JPS60262803A - Polymerization of olefin - Google Patents

Abstract

PURPOSE:To obtain a high-quality polymer in a high catalytic efficiency, by (co)polymerizing an olefin at a high temperature by using a catalyst comprising the three components of a transition metal-containing solid catalyst component, an organoaluminum compound and an organic chlorinated compound. CONSTITUTION:A catalyst is prepared from (A) a solid catalyst component containing at least one transition metal of Group IVa or Va of the periodic table (e.g., titanium or zirconium), (B) an organoaluminum compound (e.g., triethylaluminum or diethylaluminum chloride) and (C) an organic chlorinated compound. Examples of the organic chlorinated compounds which can be suitably used include chlorinated aliphatic hydrocarbons (e.g., 1,2-dichloroethane) and chlorinated alicyclic hydrocarbons (e.g., chlorocyclopropane). An olefin (e.g., ethylene) is (co)polymerized at a temperature >=130 deg.C by using the obtained catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a process for polymerizing or copolymerizing olefins at high temperatures of 180°C or higher using a novel Ziegler-type catalyst system.

Two methods have been implemented for producing olefin polymers at high temperatures in a polymer solution or molten state using Ziegler type catalysts. The first method is generally called a "solution method" and involves polymerizing or copolymerizing olefins using a solvent such as cyclohexane. This method uses a Ziegler geocatalyst to prepare olefins at 120-250℃, 5-
Polymerization is carried out in a polymer solution state under conditions of 50 Kf/c4.

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 under high temperature and high pressure.

It is known that these high-temperature solution polymerization methods or high-pressure ionic polymerization methods using Ziegler type catalysts have the advantage that the actuator is compact and there is a large degree of freedom in selecting the fumonomer. However, in polymerization at such high temperatures, most Ziegler-type catalysts normally exhibit high polymerization activity at the beginning of the polymerization reaction, but the polymerization activity rapidly decreases in a relatively short period of time, resulting in poor catalyst efficiency and There will be more residue. Therefore, various improvements have been made to the Ziegler-type solid catalyst for high temperatures (for example, Japanese Patent Laid-Open No. 51-1
44897, JP 54-52192, JP 56-18607, JP 56-99209
Publication No. 1987-87405, Japanese Patent Application Laid-Open No. 1987-87405
158007, JP-A-57-190009, and JP-A-58-208808), 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.

In addition, when using a metal halide such as a titanium halide compound as a solid catalyst, a device using active halogen,
It is desired that the polymerization activity per solid catalyst be sufficiently high from the viewpoint of corrosion prevention of equipment.

On the other hand, some patents disclose methods for treating Ziegler-type catalysts with halogen-containing organic compounds, in which transition metal-containing solid components are treated with halogen-containing organic compounds. Moreover, these methods are not directly aimed at improving polymerization activity. JP-A No. 50-8881, JP-A-Sho 5
8-45688, JP-A-56-98709, and JP-A-56-99206 disclose the addition of a halogen-containing compound to the polymerization system, but these methods also do not widen the molecular weight distribution of the polymer. The purpose of this method is to improve stereoregularity, but it is not necessarily satisfactory in terms of improving polymerization activity.

In order to improve the polymerization activity in high-temperature polymerization, the present inventors conducted extensive research and found that in the polymerization or copolymerization of sushi fins at temperatures of 180°C or higher, a) at least one member of the group 7a or Ma group of the periodic table; It has been discovered that an olefin polymer can be obtained with high catalytic efficiency by using a catalyst component consisting of eight components: b) an organoaluminum compound and C) a chlorinated organic compound containing a transition metal. reached.

The present invention will be explained in detail below.

Any material having fin polymerization activity can be used for the purposes of the present invention. As the transition metal, elements of group 17a of the periodic table or Va such as Ti, Zr1(f), and V are used.These may be used alone or in combination of multiple transition metals.As the transition metal, Ti It is preferable to use halides, alkoxides, and alkylated compounds as transition metal compounds, but halides are also preferably used.As solid catalyst components, transition metal compounds and other organic compounds, such as It may also be a complex with an electron donor or a complex compound with 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, containing amorphous magnesium halide as a carrier, and having a specific surface area of preferably 80 d/ or more. Examples of catalyst components include electron donors such as organic acid esters, silicic acid esters, alkoxysilicic acid esters, amines, ethers, and the like. This solid catalyst component contains, for example, 0.5 to 25% by weight of titanium, in particular about 1% 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 the pulverization treatment of magnesium halide or treatment with an electron-donating compound such as alcohol or ester.
It is prepared by reacting with .

Examples of the organoaluminum compounds used in the present invention include trialkylaluminums such as triethylaluminum, tri-n-propylaluminum, and tri-n-butylaluminum, dialkylaluminum monohalides such as diethylaluminium chloride, and alkyl aluminum compounds such as ethylaluminum sesquichloride. Alkylaluminum cybarides such as aluminum sesquichloride and ethylaluminum dichloride;
Examples include alkyl alkoxy aluminum such as diethyl ethoxy aluminum. 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.

Examples of the chlorinated organic compound that forms a catalyst system together with the above two components in the polymerization reaction include chlorinated aliphatic hydrocarbons having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, chlorinated alicyclic hydrocarbons, and chlorine. Aromatic hydrocarbons, chlorine-containing carboxylic acid derivatives, chlorinated ketones, chlorinated ethers, and the like can be used. Furthermore, as the organic chlorine compound, both - and two or more polychlorine groups can be used. Especially chlorinated aliphatic hydrocarbons having 1 to 8 carbon atoms or chlorinated IJ! Preference is given to using cyclic hydrocarbons.

Examples of chlorinated aliphatic hydrocarbons are methyl chloride,
Ethyl chloride, n-butyl chloride, 5eC-butyl chloride, t-butyl chloride, hexyl chloride, octyl chloride, 2-ethyl-
hexyl chloride, allyl chloride, 4-chloro-
Monochlorine-substituted products such as butene-1, methylene chloride,
1,1-dichloroethane, 1,2-dichloroethane, 1
゜8-Trichloropropane and other dichlorine substituted products, chloroform, methylchloroform, pentachloroethane, hexachloroethane, 111゜2-trichloroethylene, 1
．． Examples include polychlorine moieties such as 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, - or di-substituted aliphatic hydrocarbons having 1 to 8 carbon atoms are preferred, particularly 1.2
-dichloroethane and 1,2-dichloroprobanca are preferably used.

The polymerization conditions in the present invention are 180°C or higher, preferably 1
85°C to 850°C, more preferably 150°C to 270°C
The temperature and pressure are 5 to 100 Kp/d in the case of solution method,
Preferably 10 to 50 h/d, in the case of high-pressure ion method, the speed is 850 to 8500'I4/d, preferably 700 to
The polymerization is carried out at 1800 Kf/d, and either batch or continuous polymerization is possible.

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

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 chlorinated organic compound base can be varied within a wide range. The amount of chlorinated organic compound per mole of organoaluminum compound is 0.
The amount ranges from 0.005 to 100 mol, preferably from 0.01 to 25 mol. The ratio of the chlorinated organic compound to the transition metal is preferably between 0.1 mol and 100 mol, particularly preferably between 1 mol and 50 mol, per gram atom of the transition metal. The molar ratio of organoaluminum to transition metal is 1 to 200, preferably 2 to 100.

The catalyst system according to the invention has a significantly high activity, typically containing 10-6 to 10 transition metals per 14 volumes of solvent or polymerization vessel.
A concentration of milligram atoms is used, preferably from 10@-5 to 10@milligram atoms. The concentration of the organoaluminum compound and the chlorinated organic compound is also preferably 10 mmol or less per 14 mmol.

The olefin used in the present invention has 2 to 20 carbon atoms,
Preferably olefins with 2 to 10 terminal unsaturations, such as ethylene, propylene, phthene-1,4-
Examples include methylpentene-1, hexene-1, octene-1, 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 per solid catalyst is high, so that the catalyst in the resulting polymer is The amount 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.
The present invention is not limited in any way by the following examples unless the gist thereof is exceeded.

Example 1 (1) Preparation of solid catalyst component, commercially available anhydrous magnesium chloride 10v1 manufactured by Toho Titanium Co., Ltd. TAC181 (TiC 1/3 AeCe3) 10
2 was ball milled for 20 hours to obtain a solid catalyst component.

Analysis of this powder revealed Ti 1o, 9%, A/1.
8%, C674.6%, and Mg 12.0% (all weight %).

(2) Polymerization of ethylene Place the autoclave with a stirrer under nitrogen. After sufficient replacement with 500 gt of kerosene.

Triethylaluminum Q, 5 mmol, was added. After raising the temperature to 200℃, the total pressure of ethylene was 20℃.
It was added until it reached Kf/ci. Solid catalyst component 8.2 cape prepared in +1+ above and 1.2-dichloroethane 0
．． Polymerization was started by adding 0.5 mmol. After that, while keeping the total pressure constant while continuously supplying ethylene,
Polymerization was carried out at 00°C for 1 hour. After the polymerization was completed, the resulting polymer was filtered and dried under reduced pressure at 60°C. The yield of polymer was 81.6F. In this case, the polymerization activity is 9,88
0f polymer/f solid catalyst/hr, 90,600
ftlK combination/f transition metal/hr.

When polymerization was carried out under the same conditions without adding 1.2-dichloroethane, the polymerization activity was 1,780r polymer/1.
It was a solid catalyst/hr.

Comparative example 1 The same procedure as in Example 1 was carried out except that the polymerization temperature was 50°C.

The polymerization activity was 8.8209 polymer/V solid catalyst/hr. When polymerization was carried out under the same conditions without adding 1,2-dichloroethane, the polymerization activity was 10,600? Polymer/1 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 Using 28 cm of the solid catalyst component prepared in Example 1 (1),
Example 1 (2
) Polymerization was carried out under the same conditions as 80.6 f polymer was obtained. In this case, the polymerization activity is 10,900P polymer/1
solid catalyst-hr, 100.00 (1 polymer/2
It was a transition metal/hr.

Example 8 +11 Preparation of solid catalyst component Commercially available VC4s y, TAC-1 manufactured by Toho Titanium Co., Ltd.
81 (Tickg ·'/B AgC#s) 102 was ball milled for 20 hours to obtain a solid catalyst component. Tokoguchi Ti 15.7%, V 12.2% analyzed this powder
, 12.4% of A, and 69.7% of Cd (all weight %).

(2) Polymerization of ethylene The polymerization temperature was 220°C, and the catalyst 8.211P prepared in Example 2 (1) was used as the solid catalyst component.
lI2-dichloropropane 0.2-dichloropropane instead of 2-dichloroethane Polymerization was carried out under the same conditions as in Example 1 (2) except that 1 Ommol was used, and a polymer of 89.71 was obtained.

The polymerization activity in this case was 12,400 P polymer/2 solid catalyst-hr and 44.40 Or polymer/f4 transfer metal/hr. l.

When polymerization was carried out under the same conditions without adding 2-dichloropropane, the polymerization activity was 4.28Of polymer/? Solid catalyst-hr.

Example 4 (1) Preparation of solid catalyst component After purging a 100V four-loop flask equipped with a stirrer, dropping funnel, and thermometer with nitrogen,
Butylmagnesium chloride 2Qmmol (l 0
m1n-butyl ether solution) was added, and 5i (Jj42
Q rrrnol 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-hebutane,
40 ml of titanium tetrachloride was added and reacted at 1.80°C for 1 hour. After the reaction was completed, it was washed with n-hebutane and dried under reduced pressure to obtain a solid catalyst component. Each solid moss contained 2.6% by weight of Ti.

(2) Polymerization of ethylene Polymerization temperature: 180°C, 1,2-dichloroethane: 0.025 mmol Solid catalyst component Example 8
Catalyst prepared in (1)? Polymerization was carried out under the same conditions as in Example 1 (2) except that 4 q was used, and <59. A polymer of sr was obtained. In this case, the polymerization activity is 8,0809 polymers/
is a solid catalyst-hr and is 811,000P polymer/f
It was a transition metal/hr. When polymerization was carried out under the same conditions without adding 1.2-dichloroethane, the polymerization activity was 1.8802 polymer/2 solid catalyst/hr.

Example 5 Example 1 except that 3.5 caps of the solid catalyst component obtained in Example 1 (1) was used and butene-1802 was added and copolymerized.
Polymerization was carried out under the same conditions as in (2) to obtain polymers 8B and 6f. The polymerization activity in this case was 9,600 P polymer/hr of solid catalyst and 88.10 Or polymer/f transition metal/hr. This copolymer contains 100 carbon atoms.
There were 15.2 ethyl groups per 0, and the density was 0.9821/-.

Claims (1)

[Scope of Claims] At a temperature of 180° C. or higher, a) a solid catalyst component containing at least one transition metal of group IV or VA of the periodic table, b) an organoaluminum compound, and C) a chlorinated organic compound. A method for polymerizing olefins, which comprises polymerizing or copolymerizing olefins using a catalyst component consisting of eight components.