JPS5815507A - Production of polyolefin - Google Patents

Abstract

PURPOSE:To obtain a highly stereoregular polymer in high activity, by employing a catalyst prepared by combining an organometallic compound/organic acid ester component with a component prepared by impregnating a carrier consisting of compounds of Mg, Si and Al and a carboxylic acid halide with a Ti compound. CONSTITUTION:A carrier is prepared by contacting, for example, by means of copulverization, a Mg halide (e.g., MgCl2) with a compound of the formula, wherein R is a 1-24C hydrocarbyl, X is a halogen and 0<=m<=4 (e.g., SiCl4), an organic carboxylic acid halide (e.g., benzoyl chloride) and an Al halide (e.g., AlCl3). A solid catalytic component is prepared by impregnating the above carrier with a titanium compound (and its adduct with an organic acid ester) (e.g., TiCl4). A polymer is obtained by (co)polymerizing an olefin in the presence of a mixture or adduct of the above solid catalytic component and an organometallic compound (e.g., triethylaluminum) and an organic acid ester (e.g., ethyl p-anisate).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for polymerizing or copolymerizing α-olefins with high activity and good stereoregularity using a novel catalyst.

As a highly stereoregular polymerization catalyst for α-olefin, a catalyst comprising a titanium chloride and an organic aluminium L compound has been known. However, in polymerization using this catalyst system, although a highly stereoregular polymer can be obtained, the catalyst activity is low, so it is necessary to remove catalyst residues from the produced polymer.

In recent years, many proposals have been made to improve the activity of catalysts. According to these proposals, it has been shown that a highly active catalyst can be obtained when a catalyst component in which titanium tetrachloride is supported on an inorganic solid carrier such as A4gC'12 is used.

However, in the production of polyolefins, it is preferable that the catalyst activity be as high as possible, and catalysts with even higher activity have been desired. It is also important that the amount of atactic moieties in the polymer is as low as possible.

As a result of intensive research on these points, the present inventors found that
Here, a new catalyst was discovered. That is,
The present invention relates to a method for producing extremely highly active and highly stereoregular polyolefins using a novel catalyst. By using the catalyst of the present invention, the monomer partial pressure during polymerization is low, and Due to the short polymerization time, the amount of catalyst residue in the produced polymer is extremely small, so the catalyst removal step can be omitted in the polyolefin manufacturing process, and the amount of atactic moieties produced in the produced polymer is also extremely small. can get.

The present invention will be explained in detail below.

The present invention includes (1) magnesium halide, (2) general formula S i (OR) J4-m (where R has 1 carbon number)
~24 hydrocarbon residues,
is 0≦m≦4), (8) an organic carboxylic acid halide, and (4) an aluminum halide. By carrying out polymerization or copolymerization of α-olefins using a solid catalyst component obtained by supporting an addition compound of The present invention relates to a method for producing polyolefins with extremely high activity and high stereoregularity.

In the present invention, (1) magnesium halide, (2
) General formula S i (OR), a compound represented by one rnx4, (8) organic carboxylic acid halide and (
4) There is no particular restriction on the method of contacting aluminum halide to obtain the solid catalyst component of the present invention, and the method may be carried out at a temperature of 20 to 400°C in the presence or absence of an inert solvent,
Preferably under heating at 50 to 300°C, usually for 5 minutes to 2
The reaction may be carried out by contacting for 0 hours, by co-pulverization, or by an appropriate combination of these methods.

Furthermore, there is no particular restriction on the reaction order of components (1) to (4); four components may be reacted simultaneously, eight components may be reacted, and then another component may be reacted. 2
After reacting the components, the other two components may be reacted,
After reacting two components, the next one component may be reacted, and then the remaining one component may be reacted.

The inert solvent used at this time is not particularly limited, and hydrocarbon compounds and/or derivatives thereof that do not normally inactivate the Ziegler type catalyst can be used.

Specific examples of cholera include propane, butane, pentane, hexane, heptane, octane, benzene, toluene, xylene, cyclohexane, various aliphatic saturated hydrocarbons, aromatic 5-aromatic hydrocarbons, alicyclic hydrocarbons, and Examples include alcohols, ethers, and esters such as ethanol, diethyl ether, tetrahydrofuran, ethyl acetate, and ethyl benzoate.

It is desirable that the co-pulverization treatment is carried out using a device such as a ball mill, a vibration mill, a rod mill, or an impact mill, usually at a temperature of 0 to 20°C, preferably 20 to 100°C, for 0.5 to 80 hours.

In the present invention, a method of obtaining a solid carrier by co-pulverizing components (1) to (4) is particularly preferably employed.

In the present invention, the proportion of component (1) magnesium halide and component (2) compound represented by the general formula S i (OR>, rnX4-O) is the molar ratio of component (1).
: Component (2) is 1:(1001-10, preferably 1:
It is 0.01-1. The usage ratio of component (8) organic carboxylic acid halide is component (1) and component (8) is 1 in molar ratio.
: 0.0016-10, preferably 1 : 0.01-1. The ratio of component (4) aluminum halide to be used is a molar ratio of component (1) to component (4) of i:o, ooi to 10, preferably 1.
Preferably, 1:0.01 to 1.

A solid catalyst component is obtained by supporting a titanium compound and/or an addition compound of a titanium compound and an organic acid ester on the thus obtained solid support.

A known method can be used to support the titanium compound and/or the addition compound of the titanium compound and the organic acid ester on the carrier. For example, a solid support is treated with excess titanium compound and/or in the presence of an inert solvent.
Alternatively, it can be carried out by bringing the titanium compound and the organic acid ester into contact with an adduct compound under heating, preferably at 50 to 800°C in the presence of an inert solvent such as n-hexane. This is conveniently carried out by heating, preferably to 10(-) to 150°C. The reaction time is not particularly limited, but may vary. For example, processing times can range from 5 minutes to 10 hours. Of course, this treatment should be carried out under an inert gas atmosphere free of oxygen and moisture. After the completion of the reaction, the method for removing unreacted titanium compounds and /le, which are adducts of titanium compounds and organic acid esters, is not particularly limited. It can be evaporated under conditions to obtain a solid powder. Another preferred method includes a method of co-pulverizing a solid support and a required amount of a titanium compound and/or a compound of a titanium compound and an organic acid ester.

In the present invention, by adding a required amount of a titanium compound and/or an addition compound of a titanium compound and an organic acid ester, the cleaning and removal step can be omitted. A method by co-grinding is preferably used for %.

In the present invention, the equipment used for co-pulverization is not particularly limited, but typically a ball mill, vibration mill, rod mill, impact mill, etc. are used, and the temperature is usually 0°C to 200°C, preferably 20'C to 100°C. The catalyst component of the present invention can be produced by co-pulverizing for 0.5 to 80 hours. Of course, the co-grinding operation should be carried out in an inert gas atmosphere, and sludge moisture should be avoided as much as possible.

The magnesium halide used in the present invention is substantially anhydrous and includes magnesium fluoride, magnesium chloride, magnesium bromide, magnesium iodide, and mixtures thereof, with magnesium chloride being particularly preferred.

General formula S i (OR) m used in the present invention
Xa -m (Here, R is a hydrocarbon residue such as an alkyl group having 1 to 24 carbon atoms, an aryl group, an aralkyl group, X is a halogen atom, and m is O≦m≦4) Examples of compounds represented by include silicon tetrachloride, monomethoxytrichlorosilane, monoethoxytrichlorosilane, monoisopropoxytrichlorosilane, mono-n-butoxytrichlorosilane, monozentoxytrichlorosilane, monooctoxytrichlorosilane, monostearoxy Trichlorosilane, monophenokiditrichlorosilane, mono p-methylphenokiditrichlorosilane, dimethoxydichlorosilane, jetoxydichlorosilane, diisopropoxydichlorosilane, di-butoxydichlorosilane, dioctoxydichlorosilane, trimethoxymonochlorosilane, triethoxymono Chlorosilane, triisopropoxymonochlorosilane, tri-n-butoxymonochlorosilane, tri-86c
m-butoxymonochlorosilane, tetraethoxysilane,
Tetraisopropoxysilane can be mentioned.

The organic carboxylic acid halide used in the present invention is a compound represented by the general formula (where X represents a hydrocarbon residue such as a monol group or an aralkyl group, and X represents a halogen atom), and specific examples include acetyl fluoride, Acetyl chloride, acetyl bromide, acetyl iodide, propionyl chloride, propionyl bromide, n-butyryl chloride, 5e
c-Butyryl chloride, t-butyryl chloride, n-valeryl chloride, invaleryl chloride, n-caproyl chloride, capryl chloride, stearoyl chloride, benzoyl chloride, benzoyl fluoride, benzoyl bromide, penzoyl iodide , toluoyl chloride, toluoyl fluoride, toluoyl bromide, naphthoyl chloride, and the like. Among these, benzoyl chloride and toluoyl chloride are particularly preferred.

Examples of the aluminum halide used in the present invention include aluminum chloride, aluminum bromide, and aluminum iodide, with aluminum chloride being particularly preferred.

As the titanium compound used in the present invention, tetravalent titanium compounds and trivalent titanium compounds are suitable. Specifically, the tetravalent titanium compound has the general formula Ti (ORnX
4-n (Here, R represents an alkyl group, an aralkyl group, or an aralkyl group having 1 to 20 carbon atoms, and X represents a halogen atom, where n is 0≦n≦4.) Titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, monomethoxytrichlorotitanium, dimethoxydichlorotitanium, trimethoxymonochlorotitanium7. Tetramethoxytitanium, monoethoxytrichlorotitanium, jetoxydichlorotitanium, trimethoxymonochlorotitanium, tetraethoxytitanium, monoinpropoxytrichlorotitanium, diisopropoxymonochlorotitanium, triisopropoxymonochlorotitanium, tetrainpropoxytitanium, monobutoxytrichlorotitanium , dibutoxydichlorotitanium, mono-2-thoxytrichlorotitanium, monophenoxyditrichlorotitanium, diphenoxydichlorotitanium, triquenoxymonochlorotitanium, tetraphenoxytitanium, and the like. As octavalent titanium compounds, titanium tetrahalides such as titanium tetrachloride and titanium tetrabromide are combined with hydrogen, aluminum, titanium, or periodic rule 1.
Examples include titanium trihalides obtained by reduction with organometallic compounds of group metals. Also, the general formula Ti (O
R) □X4-□ (where R represents an alkyl group, aryl group, or aralkyl group having 1 to 20 carbon atoms; halogenated alkoxytitanium in periodic table 1
Examples thereof include octavalent titanium compounds obtained by reducing group metals of groups 1 to 1 with 13-organometallic compounds.

As an addition compound of a titanium compound and an organic acid ester, the molar ratio of titanium compound:organic acid ester is 2=1 to 1.
:2 is preferred. These addition compounds include T
iCl4・Ca 115 C00CIHH,7'i
C14・2CsfhCOOC21b, TiCl4・p−
Cf1sOCeHsCOOC2Ha , TiC1,・C
Examples include a Hs C00Ct Ha and the like.

In the present invention, the amount of the titanium compound and/or the addition compound of the titanium compound and the organic acid ester used is not particularly limited, but the amount of the titanium compound contained in the solid product is usually 0.5 to 20% by weight. , preferably 1 to 10% by weight.

As the organometallic compound used in the present invention, organogold-1← lump compounds of groups ← to ↑ of the periodic table, which are known as components of Tegler's catalyst, can be used, but organoaluminum compounds and organozinc compounds are particularly preferred. . Specific examples include the general formula R3A3 RzAIXz RAIXz, R2Al
0RXRAI<ORX and Rs Al 2Xs organic atubenium compound (wherein R is an alkyl group or aryl group having 1 to 20 carbon atoms, X is a rogen atom),
R may be the same or different)-! or general formula R2
It is an organic zinc compound of Zn (R is an alkyl group having 1 to 20 carbon atoms and may be the same or different), and includes triethylaluminum, triisopropylaluminum, triisobutylaluminum,
Examples include tri-5eC-butylaluminum, tritart-butylaluminum, trihexylaluminum, trioctylaluminum, diethylaluminum chloride, diisopropylaluminum chloride, ethylaluminum sesquichloride, diethylzinc, and mixtures thereof.

In the present invention, the organometallic compound component is used as a mixture or addition compound of the organometallic compound and an organic acid ester.

At this time, when an organometallic compound and an organic acid ester are used as a mixture, the organic acid ester is usually 0.1 to 1 mol per 1 mol of the organometallic compound, preferably 0.2 to 1 mol.
Use 0.5 mol. When used as an addition compound of an organometallic compound and an organic acid ester, it is preferable that the molar ratio of organometallic compound:organic acid ester is 2=1 to 1:2.

In the present invention, the amount of the organometallic compound used is not particularly limited, but is usually 0.1 to 1
000 moles can be used.

The organic acid ester used in the present invention has 1 to 1 carbon atoms.
It is an ester of 24 saturated or unsaturated monobasic or dibasic organic carboxylic acids and an alcohol having 1 to 30 carbon atoms. Specifically, methyl formate, ethyl acetate, amyl acetate, phenyl acetate, octyl acetate, methyl methacrylate, ethyl stearate, methyl benzoate, ethyl benzoate, n-propyl benzoate, i-propyl benzoate, benzoic acid. Butyl, hexyl benzoate, cyclopentyl benzoate, cyclohexyl benzoate, phenyl benzoate, 4-tolyl benzoate, methyl salicylate, ethyl salicylate, methyl p-oxybenzoate, methyl p-oxybenzoate, phenyl salicylate, p- Cyclohexyl oxybenzoate, benzyl salicylate, ethyl α-resorucinate, methyl anisate, ethyl anisate, phenyl anisate, benzyl anisate, ethyl 0-methoxybenzoate, methyl p-ethoxybenzoate, methyl p-toluate, p-ethyl toluate, p-phenyl toluate, 0-ethyl toluate, m-ethyl toluate, p
Examples include methyl -aminobenzoate, ethyl p-amino17-benzoate, vinyl benzoate, allyl benzoate, benzyl benzoate, methyl naphthoate, and ethyl naphthoate.

Among these, particularly preferred is benzoic acid, 0-! or p-)ruyl acid or p-anisic acid, and methyl esters and ethyl esters thereof are particularly preferred.

The olefin polymerization reaction using the catalyst of the present invention is carried out in the same manner as the olefin polymerization reaction using a conventional Ziegler type catalyst. That is, all reactions are carried out substantially in the absence of oxygen, water, etc., in the gas phase, or in the presence of an inert solvent or with the monomer itself as the solvent. The polymerization conditions for the olefin are a temperature of 20 to 800°C, preferably 40 to 180°C, and a pressure of normal pressure to 70°C.
c9/cm2・G% preferably 2 to 60/σ1
It is 2.G. Although the molecular weight can be controlled to some extent by changing polymerization conditions such as polymerization temperature and catalyst molar ratio, it is effectively carried out by adding hydrogen to the polymerization system. Of course, using the catalyst of the present invention, a two-step or more multi-step polymerization reaction with different polymerization conditions such as hydrogen concentration and polymerization temperature can be carried out without any hindrance.

The method of the present invention is applicable to the polymerization of all olefins that can be polymerized with Ziegler's catalyst, such as the homopolymerization of α-olefins with ethylene, propylene, 1-butene, 4-methylpentene-1, and the polymerization of α-olefins with ethylene. It is suitably used for random and block copolymerization of propylene, ethylene and 1-butene, propylene and 1-butene, and the like. Copolymerization with dienes, such as copolymerization of ethylene and butadiene, and copolymerization of ethylene and 1,4-hexadiene, is also preferably carried out for the purpose of modifying polyolefins.

In the present invention, it can be particularly effectively used to polymerize or copolymerize α-olefins having 8 to 8 carbon atoms with good stereoregularity.

Examples will be described below, but these are for illustrative purposes to carry out the present invention, and the present invention is not limited thereto.

Example 1 (α) Synthesis of catalyst components 10 g of anhydrous magnesium chloride and 6 pieces of tetraethoxysilane
1 and benzoyl chloride 1.5 - Inner volume 4 containing 25 stainless steel balls with a diameter of 1 inch
After ball milling in an oOrnl stainless steel pot for 16 hours at room temperature under a nitrogen atmosphere, 6 g of anhydrous aluminum trichloride was added and milled for 1 hour at room temperature under a nitrogen atmosphere.
After 6 hours of ball milling, titanium tetrachloride 2r
After adding nl, ball milling was performed at room temperature for 16 hours under a nitrogen atmosphere. After ball milling, 1 g of the solid powder obtained contained 82 m9 of titanium.

(b) In polymerization 2, the autoclave equipped with a stainless steel induction stirrer was purged with nitrogen, 100% of hexane was added, 5 mmol of l-ethylanopenium, 1.4 mmol of ethyl benzoate, and 100 μm of the above solid powder were added, and the mixture was stirred. 550 while
The temperature was raised to ℃. The system weighs 0.5 kg at the vapor pressure of hexane.
/ryn”・G, but then the total pressure of propylene is 7
Propylene was continuously introduced so that ~/crn2.G was obtained, and polymerization was carried out for 1 hour.

After the polymerization was completed, excess propylene was discharged, cooled, and the contents were taken out and dried to obtain 182 g of white polypropylene.

The figure is the total amount of the product, including the amorphous material.

Catalyst activity is 200g polypropylene/g solids/hr-C
3PI.

21- Pressure 6800g polypropylene 7'1-hr-
(At 4He pressure,!, including solvent-soluble polymers, boiling n
- The total extraction residue rate with hebutane was 98.0.

Comparative Example 1 In Example 1, a catalyst component was synthesized and polymerized in the same manner as in Example 1 except that benzoyl chloride was not used, and 1.65 g of polypropylene was obtained.

Catalytic activity is 250g polypropylene/g solids・hr・
C3H, pressure, 7800g polypropylene/F! Ti-h
It was r-csl-16. Including solvent-soluble polymers,
The total extraction residue with boiling n-hebutane was 90.2%, which was inferior to Alternative Example IK.

Comparative Example 2 When a catalyst component was synthesized in the same manner as in Example 1 except that anhydrous aluminum trichloride was not used, 1 g of the obtained solid powder contained 421ψ titanium. It was

Propylene was polymerized in the same manner as in Example 1, except that 100 mg of the solid powder was used.
58 g of white polypropylene was obtained.

Catalyst activity: 82g polypropylene/g solids/hr-cJ
6 pressure, 1900.9 polypropylene/'l Ts-h
The total extraction residue with boiling n-hebutane, including the solvent-soluble polymer, was 85.8%.

Comparative Example 8 In Example 1, the catalyst component was synthesized in the same manner as in Example 1 except that tetraethoxysilane was not used, and 1 g of the obtained solid powder contained 41 μg of titanium. .

Polymerization of propylene was carried out in the same manner as in Example 1, except that 100 ml of the above solid powder was used, and 98 g of white polypropylene was obtained.

Catalytic activity is 140g polypropylene/g solids・hr・
Cs Ha pressure, 8500g polypropylene/gTi-
hr-CsHa pressure, and the residual rate of extraction with boiling n-hebutane, including the solvent-soluble polymer, was 83.1%.

Example 2 In Example 1, 40 g of a 1:1 (molar ratio) adduct of titanium tetrachloride and ethyl benzoate was used instead of titanium tetrachloride.
The catalyst component was synthesized in the same manner as in Example 1 except that 1 g of the obtained solid powder contained 21
Contains m9 of titanium.

Polymerization of propylene was carried out in the same manner as in Example 1, except that the above solid powder 10.0771& was used, and 87 g of white polypropylene was obtained.

Catalyst activity id, 181 polypropylene/9 solids・hr・
C3B', pressure, 6400g polypropylene/gTi-h
γ·C, H6 pressure, and the total extraction residue with boiling n-hebutane, including the solvent-soluble polymer, was 94.1%.

Examples 8-8 Catalyst components were synthesized in the same manner as in Example 1, except that components (1) to (4) shown in Table 1 were used, and propylene was synthesized in the same manner as in Example 1. Polymerization was carried out. The results are shown in Table 1.

25- Example 9 In Example IVtC, 1.4 ethyl p-anisate was substituted for ethyl benzoate and triethylaluminum.
Polymerization of propylene was carried out in the same manner as in Example 1, except that 5.0 mmol of aluminum and triisobutylaluminum were used, and 130 g of white polypropylene was obtained.

Catalyst activity is 200g polypropylene #solid/hr/C
sH6 pressure, 6800g polypropyref/gTi-h
r-C3H.

The total extraction residue with boiling n-hebutane, including the solvent-soluble polymer, was 98.8%.

Example 10 Anhydrous magnesium chloride 10g 1 tetraethoxysilane 6
ml.

6 g of anhydrous aluminum chloride and 1.5 M benzoyl chloride were placed in a 300 rnt round bottom flask, then 1
00 mA of butane was added and stirred at 100°C for 2 hours, then 50 mA of titanium tetrachloride was added and further stirred at 1°C for 2 hours.

Next, unreacted titanium tetrachloride was removed by washing with n-hexane 9 times at 100 °C, followed by vacuum drying to obtain a catalyst component. 1 g of the solid powder obtained contained 35 m9 of titanium.

Example 1 except that 100 m9 of the above solid powder was used.
When propylene was polymerized in the same manner as above, 108 g of white polypropylene was obtained.

Catalytic activity is 170g polypropylene/g solids・hr・
CsH6 pressure, 4700g polypropyref/'J
T 1-hr-CB He pressure was used, and the total extraction residue with boiling n-hebutane, including the solvent-soluble polymer, was 9.
It was 2.6%.

Patent applicant Nippon Oil Co., Ltd., 4 birds 1,”) Agent Patent attorney Ryoji Kawase
, ,'-2 Death- Procedural amendment September 3, 1980 Haruki Shimada, Commissioner of the Japan Patent Office 1. Indication of the case 1983 Patent Application No. 114378 2. Name of the invention Process for producing polyolefin 3. Person making the amendment Relationship with outside parties Patent applicant name (444) Nippon Oil Co., Ltd. 4, Agent Taesan Mansion Shinnanpeidai (Telephone number 1476-2571) 6
, Contents of the amendment (1) The following general amendment will be made to "Trisec......tetrine propoxysilane" in the second to bottom line of page 10 of the specification (the same applies hereinafter).

"Tri-5ec-butoxymonochlorosilane, tetramethoxysilane, tetraethoxysilane, tetra-propoxysilane, tetra-n-butoxysilane, tetra-5eC
-butoxysilane, tetrapentoxysilane, tetraethoxysilane" (2) Corrected to "Jkr benzoyl iodide" on page 11, lines 12-13.

(3) Correct all "550°C" on line 8 of page 21 to "5-0°C".

(4) 223ij line 7 norr 1. '6'5 y J
* "165f" color correction is complete.

(5) Correct it to r4 (lJffir4.(1) on page 24, line 9.

2-

Claims (1)

[Claims] (1) Magnesium halide, (2) General formula Si (
O/j') J4- m (where R is a hydrocarbon residue having 1 to 24 carbon atoms, X is a halogen atom, and m is 0≦m≦4
A titanium compound and/or an addition compound of a titanium compound and an organic acid ester are supported on a solid material obtained by contacting a compound represented by (8) an organic carboxylic acid halide and (4) an aluminum halide. Polymerization or copolymerization of olefins is carried out using a solid catalyst component obtained by the above-mentioned method, and a catalyst formed by combining a mixture or an addition compound of an organometallic compound and an organic acid ester. Production method.