JPS60135408A - Production of polyolefin - Google Patents

Abstract

PURPOSE:To produce a polyolefin in a high catalyst efficiency, by polymerizing an olefin by using a catalyst comprising a specified inorganic oxide support, a specified organic transition metal compound a specified water-modified organoaluminum compound. CONSTITUTION:An olefin (e.g., propylene) is (co)polymerized in the presence of a solid product obtained by contacting a fine particulate porous inorganic oxide (e.g., alumina) free of adsorbed water and having surface reactive hydroxyl groups with an organic transition metal compound of formula I [wherein M is a Group IVA-VIA transition metal, R<1> is a (substituted) hydrocarbon group, X is a halogen, p has a value of from 2 to the highest valence of metal M, and q has a value of from 0 to the valance of metal M minus 2], e.g., tetrabenzylzirconium, and a water-modified organoaluminum compound prepared by water-modifying a trialkylaluminum compound of formula II (wherein R<2> is a 1-10C alkyl), e.g., trimethylaluminum. It is possible to obtain a polyolefin in high yields and markedly improved catalyst efficiency.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing an olefin polymer. More specifically, the present invention relates to a method for producing olefin polymers and copolymers using a novel catalyst obtained by supporting an organic transition metal compound and an aqueous organoaluminum compound on a finely porous inorganic oxide.

A transition metal composition in which an organometallic compound of a transition metal of Groups 1VA-VIA of the Periodic Table of the Elements is chemically bonded to a substantially chemically inert matrix material as an initiator for an olefinically unsaturated monomer. The method using
1-25272°26419.

However, although these catalysts give high molecular weight polymers, their activity is insufficient, and the inorganic carrier substances and transition metals remaining in the polymers adversely affect the quality and physical properties of the polymers.

Therefore, in order to improve these problems, it is important to greatly improve the catalytic activity, and several proposals have been made in this regard.

Japanese Patent Publication No. 47-17722. US Pat. No. 5,635,955 describes a method in which tetraneopentyl titanium diffused onto a silica support is activated by the addition of an organoaluminum compound and used as a catalyst for olefin polymerization. Preferred organoaluminum compounds in this case are dialkylaluminum rhamnolides, such as diethylaluminum chloride.

JP-A-56-57805 describes an organometallic compound shown as 84M in a substantially inert matrix material such as alumina and 1ZrXp. A metal composition in which an organic transition metal compound represented by HfXp is bonded (M is a metal of group ⅠB of the periodic law, B+ and 几2 are hydrocarbon groups or substituted hydrocarbon groups, and X is (if present, it is a singly charged anionic or monodentate ligand, and p is 0.1 or 2) is used as an initiator to polymerize olefinically unsaturated monomers. It describes how to do this.

Preferred organometallic compounds in this case include organoaluminum compounds such as tritylaluminum and tributylaluminum.

It is also described that effects can be seen only in a specific order of addition depending on the type of organoaluminum compound used.

Japanese Patent Publication No. 55-15415 describes a method in which a reaction product of partially hydrated alumina and a tetra(hydrocarbyl) transition metal compound is hydrogenated with hydrogen and used as a polymerization initiator for 1-olefins.

Although the above catalyst improvements have resulted in a considerable improvement in activity, this is still not sufficient.

As a result of intensive studies aimed at achieving high catalytic activity and improved productivity, the present inventors have discovered that a fine-grained, porous inorganic oxide with reactive surface hydroxyl groups that does not substantially absorb adsorbed water during olefin polymerization has been developed. By using the solid product obtained by catalytically reacting an organic transition metal compound and an aqueous organoaluminium compound as an initiator, it is possible to achieve a much higher Active.

Furthermore, it was found that the activity was higher than that of the addition of organoaluminum compounds described in JP-A No. 56-57805, and that the effect was not affected by the order of addition, leading to the present invention. The invention relates to an olefin polymerization catalyst that is substantially free of adsorbed water and is comprised of a particulate, porous inorganic oxide having reactive surface hydroxyl groups, an organic transition metal compound, and an aqueous organoaluminium compound.

The present invention will be explained in detail below.

++1 Inorganic oxide carrier Alumina is particularly preferred as the inorganic oxide carrier, with a particle size of 5 to 1000μ, a specific surface area of 50 to 1ooo, and d/1.
One pore volume is preferably 0.2 to 6 d/g, particularly preferably an average particle size of 20 to 200β, 100 to 400 d/g.
It has a specific surface area of I and a pore volume of 0.5 to 2.5 ml/9.

Before use, the inorganic oxide support is treated with hot water for 2 to 50 hours at a temperature in the range of 40 to 100°C, then heated to 100°C.
Temperatures in the range from ~1000°C, particularly preferably from 300 to 6
The adsorbed water is removed by heating at a temperature of 00°C.

(2) Organic transition metal compound The organic transition metal compound used in the present invention has the general formula R"M
Xq (M is a transition metal of groups ■A to ■A of the periodic table,
is a hydrocarbon group or a substituted hydrogen group, X is a halogen, p and q are integers, p is 2 to the highest valence of the metal M, and q is 0
Specific examples of organic transition metal compounds represented by (value 2 less than the valence of metal M) are tetrabenzylzirconium, f-trabensyltitanium, tetrabenzylhafnium, tetraneopentylzirconium, tetraneopentyltitanium, and tetraneo. fil zirconium,
Examples include tetraneophyl titanium, tetraneophyl hafnium, and tetraallyl zirconium.

(3) Water-erodible organoaluminum compound The water-erodible organoaluminum compound used in the present invention is:
It can be obtained by reacting water with a trialkylaluminum represented by the general formula A4(2) (in the formula A4 represents an alkyl group of 1 to 10), preferably trimethylaluminum or triethylaluminum.

The reaction method is not particularly limited, and examples include methods of dropping water onto the trialkylaluminum as a liquid or dissolved in an F6 medium, or contacting the water in the form of a mist or steam, but particularly preferred are , a method of manufacturing by carefully reacting with a compound containing water of crystallization, such as copper sulfate pressure hydrate.

There are no particular restrictions on the reaction conditions for modifying the organoaluminum compound with water, but preferably the molar ratio of water to the organoaluminum compound is 0.1:1 to 2.5.
:1 is particularly preferably 0.3:1 to 2:1, and the reaction temperature is preferably -80 to 100°C, particularly preferably -20 to 50°C, for 5 minutes to 100 hours, particularly preferably 1 Process for ~50 hours.

The structure of the water-erodible organoaluminum compound obtained by such a reaction is very complex, and probably has the general formula luminoxane <flt is a hydrocarbon group, n is 1 to 50
It is thought to have the structure shown by (an integer up to).

In the present invention, the solvent used in the catalytic reaction of the inorganic oxide support, the organic transition metal compound, and the water-erodible organoaluminum compound must be inert and must have been dehydrated and deoxidized. Examples of inert solvents include aromatic hydrocarbons such as benzene, toluene, and xylene, saturated aliphatic hydrocarbons such as n-pentane, n-hexane, and n-hebutane, and alicyclic hydrocarbons such as cyclohexane and methylcyclohexine. Hydrocarbons are used.

The supported amount of all transition groups of the 1st vA -vl A group in the solid catalyst of the present invention is preferably 0.05 to 1.0 mmol/g, particularly preferably 0.1 to 0.5 mmol/g.

The reaction of the water-erodible organoaluminum compound and organic transition metal compound with the inorganic oxide carrier is carried out in an appropriate order or by adding them simultaneously.

The number of grams of aluminum and transition metals of Groups ■A to ■λ in the solid catalyst of the present invention is 0.05:1 to i00.
:1 is preferred, particularly preferably 01:1 to 25:1, and since many of the organic transition metal compounds used in the present invention are thermally unstable, when using such compounds, The reaction temperature must be kept low enough to prevent decomposition.

The olefins used in the present invention include α-olefins such as ethylene, propylene, and butene-1,
Not only these homopolymerizations but also copolymerizations are possible.

As the polymerization or copolymerization method, various polymerization methods can be carried out, such as solution polymerization or monopolymerization in the presence of an inert hydrocarbon or liquefied monomer, and gas phase polymerization in the absence of a solvent. .

Polymerization temperature is room temperature to 300℃, pressure is atmospheric pressure to 1000℃
It can be carried out in a range of atmospheric pressures. Furthermore, by allowing hydrogen to exist in the polymerization system, the molecular weight of the produced polymer can be easily controlled.

Next, the present invention will be explained in detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples in any way. In addition, in Examples and Comparative Examples, isotactic index (II) is the amount of solid remaining after extraction with boiling n-hebutane for 16 hours using a Soxhlet extractor.
The ether insoluble portion (IE) is the amount of solid remaining after extraction with boiling diethyl ether for 8 hours using a Soxhlet extractor, expressed in %.

Example 1 CuS04・sH,o 57.5g (0.15mol)
was suspended in 100 ml of toluene, and a mixed solution of 50 g (0.52 mol) of trimethylaluminum (0.52 mol) and 150 ml of toluene was constantly added dropwise at 20° C. while stirring. After the dropwise addition was completed, the reaction was further continued at 20° C. for 48 hours. Next, the reaction solution was filtered to remove the solid sulfuric acid, and then washed with toluene under vacuum. By removing 1 and unreacted trimethylaluminum, 17& methylaluminoxane was obtained.

Preparation of catalyst High-purity r-alumina (ACP-1 manufactured by Catalyst Kasei Co., Ltd. Average particle size: Approx. average particle size: Relative area: approx. 500 g/g; Pore volume: approx. 0.7
d/g) was treated with hot water for 60 hours and then washed with acetone.

This was heated at 450° C. for 6 hours in a dry nitrogen atmosphere to remove adsorbed water.

This alumina 0.75.9 was suspended in toluene 10m/methylaluminoxane 551119 (0.6 mmol aluminum unit) dissolved in toluene.
added. After stirring this mixture for 50 minutes, 0.16M of tetrabenzylzirconium dissolved in toluene was added.
1 d of the solution was added and stirring was continued for an additional 30 minutes.

The solid catalyst 14i prepared in this way was 0.2 mmol.
/El of zirconium and 0.8 mmol/g of aluminum.

A 21 stainless steel autoclave equipped with a stirrer was vacuum degassed and replaced with nitrogen, and then the above solid catalyst slurry and 500 g of liquid propylene were charged.

While stirring, the temperature was raised to 70°C, and the mixture was stirred for 1 hour. After completion of Togane, unreacted propylene was removed to stop the reaction, and the polymer was taken out. White, granular polypropylene 255
! 1 is numbered 1, and the polymerization activity is 1470 g pp/im.
It was mol・7rr-hr. Moreover, II of the polymer was 658%, 11%, or 708%.

Examples 2 to 6 Catalysts were prepared and propylene was combined in the same manner as in Example 1, except that methylaluminoxane was added in 1 and the order of addition was changed. The results are shown in Figure 1.

Comparative Example 1 A catalyst was prepared and a propylene chassis was prepared in the same manner as in Example 1 except that methylaluminoxane was not added. The results are shown in Table 1.

Comparative Example 2 A catalyst was prepared and propylene was polymerized in the same manner as in Example 1, except that triethylaluminum was used instead of methylaluminoxane. The results are shown in Table 1.

Comparative Example 5 A catalyst was prepared and propylene was polymerized in the same manner as in Comparative Example 2 except that the order of addition of triethylaluminum and tetrabenzilyl heptinium was changed. The results are shown in Table 1.

/ / / \ /' / Example 7 Preparation of catalyst 0.58 g of alumina, which had been heat-treated to remove adsorbed water in the same manner as in Example 1, was suspended in toluene, and dissolved in toluene. methylaluminoxane 18
(2) (0.5 mmol aluminum unit) was added. After stirring the mixture for 30 minutes, a 0.1 (5M solution) of tetrabenzylzirconium dissolved in toluene was added.
5 d was added, and stirring was further performed for 50 minutes to obtain a solid catalyst slurry.

A 21 stainless steel autoclave equipped with a stirrer was vacuum degassed and replaced with nitrogen, and then 800 d of n-hexane and the above solid catalyst slurry were charged. While stirring, the temperature was raised to 70°C and the ethylene partial pressure was reduced to 4. okg/crI was maintained and polymerization was carried out for 1 hour. After the polymerization was completed, unreacted ethylene was removed to terminate the reaction. The polymer was separated and dried to obtain white, granular polyethylene 175Ii. Polymerization activity is 2 i 901 P) A/mmol Z
It was r-hr.

Comparative Example 4 A catalyst was prepared and ethylene was polymerized in the same manner as in Example 6, except that methylaluminoxane was not added, and 78 g of white, granular polyethylene was obtained. Polymerization activity is 980
11 Ph) r/m mol Zr-hr.

Patent Applicant Toyo Koutatsu Kogyo Co., Ltd. Procedural Amendment 1 May 1978 88 Patent S'l Office Commissioner Kazuo Wakasugi Indication of Case 1 1982 Patent Application No. 242061 Title of Invention Process for Manufacturing Polyolefin 4 Supplement 1F Order Number of inventions increased from spontaneous 5th supplement iEK dated 0 6. Detailed description of the invention in the specification subject to the amendment 7. Contents of the amendment (1) [Trityl aluminum J” described in specification Vif page 4, lines 3 to 4 er triethylaluminum”.

(2) r 1470 gpp described on page 13, lines 5-6
/mmol・Zr-hrJ'i7 [14706PP/
Correct it as mmolZr・hrJ.

(3) From the left of the same 15 negative table, r (g
pp/m mo1Zrhrmonthtr (gPP/m m
Correct it as o'l Zr-hr month.

Claims (1)

[Claims] 1) The general formula A MXq (
M is a transition metal of Groups 1 VA to VIA of the periodic table, fLI
is a hydrocarbon group or a substituted hydrocarbon group, X is a halogen, p
and q is an integer, p is the value of 2 to the highest valence of metal M, and q
is a value of 0 to 2 less than the valence of the metal M), and a trialkylaluminium compound represented by the general formula AlR1 (where 1 is an alkyl group having 1 to 10 carbon atoms) are modified with water. 1. A method for producing an olefin polymer, which comprises polymerizing or copolymerizing an olefin in the presence of a solid product obtained by catalytically reacting a water-modified organic aluminum compound obtained by the above-mentioned method.