JPS6178804A - Production of olefin polymer - Google Patents

Abstract

PURPOSE:To obtain a highly stereoregular olefin polymer in high yields, by polymerizing an olefin by using a magnesium halide containing a specific compound and a titanium halide as a catalyst. CONSTITUTION:The purpose olefin polymer is obtained by contacting an olefin with a catalyst comprising a solid catalyst compound containing a magnesium halide and a titanium halide, an organoaluminum compound and an ether of the formula (wherein R<1>-R<3> are each a saturated or unsaturated hydrocarbon residue, including a substituted phenyl group, and R<4> is a hydrocarbon group). As the magnesium halide used, magnesium chloride is preferable and further preferably anhydrous. As the titanium halide, titanium chloride is particularly preferable. In the preparation of said solid catalyst component, the addition of an electron donor is desirable.

Description

[Detailed description of the invention] Background of the invention Technical field The present invention relates to a method for producing olefin polymers.

More specifically, the present invention provides a method for producing C8 olefin polymers that can be used to polymerize α-olefins having a carbon f5 number of 3 or more by using a specific catalyst to obtain a highly 1γ regioregular polymer in high yield. Regarding manufacturing methods.

Until now, catalyst systems consisting of a solid catalyst component in which a titanium compound is supported on magnesium halide and an organoaluminum compound have higher polymerization activity than conventional catalyst systems.
It has been suggested that the need to remove catalyst residues from polymers may be eliminated.

Prior Art However, this supported catalyst has low stereoregularity;
Although it has been considered impossible to omit the extraction step, in recent years improvements in cocatalyst systems have significantly improved stereoregularity. Esters (Special Publication Publication No. 56-3) as polymerization additives
976, JP-A-58-157808, etc.) and phenyl group or alkyl-based silicon compounds (JP-A-57-63310, JP-A-57-63311, etc.) to achieve a certain degree of high activity. - It is known that highly stereoregular polymerization is possible. However, even with these proposed additives, it is difficult to realize a non-decontamination and non-extraction process, and further improvements have been desired.

11 11 ■ Therefore, the present inventors have been diligently searching for polymerization additives with high a-activity and stereoregularity that can realize a process without catalysis or extraction. As a result, surprisingly, by using an ether having a specific structure, highly active, 8-stereoregular polymerization was realized, and the present invention was achieved.

That is, the method for producing an olefin polymer according to the present invention is as follows:
The olefins are combined with (A) a solid catalyst component containing magnesium halide and titanium halide as essential components, (8
) contacted with a catalyst consisting of an organoaluminum compound and a specific ether represented by formula (C) t!
(Φcombined) (wherein, R
1-R3 is a saturated or unsaturated hydrocarbon residue (including substituted hydrocarbon residues). However, one or two of R1 to R3 are phenyl groups (including @-substituted phenyl groups).

R4 is a hydrocarbon group. ) According to the catalyst of the present invention, polyolefins can be produced only in high yields.
1 as a highly stereoregular one.

DETAILED DESCRIPTION OF THE INVENTION The catalyst according to the invention consists of three specific components: (A), (B) and (C).

Solid catalyst component (A) The solid catalyst component (A) used in the present invention contains magnesium halide J3 and titanium halide as essential components.

Magnesium halides include magnesium chloride,
Magnesium bromide and magnesium iodide can be used. Preferably it is magnesium chloride, and it is further desirable that it is substantially anhydrous.

As the titanium halide, titanium chloride, bromide and iodide can be used. Preferred is a chloride, examples of which include titanium tetrachloride and titanium trichloride, with titanium tetrachloride being particularly preferred. Further, an alkoxy group-containing titanium compound represented by the general formula Ti(OR) CI4 (R is an alkyl group) can also be used.

In preparing the solid catalyst component of the present invention, various electron donors may be added, and are also preferred. Examples of the electron donor include M-containing compounds and nitrogen-containing (- compounds).

As the acid-containing compound, ether, ketone and emenol can be used, but nisal is preferably used.

As the ester, carboxylic esters are mainly used, and examples of the aliphatic carboxylic esters include ethyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, methyl methacrylate, diethyl oxalate, and dibutyl maleate. Examples of aromatic carboxylic acid esters include ethyl benzoate, methyl o-toluate, diethyl phthalate, and dihebutyl phthalate. Particularly preferred among these Nisdels are phthalate esters such as diethyl phthalate and dihebutyl phthalate.

In preparing the solid catalyst component, it is desirable to first pre-treat magnesium chloride. This can be carried out using pulverization or dissolution/precipitation techniques. Grinding of magnesium chloride can be carried out using a ball mill or a vibration mill. Magnesium chloride can be dissolved using a hydrocarbon or halogenated hydrocarbon as a solvent, and alcohol, phosphate ester, titanium alkoxide, etc. as a dissolution promoter. It can be carried out using Precipitation of dissolved magnesium chloride can be carried out by adding a poor solvent, a halide, an electron donor such as an ester, or methylhydrodiene polysiloxane. For details of such pretreatment of magnesium chloride, see JP-A-53-
No. 45688, No. 54-31092, No. 57-180
No. 612, No. 58-5309 and No. 58-5310
You can refer to the Tsukinkin Gazette.

The order of contacting the pretreated magnesium chloride with the titanium halide and the electron donor can also be determined by forming a complex of the titanium halide with the electron donor and then contacting this complex with the magnesium chloride. Magnesium chloride and an electron donor can also be brought into contact by contacting magnesium chloride and a titanium halide and then contacting an electron donor. (or by contacting with titanium oxide).

The contact may be carried out by pulverization using a ball mill, vibration mill, or the like, or by adding magnesium chloride or an electron donor-treated product of magnesium chloride to the liquid phase of titanium halide.

Washing with an inert solvent may be performed after contacting the three or four components or at an intermediate stage of contacting each component.

The titanium halide content of the solid catalyst component thus produced is about 1 to 2 (lffi%), and the molar ratio of the electron donor to the titanium halide is about 0.05 to 2.0.

Organoaluminum Compound (B) As the organoaluminum compound (B) used in the present invention, trialkylaluminum is preferable. Examples of the trialkylaluminium include trimethylaluminum, triethylaluminum, tri-butylaluminum, and tri-n-1-silno'aluminum. Particularly preferred is (, U, l-ethylaluminum).

Furthermore, organoaluminum compounds such as )'-ru-1-luminium halides and alkylaluminum alkoxides can also be used in combination.

Organoaluminum compound (B) used in polymerization
And solid touch! ! ! The cell ratio of the titanium halide in (Δ) is usually in the range of 10 to 1000.

Ether Compound (C) Component (C) used in the present invention is an ether represented by the general formula. In the formula, R1-R3 are saturated R1 or unsaturated hydrocarbon residues, generally having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, an alkyl group or an alkenyl group (halogen, phenyl group, (including substituted derivatives substituted with ), or phenyl groups (halogens, alkyl groups (
In particular, lower alkyl groups), phenyl group substitutions, and A conductors). However, one or two of R1 to R3 are phenyl groups (including substituted derivatives with halogen or alkyl groups (particularly lower alkyl groups)). R4 is a hydrocarbon group. Specific examples of such ether compounds include α-cumyl methyl needle, α-cumyl ethyl ether, 1,1-diphenylethyl methyl ether, 1゜1-diphenylethyl ethyl ether, α-cumyl tertiary Butyl ether, diα-cumyl ether, 1.1
-ditolylethyl methyl ether, 1,1-ditolylethyl ethyl ether, bis(1,1-ditolylethyl)
Examples include ether, 1-tolyl-1-methylethylmethyl ether, and the like.

The molar ratio of the ether compound (C) and the organoaluminum compound (B) used is usually 0.01 to 1.0, preferably t40.02 to 0.5.

The polymerization of olefins using the catalyst system of the present invention is suitably carried out in the homopolymerization of ethylene, propylene, and butene, or in the copolymerization of a combination of these polymers.

The polymerization can be carried out in the presence or absence of an inert solvent, ie bulk polymerization in the gas or liquid phase. m
Golden ball type T, continuous type or batch type is fine. The molecule m of the polymer can be adjusted by controlling the hydrogen 81 degrees of the polymerization tank. Polymerization temperature is 0 to 200°C, preferably 50 to 1
A range of 00°C is selected. The polymerization pressure varies between 1 and 100 atmospheres.

Experimental Examples Example 1 (1) Preparation of solid catalyst component In a three-liter glass flask (equipped with a thermometer and stirring bar) with an internal volume of 5001 and purged with nitrogen, 751 purified hebutane,
751 of titanium tetrabutoxide and 10 g of anhydrous magnesium chloride are added. Then, the flask was heated to 90°C and the magnesium chloride was completely dissolved over 2 hours. Next, the flask is cooled to 40° C. and 15 ml of methylhydrodiene polysiloxane is added to precipitate magnesium chloride/titanium tetrabutoxide. After washing this with purified butane, 8.71% of silicon tetrachloride and 1.81% of dihebutyl phthalate were added, and the mixture was heated to 50°C.
Hold for 2 hours. Thereafter, the mixture was washed with purified butane, and titanium tetrachloride 251 was added to the colander and kept at 90°C for 2 hours. This was washed with purified butane to obtain a solid catalyst component.

The titanium content in the solid catalyst component was 3.0% by weight, and the diheptyl phthalate content was 25.0% by weight.

(2) A stainless steel autoclave with a polymerization internal volume of 3 liters was purged with nitrogen, containing 1.5 liters of purified hebutane, 0.75 g of triethylaluminum (B), α-cumyl methyl ether (C)O, ICI, and the above solids. Catalyst component (A) 50
mq, and hydrogen in an amount equivalent to a partial pressure of 0.15 k (1/cm2).Then, the autoclave was heated to 7 mq.
After raising the temperature to 0℃, add 7 kg/cm2G of propylene.
Initiate polymerization by increasing the pressure to n, and continue polymerization for 3 hours while replenishing propylene to maintain this pressure.

After 3 hours, the introduction of the 7mer was stopped and the unreacted 7mer was purged to terminate the polymerization.

When the produced polymer was separated from heptane and dried,
764.5° of polypropylene powder was poured. When heptane was removed from Tonami by heating, amorphous hand coalescence was observed.4.
1 g was obtained. The proportion of amorphous j, Q coalescence among all hand coalescences (hereinafter referred to as APP byproduct rate) was 0.53%.

Further, the boiling n-hebutane insoluble content (hereinafter abbreviated as Pit) of this polypropylene powder was 97.1%. The polymer yield per liter of solid catalyst (hereinafter referred to as CY and approximately 1゛) is 1
It was 5372. MFR (melt flow rate: measured according to ΔSTM-D-1238) was 1.
94, and high specific gravity was 0.46.

Example 2 A solid catalyst component (Δ) was prepared in the same manner as in Example 1, and the procedure was carried out in the same manner as in Example 71 PAl except that 0.11 g of α-cumylethyl ether (C) was used as the polymerization additive. Ta.

As a result, a polypropylene powder of 748.1 (j) was obtained, and the APP by-product rate was 0.69%.

Pll is 96.4%, CY is 15067, MFR is 2.
11. High specific gravity was 0.46.

Claims (1)

[Claims] Olefins, (A) solid catalyst component containing magnesium halide and titanium halide as essential components, (B) organoaluminum compound, and (C) formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ A method for producing an olefin polymer, characterized by polymerization in contact with a catalyst consisting of a specific ether represented by (wherein R^1 to R^3 are saturated or unsaturated hydrocarbon residues (substituted (including hydrocarbon residues).However, R^1
One or two of ~R^3 are phenyl groups (including substituted phenyl groups). R is a hydrocarbon group. )