JPS633008A - Production of polyolefin - Google Patents

Abstract

PURPOSE:To obtain a high-purity and high-molecular weight polyolefin at normal temperature by polymerization of an olefin in the presence of a catalyst consisting mainly of an oxygen-contg. titanium compound and reaction product from water and organoaluminum compound. CONSTITUTION:The objective polyolefin can be obtained by polymerization of an olefin (pref. 2-10C alpha-olefin) in the presence of a catalyst of novel composition consisting mainly of (A) an oxygen-contg. titanium compound (e.g. tetramethoxytitanium, diisopropoxytitanium dichloride) and (B) an aluminoxane, a reaction product from water and an organoaluminum compound (e.g. trimethylaluminum, triisobutylaluminum). USE:The polyolefin thus obtained is useful as a raw material for blend bases, adhesives, electrical insulating materials, and various molded articles.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for producing polyolefin, and more particularly, to a method for producing polyolefin with high purity and high molecular weight at room temperature by using a catalyst with a novel composition. .

[Prior Art and Problems to be Solved by the Invention] As a method for producing polyolefins by polymerization reaction of olefins, for example, JP-A-58-19309 discloses (cyclopentagenyl)zirconium dichloride, aluminoxane, That is, a method is disclosed in which an olefin is polymerized in the presence of a catalyst in combination with a compound having an An-0 bond in the molecule.

When this method is applied, for example, to the polymerization of propylene, it has the advantage that polypropylene having an atactic structure can be obtained as a product of extremely high purity.

However, in such a method, if the polymerization reaction is carried out at room temperature, the resulting atactic polypropylene will have a low molecular weight, so in order to obtain a high molecular weight product, it is necessary to polymerize at an extremely low temperature.
There is a problem in that it leads to an increase in manufacturing costs.

An object of the present invention is to solve these conventional problems and provide a method for producing a polyolefin with high purity and high molecular weight at room temperature.

[Means and effects for solving the problem] As a result of intensive research to achieve the above object, the inventor discovered that the reaction between an oxygen-containing titanium compound, water and an organoaluminium compound was produced as an olefin polymerization catalyst. The present invention was completed based on the discovery that a novel effect can be obtained by using a catalyst with a novel composition consisting of a combination of these substances.

That is, the method for producing a polyolefin of the present invention is characterized by polymerizing an olefin in the presence of a catalyst whose main components are an oxygen-containing titanium compound and a reaction product of water and an organoaluminum compound.

Olefins to which the method of the present invention can be applied are not particularly limited, but include, for example, α-olefins having 2 to 10 carbon atoms. Furthermore, these olefins may contain dienes such as butadiene, isoprene, chloroprene, and ethylidene norbornene as comonomers.

The polymerization catalyst used in the method of the present invention contains an oxygen-containing titanium compound as a first essential component and a reaction product of water and an organoaluminum compound as a second essential component.

First, the oxygen-containing titanium compound that is the first essential component is not particularly limited, and for example, the oxygen-containing titanium compound has the formula: T
i (OR1)nx4-n[R1 represents an alkyl group having 1 to 20 carbon atoms, X represents a halogen atom, n is 0
<Represents an integer satisfying n≦4]; Formula: Ti (OR2). (OR3) 4-ffl [R2 and R3 are different from each other and each has the same meaning as R1 above, and m represents an integer satisfying O < m <4]; Formula: Ti(OR') statement (OCOR
5) 4-cross [R4 and R5 may be the same or different, each represents the same meaning as R1 above, and the sentence represents an integer satisfying O<1<4]: Formula A titanium polymer represented by the formula % [ represents the same meaning as R1 above, and k represents an integer satisfying 2≦≦20]; and T i (OR7) 2 (acac) 2 [R7
has the same meaning as R1 above, and acac represents an acetylacetonato group], T i 0 (acac)2
, [T i (acac)3] 2-T i C16, and other acetylacetonato compounds are suitable. Specifically, tetramethoxytitanium, tetraethoxytitanium, tetranormalpropoxytitanium, tetraisopropoxytitanium, tetrabutoxytitanium, tetra-2-ethylhexoxytitanium, tetrastearoxytitanium, triethoxytitanium monochloride, diisopropoxy These include titanium dichloride, diisoduloboxybisacetylacetonatotitanium, di-n-butylbisacetylacetonatotitanium, etc.

On the other hand, the second essential component is a reaction product of water and an organoaluminum compound, ie, aluminoxane. Examples of organoaluminum compounds include, but are not limited to, those represented by the R3A statement (R represents an argyl group having 1 to 8 carbon atoms), particularly trimethylaluminum, triethylaluminum, and triisobutyl. Aluminum and the like are preferred. This second essential component is, in addition to the above-mentioned reaction product between water and organoaluminium, a reaction product between a water-containing compound such as copper sulfate Miki salt and an organoaluminum, or a reaction product between these reaction products and an organic aluminum. Mixtures with aluminum compounds can also be used.

The polymerization catalyst used in the present invention is a combination of the above-described first and second essential components, and these components are added to the reaction system in a predetermined amount. What is the concentration of each component?

81 essential components are 0.0001 to 0.5 mmol/also,
Preferably, the amount of O,OO is set to 1 to 0.1 mmol/cross, and the second essential component is set to 1 to 100,000 mmol/cross, preferably ioo to 10,000 mmol/cross.

In the present invention, the olefin polymerization reaction is carried out as follows. That is, first, as the polymerization solvent, aliphatic hydrocarbons, aromatic hydrocarbons, alicyclic hydrocarbons, etc. are suitable, and specific examples include hexane, heptane, toluene, xylene, benzene, etc. . After adding the catalyst component of the present invention described above to a predetermined concentration into the polymerization solvent, heolefin gas is introduced into the solvent to carry out a polymerization reaction. In this case, 1
A homopolymer can be obtained by introducing different types of olefin gases, and a desired copolymer can be obtained by introducing two or more types of olefin gases at predetermined partial pressures. The pressure of the olefin gas at this time is normal pressure ~ 50 k
g/cm2G, preferably normal pressure to 20kg/Cll
2G, reaction temperature is 0-200℃, preferably 20-15
Set each to 0℃. Further, at this time, for example, hydrogen gas or the like may be introduced into the reaction system as a molecular weight regulator.

[Example] Example 1 (1) Preparation of aluminum catalyst component (second essential component) 47.4% of trimethylaluminum in 200% of toluene
m7 (492 mmol) and sulfur m copper 5 water tjz (Ca
35.5 g (142 mmol) of SO3.5H20) was added and reacted for 24 minutes at 20° C. under an argon stream. Next, copper sulfate was removed from the resulting reaction solution, and toluene was distilled off to obtain 12.4 g of methylaluminoxane in the form of white crystals.

(2) Polymerization of olefin (manufacture of polypropylene) Contents [In a 1M autoclave, 400% of toluene and the above (
6 mmol of methylaluminoxane obtained in step 1) in terms of aluminum equivalent, and 0.01 tetraethoxytitanium.
1 mmol was added sequentially and the temperature was raised to 50°C. 6 Then, propylene was continuously introduced into the autoclave, and the propylene partial pressure was maintained at 8 kg/cm2G and polymerized at 50°C for 4 hours. 1 After completion of the reaction. The solvent was distilled off, and the resulting polymer was deashed and washed with a siic acid-methanol mixture and then with methanol, and dried under reduced pressure to obtain 2.3 g of a polymer.

The polymer obtained here is a polypropylene with a 100% atactic structure and a weight average molecular weight (Rw) of 2.
, 152,000, number average molecular weight (Fan) is 51°,
000, Mw/Mn was 41.9.

Example 2 1.1 g of a polymer was obtained in the same manner as in Example 1, except that tetraisopropoxytitanium was used as the titanium catalyst component (first essential component). This polymer is a 100% atactic polypropylene with a Mw of 1.17
2,000, Mn is 10.000, M w / M n
was 114.3.

Example 3 1.8 g of a polymer was obtained in the same manner as in Example 1 except that diisopropoxytitanium dichloride was used as the titanium catalyst component. This polymer is 100% active polypropylene and has a Mw of 1,310. OOO
, Mn is 10.000, M w / M n is 137.
It was 7.

Example 4 0.5 g of a polymer was obtained in the same manner as in Example 1, except that titanium monoisopropoxy trisstearate was used as the titanium catalyst component.

This polymer is 100% atactic polypropylene with a Mw of 806,000. Mn is 6, 200
, Mw/Mn was 128.9.

Example 5 0.8 g of a polymer was obtained in the same manner as in Example 1, except that bis[titanium trisacetylacetonate cotitanium hexachloride was used as the titanium catalyst component. This polymer is a 100% atactic polypropylene with an Mw of 868.000 and an Mn of 7.000. Mw
/Mn was 127.1.

Comparative Example The same procedure as in Example 1 was carried out except that dicyclopetagenyl titanium dichloride containing no oxygen atoms was used as the titanium catalyst component. As a result, 1.1 g of polypropylene having a 100% atactic structure was obtained. This one is M
w is 43.000, Rn is 4 + OOO, :d w
/Mn was 11.3, which was one molecular weight low. Note that in order to obtain a sufficiently high molecular weight product in this system, it was necessary to set one reaction at a temperature of -50 to 0°C.

Example 6 400 J of toluene was added to an autoclave with an internal volume of 1 liter.
6 mmol of aluminum equivalent of methylaluminoxane obtained in (1) of Example 1 and 0.01 mmol of tetraethoxytitanium were sequentially added, and the temperature was raised to 50°C.

Next, propylene and ethylene were mixed in an autoclave at a propylene partial pressure of 7 kg/cab2G and an ethylene partial pressure of 2.
kg/ca+2G, and copolymerization reaction was carried out at 50°C for 2 hours. After the completion of the reaction, the solvent was distilled off and the product was converted into a dilute hydrochloric acid-methanol mixture.

Then, 7.41 g of a copolymer was obtained by deashing and washing with methanol and drying under reduced pressure.

The copolymer obtained here has a propylene content of 61 mol%
It was an ethylene-propylene copolymer with a weight average molecular weight of 1,714,000 and a number average molecular weight of 56,700. Also, the density of this copolymer is 0.8795g/,
It was J.

[Effects of the Invention As is clear from the above explanation, according to the method of the present invention,
Because high-purity, high-molecular-weight polyolefins can be produced at room temperature, their industrial value is extremely high in the field of producing polyolefins, which are useful as blend base materials, adhesives, electrical insulation materials, and materials for various molded products. It's large.

Procedural amendment May 25, 1988 Commissioner of the Patent Office Black 1) Yu Akira 1, Indication of the case 1988 Patent Application No. 146039 2, Name of the invention Process for producing polyolefin 3, Person making the amendment Related Patent applicant name: Idemitsu Kosan Co., Ltd. 4, agent 5, date of amendment order Voluntary action (1) "Producing polyolefin at room temperature..." stated on page 1, lines 13-14 of the specification. Correct to "...manufacture polyolefin...".

(2) "At room temperature" stated in page 2, line 14 of the specification is corrected to "over a wide temperature range, preferably at room temperature or at a temperature slightly higher than room temperature."

(3) "At room temperature" as stated in page 12, line 6 of the specification section, should be corrected to "over a wide temperature range, preferably at room temperature or at a temperature slightly higher than room temperature, without consuming a large amount of energy." .

Claims (1)

[Claims] 1. A method for producing a polyolefin, which comprises polymerizing an olefin in the presence of an oxygen-containing titanium compound and a catalyst whose main components are a reaction product of water and an organoaluminum compound.