contains at least magnesium, halogen, and trivalent titanium. Furthermore, this solid titanium catalyst component [Al
I3 An electron donor may be included if necessary.

A method for preparing the titanium complex compound [I] obtained from titanium trichloride and the electron donor (a) used in the present invention will be explained.

Titanium trichloride is obtained by reducing titanium tetrachloride by contacting it with hydrogen, metals such as metal magnesium, metal aluminum, and metal titanium, or organometallic compounds such as organomagnesium compounds, organoaluminum compounds, and organozinc compounds. Titanium trichloride and the like are preferably used.

Specifically, the following compounds are used as the electron donor (a) used in preparing the titanium complex compound [1].

Amines such as methylamine, ethylamine, dimethylamine, diethylamine, ethylenediamine, hexamethylenediamine Pyrrole, pyrrole such as methylpyrrole, dimethylpyrrole Viroline, pyrrolidine: Indole: Pyridine, methylpyridine, ethylpyridine, propylpyridine, dimethylpyridine, Pyridines such as ethylmethylpyridine, trimethylpyridine, phenylpyridine, benzylpyridine, and pyridine chloride; piperidine, quinolines,
Nitrogen-containing cyclic compounds such as isoquinoline melon.

Cyclic oxygenated compounds such as tetrahydrofuran, 1,4-cineole, 1,8-cineole, pinolfuran, methylfuran, dimethylfuran, diphenylfuran, benzofuran, coumaran, phthalane, tetrahydropyran, pyran, ditedropyran, methanol, ethanol, propatool , pentanol, hexanol, octatool, dodecanol, octadecyl alcohol, oleyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, isopropyl alcohol,
Alcohols with 1 to 18 carbon atoms, such as 2-ethylhexyl alcohol and isopropylbenzyl alcohol; carbon atoms that may have a lower alkyl group, such as phenol, cresol, xylenol, ethylphenol, propylphenol, nonylphenol, cumylphenol, and naphthol; 6 to 20 phenols.

Ketones with 3 to 15 carbon atoms such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, acetylacetone, and benzoquinone Aldehydes with 2 to 15 carbon atoms such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde, and naphthaldehyde Methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl valerate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate,
Ethyl crotonate, ethyl cyclohexanecarboxylate,
Methyl benzoate, ethyl benzoate, propyl benzoate,
Butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate, ethyl toluate, amyl toluate,
Ethyl ethyl benzoate, methyl anisate, maleic acid n
-butyl, diisobutyl methylmalonate, di-n-hexyl cyclohexenecarboxylate, diethyl nadic acid, diisopropyl tetrahydrophthalate, diethyl phthalate, diisobutyl phthalate, di-n-butyl phthalate, di-2-ethylhexyl phthalate, γ-butyrolactone , δ−
Organic acid esters having 2 to 30 carbon atoms such as valerolactone, coumarin, phthalide, and ethylene carbonate; Acid halides having 2 to 15 carbon atoms such as acetyl chloride, benzoyl chloride, toluic acid chloride, and anisyl chloride; methyl ether, ethyl ether; Isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole, diphenyl ether epoxy-p-
Ethers and diethers with 2 to 20 carbon atoms such as menthane; Acid amides such as acetic acid amide, benzoic acid amide, and toluic acid amide: methylamine, ethylamine, diethylamine, tributylamine, piperidine, tribenzylamine, aniline, pyridine , amines such as picoline and tetramethylene diamine; nitriles such as acetonitrile, benzonitrile, and tolnitrile; acid anhydrides such as acetic anhydride, phthalic anhydride, and benzoic anhydride; and the like.

Further, as the electron donor (a), the following general formula [r
Organosilicon compounds represented by a] can also be used.

Rn S l (0”) a-n = [
I′a] [wherein R and R′ are hydrocarbon groups,
0>n<4] Examples of the organosilicon compound represented by the above general formula [Ia] include trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyljethoxysilane, and diisopropyldimethoxy. Silane, t-butylmethyldimethoxysilane, t
-Butylmethyljethoxysilane, t-amylmethyljethoxysilane, diphenyldimethoxysilane Phenylmethyldimethoxysilane, diphenyljethoxysilane, bis0-)lyldimethoxysilane, bism-)lyldimethoxysilane, bisp-tolyldimethoxysilane , bis p-)lyldiethoxysilane, bisethyl phenyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyljethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, methyltrimethoxy Silane, n-propyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, phenyltrimethoxysilane, γ-
Chlorpropyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, t-butyltriethoxysilane, n-butyltriethoxysilane, 1so-butyltriethoxysilane, phenyltriethoxysilane, aminopropyltriethoxysilane Ethoxysilane, chlortriethoxysilane, ethyltriisopropoxysilane, vinyltributoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, 2-norbornanetrimethoxysilane, 2-norbornanetriethoxysilane, 2-norbornanemethyldimethoxysilane, silicon Ethyl acid, butyl silicate, trimethylphenoxysilane, methyltriaryloxysilane, vinyltris(β-methoxyethoxysilane), vinyltriacetoxysilane, dimethyltetraethoxydisiloxane, and the like are used.

Furthermore, as the electron donor (a), the following general formula [
An organosilicon compound represented by [na] can also be used.

SiR+R2, (OR3) 3-, - [na
[In the formula, R1 is a cyclopentyl group or a cyclopentyl group having an alkyl group, and R2 is an alkyl group]
It is a group selected from the group consisting of a cyclopentyl group and a cyclopentyl group having an alkyl group, R3 is a hydrocarbon group, and m is 0≦m≦2. ] In the above formula [na], R1 is a cyclopentyl group or a cyclopentyl group having an alkyl group, and R
Examples of 1 include cyclopentyl groups having alkyl groups other than cyclopentyl groups, such as 2-methylcyclopentylpentyl group, 2-ethylcyclopentyl group, 2,3-dimethylcyclopentyl group.

In the formula [n a], R2 is either an alkyl pentacyclopentyl group or a cyclopentyl group having an alkyl group, and R2 is, for example, a methyl group, an ethyl group, a propyl pentaisopropyl group, a butyl group, a hexyl group, etc. The cyclopentyl group and the cyclopentyl group having an alkyl group exemplified as the alkyl group or R1 can be similarly mentioned.

Further, in the formula [na], R3 is a hydrocarbon group,
Examples of R3 include hydrocarbon groups such as an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group.

Specifically, as such an organosilicon compound, +1
Trialfoxysilanes such as cyclopentyltrimethoxysilane, 2-methylcyclopentyltrimethoxysilane, 2.3-dimethylcyclopentyltrimethoxysilane, and cyclopentyltriethoxysilane; dicyclopentyldimethoxysilane, bis(2-methylcyclopentyl)dimethoxysilane, bis( Dialkoxysilanes such as 2,3-dimethylcyclopentyl)dimethoxysilane and dicyclopentyljethoxysilane; tricyclopentylmethoxysilane, tricyclopentylethoxysilane, dicyclopentylmethylmethoxysilane, dicyclopentylethylmethoxysilane, dicyclopentylmethylethoxysilane, cyclopentyl Examples include monoalkoxysilanes such as dimethylmethoxysilane, cyclopentyldiethylmethoxysilane, and cyclopentyldimethylethoxysilane.

As these electron donors (a), nitrogen-containing cyclic compounds are preferable, and pyridine and pyridine derivatives are particularly preferable.

Electron donor (a) used in preparing a titanium complex compound from the above electron donor (a) and titanium trichloride
) is at least 0 per mole of titanium trichloride.
．． The amount is 5 mol or more, preferably 1 mol or more, particularly preferably 2 to 5 mol. The upper limit of the amount of electron donor (a) to be used is not particularly limited, but considering economic efficiency, it is preferably 1000 mol or less, more preferably 1 mol or less, per 1 mol of titanium trichloride.
00 mol or less, particularly preferably 10 mol or less.

Further, the contact between titanium trichloride and the electron donor (a) is preferably carried out at a temperature of usually -100 to 300°C, preferably -50 to 100°C.

The above reaction may be carried out using the electron donor (a) as a solvent. Generally, it is preferable to carry out the reaction using an inert hydrocarbon solvent as described below.

In addition, a complex obtained from titanium trichloride and an electron donor (a) 1) is generally in the form of a composition of titanium trichloride and an electron donor, and the amount of electron donor (a) is usually 1 mole of titanium trichloride. ~10 mol, preferably 2 to 5 mol, particularly preferably
The composition is 2.5 to 4 moles.

In the present invention, the halogen-containing magnesium compound [n] used in the preparation of the solid titanium catalyst component [A] specifically includes halogenated magnesium chloride, magnesium bromide, magnesium iodide, magnesium fluoride, etc. Magnesium; alkoxymagnesium halide phenoxymagnesium chloride such as methoxymagnesium chloride, ethoxymagnesium chloride, isopropoxymagnesium chloride, butoxymagnesium chloride, octoxymagnesium chloride,
Alkoxymagnesium halides such as methylphenoxymagnesium chloride: ethylmagnesium chloride, propylmagnesium chloride,
Butyl magnesium chloride, hexyl magnesium chloride,
Alkyl magnesium halides such as amyl magnesium chloride are used.

Among these, magnesium chloride, alkoxymagnesium chloride, and the like are particularly preferably used.

Such a halogen-containing magnesium compound [n] is
For example, it can be activated and used by the following method.

(1) Directional flow of pulverizing a halogen-containing magnesium compound The magnesium compound thus obtained generally has a specific surface area of 20 i/g or more, preferably 50 i/g or more.
It is more than nr/g.

When subjecting the magnesium compound to pulverization treatment, an electron donor (b) may be present. This electron donor (b)
As the electron donor (a), the above-mentioned electron donor (a) can be used.

(2) Halogen-containing magnesium compound and electron donor (
A magnesium complex compound is prepared from b), and then this complex compound is reacted with an electron donor-reactive reagent.As the electron donor (b), specifically, the electron donor (a) as described above is used. Preferably, alcohols such as ethanol and 2-ethylhexyl alcohol are used.

It is also regrettable that the electron donor (b) is used as an electron donor-reactive reagent.
) Any compound can be used as long as it is capable of reacting with the compound, and examples of preferable compounds include organometallic compounds and halogen-containing silicon compounds as described below.

Specifically, for example, activating the halogen-containing magnesium compound [n] by reacting a complex of magnesium chloride and alcohol with an organometallic compound such as an organoaluminium compound or an organomagnesium compound, or a halogen-containing silicon compound. I can do it.

In addition, in the method illustrated above, a halogen-free magnesium compound can also be used as the magnesium compound. In that case, it is necessary to use the halogen-containing compound at least once in the process of activating the halogen-containing magnesium compound [n]. The above-mentioned halogen-free magnesium compounds include dialkoxymagnesiums such as jetoxymagnesium and dibutoxymagnesium, dialkylmagnesiums such as diphenoxymagnesium, dialkylmagnesiums such as diethylmagnesium and dibutylmagnesium, diallylmagnesiums such as diphenylmagnesium, and magnesium stearate. For example, magnesium salts such as

Further, as the halogen-containing compound, any compound can be used as long as it can halogenate the halogen-free magnesium compound, and specifically, halogen-containing silicon-1t-butyl chloride such as silicon tetrachloride can be used. Examples include halogen-containing branched chain hydrocarbon halides such as halogen-containing branched hydrocarbons.

In the present invention, as the organometallic compound [III] used in the preparation of the solid titanium catalyst component [Al], organometallic compounds of metals from Groups 1 to M of the periodic table are used. Compounds such as are used.

(1) R1, Al (OR2), H, X.

(In the formula, R1 and R2 usually have 1 to 15 carbon atoms,
Preferably it is a hydrocarbon group containing 1 to 4, and these may be the same or different from each other. X represents a halogen atom, LO<m≦3, n is 0≦n<3, p is 0≦p<3, q is a number of O≦q<3, and m + n +p
+ q = 3).

(2) A complex alkylated product of Group (I) metal and aluminum, represented by MIAIR+4 (wherein Ml is Li, Na, or Ni, and R1 is the same as above).

(3) RIR2M2 (In the formula, R1 and R2 are the same as above.

M2 is Mg, Zn or Cd)
or group m dialkyl compounds.

As the organoaluminum compound belonging to the above (1), the following compounds can be exemplified.

General formula R1, At(OR2)3, (wherein R1 and R2 are the same as above. m is preferably a number of 1.5≦m≦3), general formula R1, AIX,
.

(In the formula, R1 is the same as above. X is halogen, m is preferably O<m<3), General formula R1, AIH,.

(In the formula, R1 is the same as above. m is preferably 2≦m<3
), general formula R1, Al(OR2), X.

(In the formula, R1 and R2 are the same as above. X is halogen,
O<m≦3.0≦n<3.0≦q<3, m + n +
q = 3).

More specifically, the aluminum compounds belonging to (1) include trialkyl aluminum such as hexatriethylaluminum and tributylaluminum; trialkenylaluminum such as triisoprenylaluminum; dialkylaluminum alkoxide such as diethylaluminum ethoxide and dibutylaluminum butoxide. Alkylaluminium sesquialkoxides such as ethylaluminum sesquiethoxide, butylaluminum sesquibutoxide, partially alkoxylated alkylaluminums having an average composition represented by R' 2 , 5 A l (OR2) s , s etc.: diethyl; dialkylaluminum halides such as aluminum chloride, dibutylaluminum chloride, diethylaluminum bromide; alkylaluminum sesquihalides such as ethylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquipromide;

Partially halogenated alkylaluminiums such as alkylaluminum cybarides such as ethylaluminum dichloride, propylaluminum dichloride, butylaluminum dibromide, dialkylaluminum hydrides such as diethylaluminum hydride, dibutylaluminum hydride, ethylaluminum dicdride, provil Other partially hydrogenated alkylaluminums such as alkylaluminum dihydrides such as aluminum dihydride: partially alkoxylated and halogenated alkyls such as ethylaluminum ethoxychloride, butylaluminum butoxychloride, ethylaluminum ethoxybromide, etc. Aluminum can be mentioned.

Compounds similar to (1) include organoaluminum compounds in which two or more aluminum atoms are bonded via one oxygen atom or nitrogen atom. Examples of such compounds include (C2Hs)2AIOA1 (
C2H6)2, (CaHs) 2AIOAl (C4H
9)2, (C2H8)2AINAl (C2H5)22
Examples include H5 methylaluminoxane.

Examples of the compound belonging to the above (2) include LiA1(C2H3) jl LiAl(CvH+5)a and the like.

Among these, organoaluminum compounds are preferably used, and halogen-containing alkyl aluminums are particularly preferably used.

Such an organometallic compound [III] may be used in contact with the electron donor (b) as described above, if necessary.

The organometallic compound [III] and the titanium complex compound [r] as described above usually have an Al/Ti (atomic ratio) of 1 to 10.
00, preferably 2 to 500, particularly preferably 3 to 100.

A solid state is prepared by contacting a titanium complex compound obtained from titanium trichloride and an electron donor (a), [n] a halogen-containing magnesium compound, and [III] an organometallic compound, which is prepared as described above. titanium catalyst component [Al
is obtained. In this contact, an electron donor (d) may be present together if necessary. This electron donor (d)
As the electron donor (a), the above-mentioned electron donor (a) can be used.

The solid titanium catalyst component [Al
contains at least magnesium, halogen and trivalent titanium, and optionally an electron donor (d).

In contacting the trivalent titanium complex compound [I], the halogen-containing magnesium compound [n], and the organometallic compound [III], the trivalent titanium complex compound [■] and the halogen-containing magnesium compound [I [] Trivalent titanium/
It is desirable to use an amount such that magnesium (atomic ratio) is 0.00001 to 0.1.

Further, in the contact, it is preferable to carry out the contact in the presence of an inert hydrocarbon solvent, which will be described later.

Such a solid titanium catalyst component [In Al, the halogen/trivalent titanium (yl, child ratio) is 5 to 5000, preferably 10 to 2000, and the magnesium/trivalent titanium (yl) ratio is 5 to 5000, preferably 10 to 2000,
/C11v ratio) is 5 to 100,000, preferably 10 to
It is desirable that it is 5000.

This solid titanium catalyst component [Al contains magnesium halide whose crystal size is small compared to commercially available magnesium halide, and its specific surface area is usually about 2 On.
? /g or more, preferably about 50 to 1000 go/g,
More preferably, it is about 80 to 500 d1g. Since the solid titanium catalyst component (Al) is a catalyst component formed by the above-mentioned components, its composition is not substantially changed by hexane washing.

Next, [
B] The organometallic compound [B] includes the above-mentioned organometallic compound [II
I] is used.

Further, to explain the [C] electron donor (C) used as necessary in the olefin polymerization catalyst according to the present invention, this electron donor (C) is similar to the electron donor (a) described above. Organic acid esters such as ethyl benzoate and methyl toluate are preferably used.

In the present invention, the solid titanium catalyst component [Al
and an organometallic compound [B] A propylene copolymer is produced using an olefin polymerization catalyst to which an electron donor [C] is added as necessary.

At this time, the olefin polymerization catalyst may be prepolymerized with a polymerizable monomer to be described later.

This prepolymerization is carried out at a rate of 0.1 per gram of olefin polymerization catalyst.
This is carried out by prepolymerizing the polymerizable monomer in an amount of up to 500 g, preferably 0.3 to 300 g, particularly preferably 1 to 100 g.

In the prepolymerization, a catalyst can be used at a much higher concentration than the catalyst concentration in the system in the main polymerization.

The concentration of the solid titanium catalyst component [A] in the prepolymerization is usually about 0.01 to 200 mmol, preferably about 1 to 100 mmol, particularly preferably about 1 to 100 mmol, in terms of titanium atoms, per 1 g of the inert hydrocarbon medium described below. A range of 1 to 50 mmol is desirable.

The amount of organometallic compound [B] is determined by the amount of solid titanium catalyst component [
0.1-500g per 1g of A3, preferably 0.3-500g
The amount may be such that 300 g of copolymer is produced.
Usually about 061 to 100 mol, preferably about 0.5 to 5 mol per mol of titanium atom in solid titanium catalyst component [A]
An amount of 0 mol, particularly preferably 1 to 20 mol is desirable.

The electron donor [C] is optionally used in an amount of 0 to 10 mol, preferably 0 to 2 mol, particularly preferably 0 to 1 mol, per mol of metal atom in the organometallic compound [B = .

Prepolymerization is preferably carried out under mild conditions by adding the below-mentioned polymerizable monomer and the above catalyst component to an inert hydrocarbon medium.

Specifically, the inert hydrocarbon medium used in this case includes propane, butane, pentane, hexane, heptane, octane, decane, dodecane, aliphatic hydrocarbons such as kerosene, cyclopentane, cyclohexane, methylcyclopentane, etc. Alicyclic hydrocarbons.

Examples include aromatic hydrocarbons such as benzene, toluene, and xylene, ethylene chloride, halogenated hydrocarbons such as chlorobenzene, and mixtures thereof. Among these inert hydrocarbon media, it is particularly preferable to use aliphatic hydrocarbons. Incidentally, the prepolymerization can be carried out using the polymerizable monomer itself as a solvent, or it can be carried out substantially in the absence of a solvent.

The polymerizable monomer used in the prepolymerization may be the same as or different from the polymerizable monomer used in the main polymerization described later, and is specifically preferably propylene. These polymerizable monomers may be used alone or in combination of two or more kinds.

Reaction temperature +L during prepolymerization Usually about -20 to 100
°C, preferably about -20 to 80 °C, more preferably 0
It is desirable that the temperature is in the range of ~40°C.

In addition, in the prepolymerization, a molecular weight regulator such as hydrogen can also be used. Such molecular weight regulators are
Intrinsic viscosity [V] of the copolymer obtained by prepolymerization measured in decalin at 135°C: about 0.2 dl/g or less, preferably about 0.5 to 10 dl/g. desirable.

The prepolymerization is carried out using the solid titanium catalyst component [A
About 0.1-500g per 11g, preferably about 0.3
It is desirable to carry out the reaction so that ~300 g, particularly preferably 1 to 50 g, of the copolymer is produced.

Prepolymerization can be carried out batchwise or continuously.

In this polymerization, the polymerizable monomers that can be used in the copolymerization with propylene include ethylene and a-olefins having 4 to 20 carbon atoms, such as 1-butene, 1-pentene, 1-hexene, 4- Methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-
Tetradecene, 1-hexadecene, 1-octadecene,
1-eicosene may be mentioned.

Furthermore, 5-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 6-methyl-1,6-octadiene, 7-methyl-1,6-octadiene, 6-ethyl-1
, 6-octadiene, 6-broby-1,6-octadiene, 6-butyl-1,6-octadiene, 6-methyl-1,6-nonadiene, 7-methyl-1,6-nonadiene, 6-nityl-1,6- Nonadiene, 7-ethyl-1
, 6-nonadiene 6-methyl-1,6-zocadiene,
7-methyl-1,6-zocadiene, 6-methyl-1,6
- Polyenes such as conjugated dienes and non-conjugated dienes such as dienes such as undecadiene, 1,5-hexadiene, 1,7-octadiene, 1,9-nonadiene, isoprene, and butadiene can also be used as polymerizable monomers. . These polymerizable monomers can be used alone or in combination to copolymerize with propylene.

Main polymerization of propylene and the above polymerizable monomer:
Dai Usually carried out in the gas or liquid phase.

When the main polymerization takes the reaction form of slurry polymerization, the above-mentioned inert hydrocarbons can be used as the reaction solvent, and a polymerizable polymer that is liquid at the reaction temperature can also be used.

In the production method of the present invention, the solid titanium catalyst component [
Al is usually about 0.001 to 0.5 mmol, preferably about 0.0 mmol in terms of titanium atoms per polymerization volume IQ.
It is used in an amount of 0.05 to 0.1 mmol. In addition, there are usually about 1 to 2 metal atoms per mole of titanium atoms in the prepolymerization catalyst component in the organometallic compound [B]IL polymerization system.
000 mol, preferably about 5 to 500 mol. Sara & He Electron donor [C]+!
Force used as required (in that case organometallic compound [
The amount used is usually 0 to 10 mol, preferably 0 to 2 mol, and particularly preferably 0 to 1 mol per mol of metal atom in B].

If hydrogen is used during the main polymerization, the molecular weight of the resulting copolymer can be adjusted, and a copolymer with a high melt flow rate can be obtained.

In the present invention, the polymerization temperature method of propylene and the polymerizable polymer is usually about 20 to 200 tons, preferably about 5 tons.
Pressure scaled from 0 to 100'C, usually normal pressure to 100k
g/es), preferably about 2 to 50 kg/i.

In the production method of the present invention, polymerization can be carried out in any of batchwise, semi-continuous, and continuous methods. Furthermore, the polymerization can be carried out in two or more stages by changing the reaction conditions.

At this time, by adjusting the amount of electron donor [C] as necessary, the crystallinity of the resulting propylene copolymer,
Stereoregularity can be easily controlled.

According to the production method according to the present invention, the repeating unit (a) derived from propylene is 98 to 2 mol%, preferably 9
The range is 0 to 10 mol%, particularly preferably 80 to 20 mol%, and the repeating unit (a) derived from the above polymerizable monomer is 2 to 98 mol%, preferably 10 to 90 mol%, particularly preferably 420 A propylene random copolymer having a content in the range of 80 mol % is obtained.

The propylene copolymer described above has excellent random composition distribution.

Regarding the propylene copolymer obtained by the method of the present invention, as an index of randomness and composition distribution, for example, the randomness parameter (herein referred to as B value) proposed by Coleman et al. (B, D, Cole-man et al.
and T, G, Fox, J, Polym,
Sci., Al., 3183 (1963)).

This B value is defined as follows.

B=P+2/ (2P+・P2) Here, p,, p2 is the content fraction of the first monomer and the second monomer, and PI2 is the (first monomer) - (second monomer) in the total bimolecular chain.
monomer) chain proportion.

The B value follows Bernoulli statistics when 1, blocky when B<1, alternating when B>1, and alternating copolymer when B=2.

Furthermore, in the present invention, since the yield of copolymer per titanium-based catalyst is high, there is little catalyst residue in the copolymer. A white copolymer is obtained without any coloring.

1 Riri-no-J By the method for producing a copolymer using the titanium-based catalyst according to the present invention, a copolymer with excellent randomness and composition distribution can be obtained.

The present invention will be explained below with reference to Examples. The present invention is not limited to these Examples.

[Solid catalyst component [Preparation of A] In a stainless steel pot with an internal volume of IQ, 30 g of magnesium chloride and 25. diameter stainless steel pole 5
0 pieces were added under a nitrogen atmosphere, shaken at room temperature for 48 hours,
An activated halogen-containing magnesium compound [n] was prepared by pulverizing magnesium chloride. The specific surface area of this halogen-containing magnesium compound [n] was 97 r/g, while titanium trichloride 4. 3g purified n-heptane 40
10 ml of distilled and purified gin while suspending in ml of
After stirring and mixing at room temperature for 16 hours, unreacted pyridine and the solvent were distilled off under reduced pressure to prepare a titanium trichloride/pyridine complex. 15 g of the above pulverized magnesium chloride and the above titanium trichloride/pyridine complex. 5
4■ was suspended in purified hebutane, and while stirring and mixing, 1 mole of ethylaluminum sesquichloride equivalent to 15 mmol was added.
A solid catalyst component was obtained by adding a hexane solution of No. 9 and stirring at room temperature for 16 hours. The solid catalyst component was thoroughly washed with heptane. The content of titanium atoms in the solid catalyst component was 0. After adding 600 ml of purified decane to a 111 glass flask equipped with a stirrer, propylene was added at 60 Q/hr.
Ethylene was supplied at a flow rate of 40 Q/hour. After adding 1 mmol of triethylaluminum to this, 0.00225 mmol of solid titanium catalyst component [A] was added per titanium thickness to start polymerization. Polymerization was carried out at 40°C for 1 hour. , do not stop the polymerization by adding a mixture of methanol and hydrochloric acid into the polymerization vessel.Pour the reaction solution into a large amount of methanol and send it to the vessel to precipitate the polymer.The obtained polymer is washed with methanol that escapes through the filtration, and dried under reduced pressure. The yield of the obtained polymer was 31.6 g, and the activity was 1.
The composition was 4000 g/mM-Ti.The propylene content was 44.0 mol%.The B value was 0.84.Propylene was mixed at a flow rate of 80 g/hour and ethylene at a flow rate of 20 s+/hour. Polymerization was carried out in the same manner as in Example 1, except that the yield of the obtained polymer was 10.0 g, and the activity was 44.
The composition was 40 g/mM-Ti.The propylene content was 67.3 mol%.The B value was 0.91. Polymerization was carried out in the same manner as in Example 1 except that μ was supplied.The yield of the obtained polymer was 13.4g1.The activity was 596.
0 g 7mM-Ti The composition had a propylene content of 20.3 mol%. The B value was 0.90. Propylene was supplied at a flow rate of 20 Q/hour and ethylene at a flow rate of 80 g/hour Polymerization was carried out in the same manner as in Example 1, except that the yield of the obtained polymer was 19.4 g, and the activity was 86.
The composition was 20 g/mM-Ti with a propylene content of 67.3 mol% and a B value of 0.89.180 ml of purified hexane was added to a 400 ml glass flask equipped with a stirrer. After adding 20 ml of 1,5-hexadiene, propylene was supplied at a flow rate of 50 i/hr and LX was supplied at a flow rate of 20 Q/hr, and 2.0 ml of triethylaluminum was added thereto.
After adding 0 mmol of solid titanium catalyst component [A], 0.02 mmol of solid titanium catalyst component [A] was added per titanium atom to start polymerization. Polymerization was carried out at 40°C. 48 minutes after the start of polymerization, the viscosity of the polymerization system increased and poor stirring occurred. The polymerization was stopped by adding a mixture of methanol and hydrochloric acid to the system, and the reaction solution was poured into a large amount of methanol and sent to the factory. The polymer was precipitated. It was dried and collected.

The yield of the obtained polymer was 38.8 g. At this yield, the activity was 1690 g 7mM-Ti, but the actual activity is thought to be even higher. The composition had a propylene content of 91.9 mol% and a crystallinity of 14.4% as measured by X-ray of a quenched press sheet. 1 mmol of triethylaluminum, benzoic acid as an electron donor. Polymerization was carried out in the same manner as in Example 5, except that 0.1 mmol of ethyl and 0.01 mmol of solid titanium catalyst component [A] per titanium atom were used, and the polymerization time was 1 hour. The yield was 11.9 g. With this yield, the activity was 1190 g 7mM-Ti. It is thought that the actual activity is even higher. The composition had a propylene content of 80.1 mol% and a crystallinity of 21.1% when measured by X-ray of a rapidly cooled pressed sheet. Polymerization was carried out in the same manner as in Example 5, except that 50 mL of purified hexane and 150 mL of 1.5-hexadiene were used at a flow rate.However, 24 minutes after the start of polymerization, the viscosity of the polymerization system increased and stirring became insufficient, so the system By adding a mixture of methanol and hydrochloric acid, the polymerization was stopped.The yield of the resulting polymer was 42.3g.With this yield, the activity was 2150g 7mM-Ti & the actual activity was even higher. considered to be a thing. The composition was 47.5 mol% propylene content. Using 180 ml of purified hexane and 20 ml of 1.7-metal-1,6-octadiene, propylene was supplied at a flow rate of 50 Q/hour and nitrogen at a flow rate of 20 Q/hour. Polymerization was carried out in the same manner as in Example 5 using 1.0 mmol of triethylaluminum and 0.01 mmol of solid titanium catalyst component [A] per titanium atom. The yield of the obtained polymer was 13.8 g, and the activity was 13
80 g 7mM-Ti The composition had a propylene content of 70.5 mol%.

[Brief explanation of drawings]

FIG. 1 shows an explanatory diagram of the preparation process of the olefin polymerization catalyst according to the present invention. Figure Patent Applicant Mitsui Petrochemical Industries Co., Ltd. Agent Patent Attorney Shun Suzuki

Claims (1)

[Scope of Claims] [A] [I] A titanium complex compound obtained from titanium trichloride and an electron donor (a), [II] a halogen-containing magnesium compound, and [III] an organometallic compound brought into contact with each other. The presence of an olefin polymerization catalyst formed from the obtained solid titanium catalyst component containing at least magnesium, halogen, and trivalent titanium, [B] an organometallic compound, and optionally [C] an electron donor. Below, (i
) propylene, (ii) ethylene, α having 4 or more carbon atoms;
- A method for producing a propylene copolymer, which comprises copolymerizing at least one polymerizable monomer selected from the group consisting of olefins and polyenes.