JPS61231006A - Production of olefin polymer - Google Patents

Abstract

PURPOSE:To obtain a highly stereoregular olefin polymer in high yields, by contacting an olefin with a catalyst comprising a specified solid catalyst, an organoaluminum compound and an electron-donating compound. CONSTITUTION:An olefin is polymerized by contact with a catalyst comprising a solid catalyst component (A) containing a magnesium halide, a titanium halide and a nitro compound as components, an organoaluminum compound (B) and an electron-donating compound (C). As the magnesium halide, magnesium chloride, especially anhydrous magnesium chloride is preferable. As the titanium halide, titanium trichloride is particularly desirable. As the nitro compound, an aromatic one is desirable and further a dinitro compound or a compound having both of a nitro group and another functional group is preferred to a mononitro compound.

Description

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

More specifically, the present invention relates to a method for producing an olefin polymer that can obtain a highly stereoregular polymer in high yield when applied to the polymerization of an α-olefin having 3 or more carbon atoms by using a specific catalyst. .

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

However, this supported catalyst has low stereoregularity;
Although it has been considered impossible to omit the extraction step, in recent years improvements in catalyst systems have significantly improved stereoregularity. It is known that a certain degree of highly active and highly stereoregular polymerization is possible by using a carboxylic acid ester during the preparation of a solid catalyst component (Japanese Patent Publication No. 52-367
No. 86, Special Publication No. 52-36913, Special Publication No. 52-50
Publication No. 037, etc.). However, even with these proposals, it has been difficult to realize a non-contact and non-extraction process, and further improvements have been desired.

Therefore, the present inventors have been actively searching for catalysts with high activity and high stereoregularity that can realize a non-detachment and non-extraction process. As a result, the present invention was surprisingly achieved by realizing highly active and highly stereoregular polymerization by allowing a nitro compound to exist in the solid catalyst component.

That is, the method for producing an olefin polymer according to the present invention is as follows:
The olefins are mixed into (A) a solid catalyst component containing a magnesium halide, a titanium halide, and a nitro compound as essential components, (B) an organoaluminum compound, and (C)
It is characterized by polymerization in contact with a catalyst consisting of an electron-donating compound.

According to the catalyst of the present invention, polyolefins can be obtained in high yield and with high stereoregularity.

The catalyst according to the invention has three specific components, namely (A),
It consists of (B) and (C). Within each component, combinations of the respective specific compounds of interest are possible.

(A) The solid catalyst component (A) used in the present invention contains magnesium halide (a), titanium halide (b), and nitro compound (c) as essential components.

(a) Magnesium halides Examples of magnesium halides include magnesium chloride,
Magnesium bromide and magnesium iodide can be used. Preferred is magnesium chloride, and more preferably substantially anhydrous.

(b) Titanium halide As the titanium halide, chloride, bromide and iodide of titanium can be used. Chlorides are preferred, and examples 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) CI (R is an alkyl group (carbon 4-n prime number of about 1 to 10)) can also be used.

(c) Nitro compounds Nitro compounds include aromatic (including alkaryl (alkyl carbon number approximately 1 to 15)) or aliphatic (including cycloalkyl and aralkyl) (carbon number 1 to 10)
degree) mono- and dinitro compounds. A nitro compound has a substituent other than nido 013 on the hydrocarbon group to which the nitro group is bonded, such as halogen, hydroxyl group, amino group, nitrile group, aliphatic or aromatic acyl group, alkoxy to aryloxy group, etc. thing(
The number may be (usually one for each).

Specific examples of suitable nitro compounds include aromatic compounds such as nitrobenzene, 0-nitrotoluene, 0-dinitrobenzene, m-dinitrobenzene, p-dinitrobenzene, 2,3-dinitrotoluene, 3,4-dinitrotoluene. , 0-nitrophenol, m-nitrophenol, 0-nitroaniline, m-nitroaniline, 0-nitrobenzonitrile, 0-nido-Oacetophenone, 0-
Nitrobenzophenone, m-nitrobenzophenone, 1
．． Examples include 8-dinitronaphthalene, 2,3-dinitrotoluene, and 1,5-dinitronaphthalene. Aliphatic compounds include 2-nitro-n-butane, Nido-Ocyclohexane, 1,2-dinitroethylene, 1-
Nido-o-2-acetylethylene, 1-nitro-2-aminoethylene, 1,2-dinitrocyclohexane, 1-nitro-2-acetylcyclohexane, 1-nitro-2-
Examples include cyanocyclohexane.

Among the above nitro compounds, aromatic compounds are preferred.

Further, a method using a dinitro compound or a compound having both a nitro group and another functional group is preferable to a mononitro compound.

(d) Preparation of Component A 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. Magnesium chloride can be pulverized using a ball mill or a vibration mill. Dissolution of magnesium chloride can be carried out using a hydrocarbon or halogenated hydrocarbon as a solvent and alcohol, phosphoric acid ester, titanium alkoxide, etc. as a dissolution promoter. Precipitation of dissolved magnesium chloride can be carried out by adding a poor solvent, an inorganic halide 1, an electron donor (such as an ester), or methylhydrodiene polysiloxane. For details on such pretreatment of magnesium chloride, see JP-A-53-4568.
No. 8, No. 54-31092, No. 57-180612, No. 58-5309, and No. 58-5310.

The order of contact between pretreated magnesium chloride (a), titanium halide (b), and nitro compound (c) is to form a complex of titanium halide and nitro compound, and then to contact this complex with magnesium chloride. The magnesium chloride and titanium halide may be brought into contact with each other, or the magnesium chloride and the titanium halide may be contacted with the nitro compound, or the magnesium chloride and the nitro compound may be brought into contact with the titanium halide.

The contact may be carried out by pulverization using a ball mill, vibration mill, or the like, or by adding magnesium chloride or magnesium chloride treated with a nitro compound to the liquid phase of titanium halide.

The contact time is 10 minutes after all components are in contact.
Usually it is about 100 hours.

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

The titanium halide content of the solid catalyst component thus produced is 1 to 201% by weight, and the molar ratio of the nitro compound to the titanium halide is about 0.01 to 3.0.

Ruluji A As the organoaluminum compound (B) used in the present invention, trialkylaluminum is preferred. Examples of trialkylaluminum include trimethylaluminum, triethylaluminum, trimybutylaluminum, tri-n-hexylaluminum, and the like. Particularly preferred is triethylaluminum. Moreover, organic aluminum compounds such as alkyl aluminum halides and alkyl aluminum alkoxides can also be used in combination.

Organoaluminum compound (B) used in polymerization
The molar ratio of titanium halide in solid catalyst 1 (A) is:
A range of 10 to 1000 is commonly used.

C As the electron donating compound (C) used in the present invention,
Examples include organosilicon compounds, amines, ethers, peroxides, and the like.

As the organosilicon compound, those having an alkoxy group and those having a phenyl group, cycloalkyl group, or branched alkyl group as a hydrocarbon group bonded to a silicon atom are preferable, and examples include phenyltriethoxysilane and diphenyldimethoxysilane. , 2-norbornyltrimethoxysilane, 5-ethylidene-2-norbornyltriethoxysilane, tert-butyltriethoxysilane, and tetraethoxysilane. Among these, those having 2 to 3 alkoxy groups are particularly preferred.

The amine is preferably a cycloaliphatic amine, particularly piperidine or pyrrolidine and its X9 form, especially one in which a plurality of lower alkyl groups (preferably methyl or ethyl) are emanating from the carbon atom adjacent to the nitrogen atom. ,2,
2.6.6-tetramethylbiveridine, 2.2.6.6
-Titraethylbiperidine, 2.6-dibutylbiperidine, 2.2.5.5-Ladramethylpyrrolidine, 2
Examples include ゜2.5.5-tetraethylpyrrolidine.

Ethers include the general formula R1R2R3C0R4. In the formula, R1 is an aromatic or cycloaliphatic hydrocarbon (about 1 to 15 carbon atoms), and R2, R and R
4 is a hydrocarbon group (about 1 to 10 carbon atoms). Specific examples include α-cumyl methyl ether, α-cumyl ethyl ether, 1.1-diphenylethyl methyl ether, 1.1-diphenylethyl ethyl ether, α-cumyl tert-butyl ether, diα-cumyl ether, 1.1
-ditolylethyl methyl ether, 1,1-ditolylethyl ethyl ether, bis(1,1-ditolylethyl)
Ether, 1-tolyl-1-methylethyl methyl ether, phenylmethyldimethoxymethane, diphenyldimethoxymethane, tolylmethyljethoxymethane, 2-norbornanemethyldimethoxymethane, bis(2-norbornane)dimethoxymethane, 5-ethylidene-2- Examples include norborna-methyldimethoxymethane. Examples of other ethers include 1,8-cineole, 1,4-cineole, medarcineol, and the like.

Examples of peroxide include compounds represented by the following formula.

(In the formula, R1-R4 are saturated or unsaturated hydrocarbon groups (about 1 to 15 carbon atoms), and R4 is a hydrocarbon group (about 1 to 15 carbon atoms) containing or not containing an oxygen atom. ) Specific examples of such peroxides include 1.1-
Bis(tert-butylperoxy)-3,3゜5-tolumethylcyclohexane, 1,1-bis(tert-butylperoxy)cyclohexane, di-tert-butyl peroxide,
Examples include tert-butylcumyl peroxide, dig-cumyl peroxide, bis(1°1-diphenylethyl) peroxide, and 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane.

The molar ratio of the electron donating compound (C) and the organoaluminum compound (B) used is usually 0.01 to 1.0, preferably 0.02 to 0.5.

1-1 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 monomers.

The polymerization can be carried out in the presence or absence of an inert solvent, ie bulk polymerization in the gas or liquid phase. The polymerization mode may be continuous or batchwise. The molecular grouping of the polymer can be adjusted by controlling the hydrogen temperature of the polymerization tank. Polymerization temperature is 0~200℃, preferably 50~10℃
A range of 0°C is selected. The polymerization pressure is Ii! of 1 to 100 atm. The surrounding area is normal.

Experimental example Tsuji L 1) Production of titanium-containing solid catalyst component 50d of dehydrated and deoxygenated n-heptane was introduced into a 300 m flask that had been sufficiently purged with nitrogen, and then MOCI
2 (Magnesium chloride) 0.1 mol of (a), T
After introducing 0.2 mol of i(OBu)4 (tetrabutoxytitanium), it was reacted at 90°C for 2 hours to give 1vlc+c
A hydrocarbon solution of l2 was prepared. Next, 12 days of methylhydrodiene polysiloxane (20 cps) was added and reacted at 40° C. for 3 hours, resulting in the precipitation of about 409 grey-white solids. When this precipitated solid was thoroughly washed with n-hebutane and analyzed, it was found that this precipitated solid contained 12.1
% MgCl2 by weight.

From this precipitated solid, 20g (Mac + 2 = 2.43g
) was sampled to obtain 7.5 m of Si C+ 4 (silicon tetrachloride) and 0.9 m of 0-dinitrobenzene (ha).
97 g was added and reacted (30° C./1 hour in a solvent of n-hebutane 70 d, then 70° C./1 hour). After the reaction was completed, the product was washed with n-hebutane. 25 m of TlC14 (titanium tetrachloride) (0) was added to the n-heptane slurry of the obtained solid product and treated at 90°C for 1 hour. After removing the supernatant liquid, TiCl was added under the same conditions again.
A contact treatment with 4 was performed. After this treatment, the solid was washed by decantation (5 times with 200 d of n-heptane) to obtain the desired titanium-containing solid catalyst component (A) slurry. When a part of this slurry was sampled and n-hebutane was evaporated to dryness and analyzed, it was found that 4.
It was found that it contained 98% by weight of titanium.

2) In an autoclave equipped with a stirring device and having an internal volume of 3 liters of propylene polymerization, 1.5 liters of dried and degassed n-hebutane, 320 ay of phenyltriethoxysilane (C), 750 q of triethylaluminum (B) and the above solid were added. From the catalyst component (A) slurry, 50 ay of solid catalyst components were introduced in this order under a propylene atmosphere, and 200 ml of hydrogen was added to initiate polymerization. Polymerization was carried out using a propylene pressure cuff Ky/dG.
.

The test was carried out at 70°C for 3 hours. After the polymerization was completed, the remaining monomers were purged, the polymer slurry was separated from each other, and the resulting polymer products were determined by drying the powdered polymer and concentrating the furnace liquid.

The stereoregularity c (hereinafter referred to as product II) of this powder polymer was determined by a boiling 1 ln-hebutane extraction test. In addition, total II (ratio of the amount of boiling n-hebutane-insoluble polymer to the total amount of polymer produced) is: total II - amount of powder polymer x product II / (amount of powder polymer 11 liquid concentrated polymer)
It was calculated using the following relational expression. Ml (melt flow index) was measured according to ASTM-D-1238. The results obtained were as shown in Table-1.

Support i: When producing a solid catalyst component containing titanium, a solid catalyst component was produced under the same conditions and method as in Example-1, except for changing the type of nitro compound (c) defined in component (A). Then, propylene was polymerized. The results obtained were as shown in Table-1.

Example 1 was repeated, but the electron donating compound defined as component (C) was changed from phenyltriethoxysilane to the compound shown in Table 2. The results of the polymerization test were as shown in Table-2.

Uragura JL Nishiko 2 In producing the titanium-containing solid catalyst component, everything was the same as Example-1 except that the nitro compound defined as component (A) was not used at all or a known electron-donating compound was used. The experiment was conducted under the same conditions and method. The results obtained were as shown in Table-1.

Claims (1)

[Claims] The olefins are mixed into (A) a solid catalyst component containing a magnesium halide, a titanium halide, and a nitro compound as essential components, (B) an organoaluminum compound, and (C)
A method for producing an olefin polymer, which comprises polymerizing it by contacting it with a catalyst made of an electron-donating compound.