JPH03263410A - Production of syndiotactic polyalpha-olefin - Google Patents

Abstract

PURPOSE:To obtain the subject resin, excellent in bulkiness and useful as plastics, etc., by supporting a catalyst composed of a specific transition metal compound and an aluminoxane on a hollow inorganic oxide in polymerizing an alpha-olefin using the aforementioned catalyst. CONSTITUTION:An alpha-olefin is polymerized using a catalyst composed of a transition metal compound having an asymmetric ligand [e.g. a compound expressed by formula I (A and B are mutually different aromatic hydrocarbon; R is 1-20C hydrocarbon residue or silicon-containing compound; Y is halogen, 1-20C hydrocarbon residue or silicon-containing compound; M is titanium, zirconium or hafnium)] and an aluminoxane [e.g. a compound expressed by formula II or III (R is 1-3C hydrocarbon residue)]. In the process, the aforementioned catalyst is supported on a hollow inorganic oxide (e.g. SiO2, having about 1mum to 0.1mm diameter; voids are preferably about 5-80%) to afford the objective polymer.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing syndiokkudic polyα-olefins. Specifically, the present invention relates to a method for producing a syndiotactic poly-α-olefin with a high yield per catalyst, a relatively large particle size, and a high bulk specific gravity.

[Prior art] The existence of syndiotactic polypropylene has been known for a long time, but the conventional method of low-temperature polymerization using a catalyst consisting of a vanadium compound, ether, and organic alumina 1 has poor syndiotactic tactility and It was hard to say that it represented the geeky characteristics of polypropylene. On the other hand, J. A. IEWIEN
It has been shown that polypropylene with good toughness, such as a syndiotactic venta r fraction exceeding 0.7, can be obtained using a catalyst consisting of a transition metal compound having an asymmetrical ligand and aluminoxane. First discovered (J, Hachim, Chem, Soc, 1988
．． 110.6255-625(i).

Furthermore, the present inventors have found that syndiotactic poly-α-olefins can be similarly obtained by polymerizing other α-olefins in a similar manner.

[Problem to be solved by the invention]

The method by J, A, 1EWlliN et al. is an excellent method in which yllil per transition metal is good and the toughness of the obtained polymer is high.
1. The problem is that the particle size and bulk specific gravity of the polymer used in 1.1 is small, the properties of the polymerization slurry are poor, and the heat of polymerization cannot be removed, resulting in poor productivity.1. Ta.

[Means to solve the problem] The inventors of the tree solved the C1l ten problem and talked about it.
Polyα, olefin with a relatively large high-to-high ratio and high syndiotough day city with a relatively high soaking degree, yield of 9
The present invention was completed after extensive investigation into the NoJ method for manufacturing. SUMMARY OF THE INVENTION The present invention provides a method for polymerizing α7 olesoin using a catalyst consisting of a transition metal compound having a Jl-symmetrical ligand and alumino-1-line. This is a method for producing a syndiotough (poly-alpha olefin) characterized by using a transition metal catalyst having 1/Y- and aluminum supported on a hollow inorganic oxide.

The transition metal compound used in the present invention 6JOi1ζ is:
]-0 Document (2,: The compounds described can be exemplified, but ・Noshiro: Δ, I\ (in the formula, r+ is different from yg)) h group hydrocarbon,
II connects A and 11 to carbon number 1 and 20 carbide ice accumulations! , (or a compound containing silicon, where X is a halogen) or a hydrocarbon residue having 1 to 20 carbon atoms. ■ is a metal raw material selected from titanium, Jill R, Tsu Jl, Hafgo J, and the like.

) can be preferably used. A, 1) -ζ can be exemplified by a monocyclic or polycyclic aromatic compound having 5 to 30 carbon atoms, specifically, Schiff 1-I beta-dihydrogen or some or all of its hydrogens have carbon atoms. A7 of l~lO
1-bar substitution (it is also possible to have a structure in which the end of the AJ retort ring is bonded to the 1-bentadiyl ring), 4-in, truolene, etc. Examples include polycyclic aromatic compounds such as, or those in which part or all of the hydrogen atoms are 7ItN with carbon atoms of 1 to 10 atoms. R is preferably a sialylmethylene group or a dialkylsilylene group, such as l? '
, Cg, R'zSi:: (In the formula, P is hydrogen or an alkyl residue having 1 to 20 carbon atoms, and may be the same or different.) Compounds represented by the following can be preferably used. , furthermore -CI? Represented by 'CR'-'-tylenno, I can also be used as an example (in the formula, P' is the same as in 11);, )X and 1
, 7゛ζ is fluorine, chlorine, bromine, iodine, or methyl,
J alkyl group such as nitrogen, propyl, butyl, etc.
Examples include aromatic compounds such as l-pentagenyl group, but chlorine and methyl are particularly preferred.

Aluminokirin Toji C can be exemplified by compounds represented by RII (in the formula, I+ is a hydrocarbon residue having 1 to 3 carbon atoms. 5 or more, preferably lf1 or more is used. The ratio of 1t alumino to the above transition metal catalyst is 10 to 10 tl.
0,000 mol times, usually 50 to 5,000 mol times.

In the present invention, (i1! Essentially, the transition metal compound and aluminokirin/ described in Section 7I are used in a hollow inorganic oxide with 1 [1 and ζ. Here, the hollow inorganic oxide is S i (12, Δ120, Cab,, N
ano, K, 0, 11 g f, l, Mn01'
It can be used as long as it has a cavity inside of various oxides such as ZrO, ZrO, etc., and the typical diameter is llt.
The porosity is about m-11, Imm and lW! i”・8 [)
χ degree, good E [: 1. ,, < is preferably 20 to 60'A from the viewpoint of supporting a large amount of the transition metal compound and i' Lumitsuki phosphorus and the strength of the supported catalyst. There are no particular restrictions on the method for producing inorganic oxides, but they can be produced by heating an inorganic oxide, usually known as crystallized water, and evaporating the water.In the T industry, volcanic glass is heated Shirasu balloons can be inserted at low cost.
) A desired composition can also be synthesized by synthesizing a fine powder of a mixture thereof and then heat-treating it.

The hollow inorganic oxide obtained in this way can be used by adding a transition metal compound, alumino-1-phosphorus (IJ), by first applying chlorine and further calcining, but it is preferable to use it after removing at least free water. (2.

There is no particular restriction on the method of loading, but in order to effectively utilize the hollow space, the inorganic oxide having a hollow space is added to a solution of a transition metal compound and aluminoquirin in 1 liter portions (7 system is reduced in pressure, and then the pressure is returned to normal pressure). By repeating +21q, the catalyst can be effectively supported.Usually, after being supported, the catalyst is washed with a hydrocarbon compound, and the unsupported catalyst is removed and used for polymerization. Although there are no particular restrictions on this, it is usually carried out at 0°C to 100°C.

In addition to the above-mentioned supported catalyst, aluminoxane can also be used in combination during polymerization, which usually gives favorable results in terms of activity.

In the present invention, α-olefins include propylene, butene-11pentene-12hexene-1, heptene-1
, octene-1, nonene-1, decene-1, undecene-1, dodecene-1, tridecene-1, tetradecene-1
1. In addition to linear α-olefins such as pentadecene-11 hexadecene-11 occudecene-1, branched α-olefins such as 3-methylbutene-1,4-methylpentene-1,4,4-dimethylpentene-1 Examples include not only these α-olefins alone but also mixtures with each other or with a small amount of ethylene.

Further, there are no particular limitations on the polymerization conditions, and solvent polymerization methods using an inert medium, bulk polymerization methods in which substantially no inert medium is present, and gas phase polymerization methods can also be used. The polymerization temperature is -100 to 200'C2 polymerization pressure and ζ is normal pressure to
It is common to carry out at 100 kg/afl. Preferably, the pressure is -100 to 100° C. and normal pressure to 50 kg/(min).

〔Example〕

The present invention will be further explained with reference to Examples below.

Example 1 200+ ng of isopropyl (cyclopangenyl-1-fluorenyl) zirconium dichloride obtained by lithiation of isopropylcyclopentagenyl-1-fluorene synthesized according to a conventional method and reacting with zirconium tetrachloride and Toyo Akzo ( 1.34g of methylaluminoxane (polymerization degree 16.2) made from chrysanthemum was heated to ff-7300m.
Dissolved in β and put it in a 101 flask, dispersed 10g of Nkirai I-YO4 manufactured by Sanki Kogyo Co., Ltd. (calcined at 600°C for 10 hours), and while stirring, put the
The operation of reducing the pressure to +nm11g and holding it for 10 minutes, then returning it to normal pressure and holding it for 10 minutes was repeated 5 times. The mixture was then filtered under a nitrogen stream to remove excess isopropyl (cyclopentadienyl-1-fluorenyl) zirconium dichloride methylaluminoxane. Then the supported catalyst is 1
A supported catalyst was obtained by washing with 00 d of toluene five times. This catalyst contained 0.04 wt x of zirconium.

0.5 g of the obtained catalyst was put into an autoclave with an internal volume of 2j2 together with 11 toluene, and the polymerization pressure was 3 kg.
/cd-G, without adding propylene 2
Polymerization was carried out at 0°C for 2 hours, followed by deashing with methanol and methyl acetoacetate, washing with aqueous hydrochloric acid, filtering, and drying to obtain 20.5 g of syndiotactic polypropylene (102,500 g of polypropylene/ (equivalent to 1 g of zirconium).

The bulk specific gravity of this polymer was 0.31 g/rdl and the average particle size was 400 μ-. Furthermore, according to C-NMR, the syndiotactic pentad fraction is 0.915, and the intrinsic viscosity (hereinafter referred to as η) measured in a tetralin solution at 135°C is 1.42.1, 2.4- The MW/MN measured with Trichroma benzene was 2.2.

Comparative Example 1 The isopropyl(cycL2pentagenyl-1-fluorenyl)zirconium dichloride obtained in Example 1 was treated with 1. h
Example 1 was carried out in the same manner as in Example 1, except that g and 0.11 g of methylaluminodi-1-sane were used, and 48.2B of polymer was obtained (this corresponds to 241,000 g of polypropylene/1 g of zirconium). The bulk specific gravity of this polymer is 0.
The average particle size was 21 g/Id and 50 μm. Also, according to C-NMR, the syndiotactic pentad fraction is 0.920, and η is 1.40.1, 2.4.
- MW/MN measured with trichlorobenzene was 2.3.

Example 2 The same procedure as Example 1 was carried out except that 0.17 g of methylaluminoxane was used in combination during the polymerization. Tokoro 47g of polymer
This corresponds to 1 g of 235,000 g polypropylene/Si)reconium obtained. ). The bulk specific gravity of this polymer is 0
．． The particle size was 40 g/m, and the average particle size was 420#.

According to 13C-NMR, the syndiotactic pentad fraction is 0.922, and η is 1.42.12.4.
- MW/MN measured with trichlorobenzene was 2.3.

〔Effect of the invention〕

When the method of the present invention is carried out, a highly active and bulky compound α-j [5, twin 4.1 (), 4 '6 and 1. Industrial IS is extremely self-reliant.

[Brief explanation of drawings]

FIG. 1 is a 11-diagram to aid understanding of the present invention.

Claims (1)

[Claims] A method for polymerizing α-olefin using a catalyst consisting of a transition metal compound having an asymmetrical ligand and aluminoxane, in which the transition metal compound having an asymmetrical ligand and aluminoxane are supported on a hollow inorganic oxide. A method for producing syndiotactic polyα-olefin, characterized by: