JPH0557282B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention utilizes a novel Ziegler type catalyst system.
This invention relates to a method for polymerizing or copolymerizing olefins at high temperatures of 130°C or higher.

The following two methods have been implemented for producing olefin polymers at high temperatures in a polymer solution or molten state using a Ziegler type catalyst. The first method is generally called the "solution method" and involves polymerizing or copolymerizing olefin using a solvent such as cyclohexane. This method uses a Ziegler type catalyst to polymerize olefin in a polymer solution state at 120-250°C and 5-50 kg/cm ² . The second method is generally called the "high-pressure ion method" and involves polymerizing or copolymerizing the olefin in a molten state without a solvent at high temperature and high pressure.

These high-temperature solution polymerization methods and high-pressure ionic polymerization methods using Ziegler type catalysts are known to have the advantage of compact reactors and a high degree of freedom in selecting comonomers. However, in polymerization at such high temperatures, most Ziegler-type catalysts usually exhibit high polymerization activity in the early stage of the polymerization reaction;
Polymerization activity decreases rapidly in a relatively short period of time, catalyst efficiency deteriorates, and a large amount of catalyst residue remains after polymerization. Therefore, various improvements have been made to the Ziegler type solid catalyst for high temperatures (for example, Japanese Patent Application Laid-Open No. 51-144397, Japanese Patent Application Laid-Open No. 54-52192,
JP-A-56-18607, JP-A-56-99209, JP-A-57-87405, JP-A-57-153007
Publication No. 190009, Japanese Patent Application Publication No. 1983-
208303), but none of these can be said to be satisfactory in terms of catalytic activity. Particularly with transition metal catalysts such as Ziegler type catalysts, catalyst residues in the polymer have an adverse effect on quality, so if there is a large amount of residues, large-scale equipment such as a catalyst removal process or a polymer purification process is required. Furthermore, when a metal halide such as a titanium halide compound is used as a solid catalyst, it is desired that the polymerization activity per solid catalyst be sufficiently high in order to prevent corrosion of equipment and equipment caused by active halogen.

On the other hand, although there are a number of patents that disclose methods for treating Ziegler-type catalysts with halogen-containing organic compounds, most of these patents treat transition metal-containing solid components with halogen-containing organic compounds during catalyst preparation. Moreover, these methods are not directly aimed at improving polymerization activity. Tokukai Akira
Although JP-A-50-8881, JP-A-53-45688, JP-A-56-93709, and JP-A-56-99206 disclose the addition of halogen-containing compounds to the polymerization system, these The methods also aim to widen the polymer molecular weight distribution or improve stereoregularity, and are not necessarily satisfactory in terms of improving polymerization activity.

The present inventors have conducted intensive research to improve the polymerization activity in high-temperature polymerization, and have found that a) a solid catalyst component containing titanium and/or vanadium b) By using a catalyst component consisting of three components: an organoaluminum compound and c) at least one chlorinated organic compound selected from a chlorinated aliphatic hydrocarbon and a chlorinated alicyclic hydrocarbon,
The inventors have discovered that olefin polymers can be obtained with high catalyst efficiency, leading to the present invention.

The present invention will be explained in detail below.

The solid catalyst component of the present invention includes at least titanium,
It contains a type of transition metal among vanadium. It is preferable to use Ti as the transition metal. As the transition metal compound, any of halides, alkosides, and alkylated compounds can be preferably used, but halides are most preferably used. The solid catalyst component may be a composite compound of a transition metal compound and another organic compound, such as a complex with an electron donor or an inorganic salt.

A typical compound is a highly active titanium catalyst component activated by containing a magnesium compound in a solid catalyst.

For example, a solid titanium catalyst component containing titanium, magnesium and halogen as essential components,
Contains amorphous magnesium halide as a carrier, the specific surface area of which is preferably 30 m ² /g
Examples of the solid catalyst components mentioned above may include electron donors such as organic acid esters, silicate esters, alkoxysilicate esters, amines, and ethers. This solid catalyst component may contain, for example, 0.5 to 25% by weight of titanium, in particular about 1 to 25% by weight of titanium.
More preferably, the content is about 15% by weight. Such a solid catalyst component can be used, for example, at the same time or after pulverization of magnesium halide or treatment with an electron-donating compound such as alcohol or ester.
It is prepared by reacting with TiCl ₄ or TiCl ₃ .

Examples of organoaluminum compounds used in the present invention include triethylaluminum,
Trialkylaluminum such as tri-n-propylaluminum and tri-n-butylaluminum, dialkylaluminum monohalide such as diethylaluminum chloride, alkylaluminum sesquichloride such as ethylaluminum sesquichloride, alkylaluminum dichloride such as ethylaluminum dichloride, etc. Examples include halides, alkylalkoxyaluminums such as diethyl ethoxyaluminum, and the like. Further, aluminoxanes such as bisdiethylaluminoxane, alkylsiloxanes such as trimethyldiethylsiloxalane, and the like are also used. These organoaluminum compounds may be used alone or in combination of two or more.

As the chlorinated organic compound that forms the catalyst system together with the above two components in the polymerization reaction, for example, a chlorinated aliphatic hydrocarbon or a chlorinated alicyclic hydrocarbon having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, is used. be able to. Furthermore, as the organic chlorine compound, either one or two or more polychlorine substituted compounds can be used. In particular, it is preferable to use chlorinated aliphatic hydrocarbons or chlorinated alicyclic hydrocarbons having 1 to 8 carbon atoms. Examples of chlorinated aliphatic hydrocarbons include methyl chloride, ethyl chloride, n-butyl chloride, sec-butyl chloride, t-butyl chloride, hexyl chloride, octyl chloride, 2-ethyl-hexyl chloride, allyl chloride, 4-chloride. -chlorine substituted products such as -butene-1, dichlorine substituted products such as methylene chloride, 1,1-dichloroethane, 1,2-dichloroethane, 1,3-dichloropropane, chloroform, methylchloroform, pentachloroethane,
Examples include polychlorine substituted products such as hexachloroethane, 1,1,2-trichloroethylene, and 1,1,2,2-tetrachlorethylene.

Examples of chlorinated alicyclic hydrocarbons include monochlorine substituted products such as chlorocyclopropane, chlorocyclobutane, and chlorocyclohexane, and polychlorine substituted products such as hexachlorocyclohexane and hexachlorocyclopentadiene.

The above organic chlorine compounds can be used alone or in combination of two or more. Among the above compounds, mono- or dichlorinated aliphatic hydrocarbons having 1 to 8 carbon atoms are preferred, particularly 1,2-dichloroethane, 1,2
-Dichloropropane is preferably used.

The polymerization conditions in the present invention are 130°C or higher, preferably 135°C to 350°C, more preferably 150°C to 270°C.
The temperature and pressure are 5 to 100 Kg/cm ² in the case of the solution method,
Preferably 10-50Kg/ ^cm2 , in the case of high pressure ion method, 350-3500Kg/ ^cm2 , preferably 700-1800Kg/cm2.
^cm2 , and the polymerization method can be either batchwise or continuous.

In the solution method polymerization using the catalyst system of the present invention, the solvent is generally hexane, cyclohexane,
Selected from hydrocarbon solvents such as heptane, kerosene components, and toluene.

In the present invention, the chlorinated organic compound can be added to the polymerization system by any method. The chlorinated organic compound can be added alone to the polymerization system, or it can be mixed with a solid catalyst component containing a transition metal or an organoaluminum compound component before the start of polymerization. It may be added all at once, or may be added continuously or in portions during the polymerization period.

In carrying out the process of the invention, the amount of chlorinated organic compound can be varied within a wide range. The amount of chlorinated organic compound is 0.005 to 100 mol, preferably 1 mol of organoaluminum compound.
It ranges from 0.01 to 25 moles. The ratio of the chlorinated organic compound to the transition metal is preferably between 0.1 mol and 100 mol, and between 1 mol and 100 mol per gram atom of the transition metal.
Particularly preferred is between 50 mol. The molar ratio of organoaluminium to transition metal is 1 to 200, preferably 2 to 100.

The activity of the catalyst system according to the invention is extremely high, and typically the transition metal per volume of solvent or polymerization vessel is
10 ^-6 to 10 milligram atoms, preferably 10 ^-5 to ^{10 -1}
Used in concentrations of milligram atoms. The concentration of the organoaluminum compound and chlorinated organic compound is also preferably 10 mmol or less per unit.

The olefin used in the present invention has 2 or more carbon atoms.
Olefins with 20, preferably 2 to 10 terminal unsaturations, such as ethylene, propylene,
Examples thereof include 1-butene, 1-4-methylpentene, 1-hexene, 1-octene, and vinylcyclohexane. It is also possible to copolymerize a plurality of these olefins and to copolymerize these olefins with diolefins preferably having 4 to 20 carbon atoms.

When olefin polymerization is carried out at high temperatures using the catalyst system of the present invention, the activity does not drop sharply, and the polymerization activity per transition metal and solid catalyst is high, so that the resulting polymer has a high polymerization activity. The amount of catalyst remaining is small, the catalyst removal step can be omitted, and the quality of the polymer due to the remaining catalyst residue is also satisfactory.

Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to the following Examples unless the gist thereof is exceeded.

Example 1 (1) Preparation of solid catalyst component 10 g of commercially available anhydrous magnesium chloride and 10 g of TAC131 (TiCl ₃ 1/3 AlCl ₃ ) manufactured by Toho Titanium Co., Ltd.
A solid catalyst component was obtained by ball milling for an hour.
Analysis of this powder revealed that Ti10.9%, Al1.3%,
It contained 74.6% Cl and 12.0% Mg (both by weight).

(2) Polymerization of ethylene After the autoclave equipped with a stirrer in 1 was sufficiently purged with nitrogen, 500 ml of kerosene component and 0.5 mmol of triethylaluminum were added. After raising the temperature to 200°C, ethylene was added until the total pressure reached 20Kg/cm ² . 3.2 mg of solid catalyst component prepared in (1) above
and 0.05 mmol of 1,2-dichloroethane were added to initiate polymerization. After that, while continuously supplying ethylene and keeping the total pressure constant,
Time polymerization was carried out. After the polymerization was completed, the resulting polymer was filtered and dried under reduced pressure at 60°C. The yield of polymer was 31.6 g. In this case, the polymerization activity is
9880g polymer/g solid catalyst/hr, 90600
g polymer/g transition metal/hr.

When polymerization was carried out under the same conditions without adding 1,2-dichloroethane, the polymerization activity was 1780 g.
Polymer/g solid catalyst/hr.

Comparative Example 1 The same procedure as Example 1 was carried out except that the polymerization temperature was 50°C. Polymerization activity is 8320g polymer/g solid catalyst/hr
It was hot. When polymerization was carried out under the same conditions without adding 1,2-dichloroethane, the polymerization activity was
It was 10,600g polymer/g solid catalyst/hr. It is clear that the addition of 1,2-dichloroethane does not significantly increase the polymerization activity at low temperatures.

Example 2 Example 1 except that 2.8 mg of the solid catalyst component prepared in Example 1 (1) was used and 0.05 mmol of chlorocyclohexane was used instead of 1,2-dichloroethane.
Polymerization was carried out under the same conditions as in (2) to obtain 30.5 g of polymer. In this case, the polymerization activity is 10900g polymer/g
The solid catalyst/hr was 100,000g polymer/g transition metal/hr.

Example 3 (1) Preparation of solid catalyst component Commercially available VCl ₃ 6g, TAC manufactured by Toho Titanium Co., Ltd.
10 g of -131 (TiCl ₃ .1/3 AlCl ₃ ) was ball milled for 20 hours to obtain a solid catalyst component. Analysis of this powder revealed that Ti15.7%, V12.2%, Al2.4%.
It contained 69.7% Cl (both weight %).

(2) Polymerization of ethylene Polymerization temperature was 220℃, solid catalyst component was Example 2
Using 3.2 mg of the catalyst prepared in (1), 1,2-dichloropropane was used instead of 1,2-dichloroethane.
Polymerization was carried out under the same conditions as in Example 1 (2) except that 0.10 mmol was used, and 39.7 g of polymer was obtained. The polymerization activity in this case is 12,400 g polymer/g solid catalyst/hr, and 44,400 g polymer/g transition metal/hr.
It was hr. When polymerization was carried out under the same conditions without adding 1,2-dichloropropane, the polymerization activity was 4230 g polymer/g solid catalyst/hr.

Example 4 (1) Preparation of solid catalyst component 100mg equipped with stirrer, dropping funnel and thermometer
After thoroughly purging the four-necked flask with nitrogen,
Butylmagnesium chloride 20mmol (10ml
n-butyl ether solution) was added,
20 mmol of SiCl ₄ was gradually added dropwise. After reacting at 30°C for 1 hour, the mixture was reacted at 60°C for 1 hour. After thoroughly washing the precipitated white solid with n-heptane, 40 ml of titanium tetrachloride was added and reacted at 130°C for 1 hour. After the reaction is completed, wash with n-heptane,
A solid catalyst component was obtained by drying under reduced pressure. This solid contained 2.6% Ti by weight.

(2) Polymerization of ethylene Polymerization temperature 180℃, 1,2-dichloroethane
Polymerization was carried out under the same conditions as in Example 1 (2), except that 0.025 mmol of the solid catalyst component was used and 7.4 mg of the catalyst prepared in Example 3 (1) was used to obtain 59.8 g of polymer. In this case, the polymerization activity is 8080g polymer/g solid catalyst.
hr and 311,000 g polymer/g transition metal/hr. When polymerization was carried out under the same conditions without adding 1,2-dichloroethane, the polymerization activity was
It was 1830g polymer/g solid catalyst/hr.

Example 5 Using 3.5 mg of the solid catalyst component obtained in Example 1 (1), polymerization was carried out under the same conditions as in Example 1 (2) except that 30 g of butene-1 was added and copolymerized. A polymer was obtained. The polymerization activity in this case is 9600g polymer/g solid catalyst/hr, and 88100g polymer/g
It was a transition metal/hr. This copolymer contained 15.2 ethyl groups per 1000 carbon atoms and had a density of 0.932 g/cm ² .

[Brief explanation of drawings]

FIG. 1 is a flowchart to help understand the process of preparing the catalyst of the present invention. This flowchart is a representative example of an embodiment of the present invention,
The present invention is not limited to this in any way.

Claims (1)

[Claims] 1. At a temperature of 130°C or higher, a) a solid catalyst component containing titanium and/or vanadium, b) an organic aluminum compound, and c) a chlorinated aliphatic hydrocarbon, a chlorinated alicyclic hydrocarbon A method for polymerizing olefin, which comprises polymerizing or copolymerizing olefin using a catalyst component consisting of at least one chlorinated organic compound.