JPH04168105A - Catalyst for olefin polymerization, production thereof and production of olefin polymer using the same catalyst - Google Patents

Abstract

NEW MATERIAL:A yttrium compound wherein two cyclopentadienyl groups contain substituent groups which are mutually bonded through a hydrocarbon residue or Si atom and H and a substituent group selected from alkyl or aryl. USE:A catalyst for olefin polymerization, having high activity and excellent durability of activity. PREPARATION:(A) An alkaline (earth) metal salt [e.g. methylenebis (cyclopentadienyl)dilithium] of a compound wherein two cyclopentadienyl groups contain bifunctional substituent groups which are mutually bonded through a hydrocarbon residue or Si atom is brought into contact with (B) an organometallic compound (preferably bistrimethylsilylmethyllithium) of group I to group III of the table and (C) a yttrium halide (preferably yttrium trichloride) preferably by a method wherein the component A is brought into contact with the component C in the presence of an ether-based organic solvent and the reaction product is reacted with the component B.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a novel catalyst for olefin polymerization, a method for producing the same, and a method for producing an olefin polymer using the same.

(Prior Art) Ziegler-Natsuta type catalysts have been widely known as catalysts for olefin polymerization. On the other hand, not much is known about complex catalysts with yttrium as the central metal.

In recent years, several reports have been made regarding yttrium complex catalysts with cyclopentadiene as a ligand [J,
Chew, Soe, Chew, Commu
n, (1978), <22>.

994 and J, Orgioomet, Chem.
(1987), 323° 181, etc.] However, the catalysts described in these known documents are still insufficient for industrial use in terms of activity and molecular weight controllability.

(Problems to be Solved by the Invention) The present invention provides a highly active and long-lasting olefin polymerization catalyst using a yttrium compound having a sterically fixed ligand, a method for producing the same, and an olefin polymerization catalyst using the same. A method for producing a polymer is provided.

(Means for Solving the Problems) The present invention provides: 1. A catalyst for olefin polymerization consisting of a yttrium compound having the following constituent elements A and B: A: two cyclopentadienyl groups mutually containing hydrocarbon residues or silicon B: has a substituent selected from a hydrogen atom, an alkyl group, and an aryl group; 2. The following components a, b, and C are brought into contact with each other. Method for producing an olefin polymerization catalyst according to item 1: Component a: an alkali metal salt or alkali of a compound having two substituents in which two cyclopentadienyl groups are bonded to each other via a hydrocarbon residue or a silicon atom. Earth metal salt, component B: organometallic compound of groups I to ■ of the periodic table, component C:
In the presence of yttrium halide and 3. the catalyst described in item 1, the reaction mixture is expressed by the general formula CH2=CHR (wherein R represents a hydrogen atom or a hydrocarbon residue having 1 to 8 carbon atoms). A method for producing an olefin polymer, characterized by polymerizing an olefin.

(Detailed description of the invention) [Touch! ! ] The catalyst of the present invention is an olefin polymerization catalyst comprising a yttrium compound having the constituent elements A and B.

Component A is that two cyclopentagenyl groups have a substituent (ligand) bonded to each other via a hydrocarbon residue or a silicon atom.

Here, the cyclopentadienyl group refers to substituted and unsubstituted compounds having a cyclopentadiene ring, specifically cyclopentadienyl group, indenyl group, phenanthrenyl group, fluorenyl group, bicyclo[3,3,0 ) octa-1,3-genyl group, 4,5,6,7-titrahydroindenyl group, bicyclo[5,3,0]deca-8,
11-genyl group, tricyclo[5,2,1,0'', a
Examples include deca-2,5-genyl group and alkyl, alkylsilyl or alkylgermyl substituted products thereof. Among them, cyclopentadienyl group, indenyl group, fluorenyl group, 4,5.6.7-
Substituted or unsubstituted titrahydroindenyl groups are preferred.

In addition, to combine two cyclopentadienyl groups,
Hydrocarbon residues or silicon atoms are used. here,
The hydrocarbon residue is preferably an alkylene group having 1 to 4 carbon atoms in the main chain, or an alkyl group or aryl substituted product thereof. Moreover, those bonded with silicon atoms are preferably dialkyl or aryl substituted silyl groups.

Among these, methylene group, dimethylmethylene group, ethylene group, tetramethylethylene group, propylene group, dimethylsilyl group, and diphenylsilyl group are preferable.

Component B has a substituent selected from a hydrogen atom, an alkyl group and an aryl group.

The alkyl group includes an alkyl group having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, or an alkyl group having 1 to 8 carbon atoms (1 to 8 carbon atoms).
) An alkyl group having a substituted silicon group is exemplified by an aryl group having 6 to 18 carbon atoms, preferably 6 to 12 carbon atoms, or an aryl group having an alkyl (1 to 8 carbon atoms) substituted silicon. .

Among these, sterically bulky substituents, such as alkyl groups with 1 to 8 carbon atoms or alkyl groups (with 1 to 8 carbon atoms) at the α-position,
8) An alkyl group or an ortho-substituted aryl group having a plurality of substituted silyl groups, preferably one having a structure in which β-hydrogen or alkyl elimination is difficult to occur, such as a trialkylsilyl-substituted methyl group, an ortho-substituted aryl group, etc. is preferable, and specific examples include bistrimethylsilylmethyl group and mesityl group.

The catalyst having the above components A and B specifically includes the following component a having each component.

It can be prepared using b and c.

Component a having component A is an alkali metal salt or alkaline earth metal salt of a compound having a divalent substituent in which two cyclopentadienyl groups are bonded to each other via a hydrocarbon residue or a silicon atom. be.

Preferred component a is specifically a compound represented by the general formula %. Here, Q represents a hydrocarbon residue or a silicon atom, Cp and C'p represent a cyclopentadienyl group which may be the same or different, and 1Ml and M2 represent an alkali metal or alkaline earth group which may be the same or different. Ml and M represent metals, respectively.
When 2 is an alkaline earth metal, it is necessary that one halogen or alkyl group is bonded thereto. M here.

and M2 are preferably lithium, sodium, potassium, magnesium, etc.

Specific examples of component a include methylenebis(cyclopentagenyl)dilithium 1, ethylenebis(cyclopentagenyl)dilithium, ethylenebis(2-methylcyclopentagenyl)dilithium, ethylenebis(3-methylcyclopentagenyl)dilithium, ) dilithium, ethylenebis(2,3-dimethylcyclopentadienyl)dilithium 1, ethylenebis(2,4-dimethylcyclopentadienyl)dilithium, ethylenebis(2,3,4-trimethylcyclopentadienyl) Dilithium, ethylenebis(2,3,5-trimethylcyclopentadienyl)dilithium, ethylenebis(2゜3.4.5-tetramethylcyclopentadienyl)dilithium, ethylenebis(3
-ethylcyclopentagenyl) dilithium, ethylenebis(3-t-butylcyclopentagenyl)dilithium, ethylenebis(3-phenylcyclopentagenyl)dilithium, ethylenebis(3-benzylcyclopentagenyl)dilithium, Ethylenebis(3-menthylcyclopentagenyl)dilithium, isopropylidenebis(cyclopentagenyl)dilithium, 1,3-propylenebis(cyclopentagenyl)dilithium, dimethylsilylenebis(cyclopentagenyl)dilithium, dimethyl silylenebis(2,3,4,5-tetramethylcyclopentadienyl)dilithium, diphenylsilylenebis(2,3,4,5-tetramethylcyclopentadienyl)dilithium, dimethylsilylene(cyclopentadienyl-2) ,3,4゜5-tetramethylcyclopentadienyl)dilithium, dimethylsilylenebis(3
-trimethylcyclopentadienyl) dilithium, cyclohexylidenebis(3-methylcyclopentagenyl)dilithium, ethylenebis(indenyl)dilithium, ethylenebis(indenyl)disodium, ethylenebis(indenyl)dipotassium, ethylenebis(indenyl) Dimagnesium chloride, ethylenebis(indenyl)dimagnesium bromide, ethylenebis(2-methylindenyl)dilithium, ethylenebis(3-methylindenyl)dilithium, ethylenebis(4-methylindenyl)dilithium, ethylenebis(7-methylindenyl)dilithium -methylindenyl) dilithium, methylenebis(indenyl)dilithium, 1,3-propylenebis(indenyl)dilithium, isopropylidenebis(indenyl)dilithium, diphenylmethylenebis(indenyl)dilithium, cyclohexylidenebis(indenyl)dilithium,
Ethylenebis(4°5.6.7-titrahydroindenyl)dilithium, ethylenebis(fluorenyl)dilithium, 2,2-propylene(cyclohexylidenebis).

fluorenyl) dilithium, dimethylsilyl (bisindenyl) dilithium, dimethylsilyl (4°5.6.7
-titrahydroindenyl)dilithium, dimethylsilyl(cyclopentagenyl,)luorenyl)dilithium, and the like.

The components with component B have substituents selected from alkyl groups and aryl groups, preferably from Periodic Table I
It is an organometallic compound of group ~■.

Specific examples of the components include methyllithium, methylpotassium, methylsodium, methylmagnesium chloride, methylmagnesium bromide, methylmagnesium chloride, ethyllithium, diethylmagnesium, n-
Butyllithium, 5ee-butyllithium, tert-
Butyllithium, isoprenyllithium, neopentyllithium, di-tert-butylmethyllithium, phenyllithium, 0-tolyllithium, 2,6-dimethylphenyllithium, mesityllithium, 0-ethylphenyllithium, o -tert- Butylphenyllithium, 0-trimethylsilylphenyllithium, benzyllithium, neophylllithium, trimethylsilylmethyllithium, bistrimethylsilylmethyllithium, trimethylaluminum, triethylaluminum, triisobutylaluminum, dimethylaluminum chloride, ethylaluminum sesquichloride, diethylaluminum hydride, diisobutyl Examples include aluminum hydride, methylaluminoxane, and triethylboron. Among these, alkali metal or alkaline earth metal salts of trialkylsilyl-substituted methyl groups such as bistrimethylsilylmethyllithium and ortho-substituted aryl groups such as mesityllithium are preferred.

Component C is yttrium halide.

Specific examples include yttrium trichloride, yttrium tribromide, and yttrium triiodide. Among them, yttrium trichloride is preferred.

The catalyst used in the present invention can be synthesized by applying a known method. For example, preferably, the compound of component a above is mixed in an ether-based organic solution such as tetrahydrofuran, diethyl ether, or dimethoxyethane. (5 to 1 weight ratio to component C)
000 times the amount of organic solvent), the compound of component C was mixed with
In the temperature range of 00 to 200°C, component a: acid component = 0.
5:1 to 1.25:1 (molar ratio), and the resulting product is reacted with the components. Solvents used in this reaction include, for example, pentane, hexane,
Aliphatic hydrocarbons such as heptane, alicyclic hydrocarbons such as cyclohexane, aromatic hydrocarbon solvents such as benzene, toluene, etc., or the above-mentioned ether-based organic solvents (5 to 1000 times the weight ratio of the organic solvents to the components) The amount of component C used is 0.5 for the component C used at the beginning.
5, and the reaction temperature is -200 to 200°C.

In the production of the above catalyst, when an alkali metal or alkaline earth metal compound having an alkyl group or an aryl group is used as a component, during the reaction of the component,
Hydrogen gas can be used at the same time or later.

The catalyst of the present invention described above can be used alone as a reaction product for polymerization, but it may also be supported on a suitable support.
As the support used in this case, inorganic supports such as silica gel, alumina, zeolite, magnesium chloride, and magnesium oxide, and polymer supports such as polyethylene particles and polypropylene particles can be used.

〔polymerization〕

The monomer polymerized using the yttrium catalyst of the present invention is an olefin compound having a terminal double bond represented by the general formula CI (2=CH-R).

Here, R represents a hydrogen atom or a hydrocarbon residue having 1 to 8 carbon atoms, specifically, ethylene, propylene, 1-
Butene, 3-methylbutene-1,1-hexene, 4-methylpentene-1,1-octene, 1-decene, styrene, butadiene, isoprene, 1,5-hexadiene,
Examples include 7-methyl-1,7-octadiene. These monomers can be used alone or in combination of two or more.

Polymerization can be carried out in a gas phase, in a liquid phase, or by any other known method. When using a solvent, it is preferable to use an inert organic solvent, such as aromatic hydrocarbon solvents such as benzene, toluene, xylene, n-pentane, n-hexane, n-
aliphatic hydrocarbon solvents such as hebutane, n-paraffin,
Any alicyclic hydrocarbon solvent such as cyclohexane or methylcyclopentane can be used. One of the features of the present invention is that aliphatic hydrocarbon solvents are also effective.

Polymerization temperature is -20~260℃, preferably 40~200℃
It is ℃.

A molecular weight regulator can be used during polymerization. Hydrogen gas is effective as the molecular weight regulator.

Moreover, since hydrogen brings about the effect of improving catalyst activity, it is preferable to make it exist in the polymerization system.

The polymerization pressure is appropriately selected within the range of normal pressure to 3000 kg/em2G.

(Effects of the Invention) According to the present invention, by using a novel yttrium compound having a specific ligand, an olefin polymerization catalyst with high activity and excellent activity persistence can be obtained, and it is possible to obtain an olefin polymerization catalyst with a narrow molecular weight distribution and a low molecular weight Olefin polymers having a wide range of molecular weights up to high molecular weights can be produced.

(Example) Example-1 1 Supervision 11 Put 10.0 mmol of 1,2-diindenyl ethane and 120 ml of purified THF into a stirred 300 ml flask that has been sufficiently purged with nitrogen, and cool to -78°C. Then, n
-12.5 ml of a 1.6N hexane solution of butyllithium was added dropwise.

The temperature was raised to room temperature and the reaction was continued for 8 hours.

Add 1.95 g of anhydrous yttrium chloride to this at -78°C.
Slurry the slurry with 100ml of THF at 0°C.
and refluxed for 8 hours.

After the reaction was completed, the mixture was cooled to 10° C. and the solvent was distilled off under reduced pressure. After adding 100 ml of purified diethyl ether and stirring, the mixture was cooled to 10°C and the solvent was distilled off under reduced pressure. This operation was repeated twice.

Add 100 ml of purified toluene to the obtained product and heat at 0°C.
Bistrimethylsilylmethyllithium 0.67M-
15.0+*l of diethyl ether solution was added and reacted for 8 hours. After distilling off the solvent of the reaction product under reduced pressure, it was extracted with 100ml of purified toluene, and the solution was concentrated and reconstituted. The product was crystallized.

The resulting product was diluted in purified toluene to 0.063
m5oiY /+mL-) It was subjected to polymerization as a catalyst solution of toluene.

300 ml of purified toluene was introduced into a 11 autoclave equipped with a stirring blade that had been thoroughly dried and purged with nitrogen, and then 2.5 ml (0.157 ml) of the catalyst solution prepared above was introduced under a nitrogen atmosphere.
5 ol) was added, and hydrogen was added to this at a polymerization tank pressure of 2 kg/c.
*”G was introduced and stirred at 15° C. for 1 hour.

Next, after purging hydrogen and replacing the inside of the system with nitrogen, ethylene was introduced, and the polymerization tank pressure was maintained at 6 kg/cm2G.
Polymerization was carried out at 80°C for 3 hours.

As a result, 66.6 g of polyethylene was obtained, the molecular weight of which was 2.40 x 10' for Mn and 5.90 for M w.
X10' and Q value (Mw/Mn) were 2.46.

Example-2 7 An autoclave similar to Example-1 was sufficiently dried and replaced with nitrogen to produce purified toluene 3QQw+l and Example-1.
Catalyst solution used in 2.5 ml (0,157 s + mol)
was introduced, and further 1200 ml of hydrogen and ethylene were introduced, and the polymerization tank pressure was maintained at 8 kg/em'G, and polymerization was carried out at 60° C. for 3 hours.

As a result, 37.2 g of polyethylene was obtained, the molecular weight of which was 1.31 x 10' for Mn and 2.
96X10'.

The Q value was 2.26.

Example-3 In the same manner as in Example-1, the catalyst solution was mixed with 5-1 (0,31
mmol) and polymerized at 60°C in propylene.

After the polymerization was completed, the solvent was distilled off to obtain 0.47 g of polymer. The product was confirmed to be atactic polypropylene by 13C-NMR.

Example 4 11 In the same manner as in Example 1, dimethylsilylene bisindene 10.0--01 and purified THF 150 ml were placed in a stirred 300 ml flask that had been sufficiently purged with nitrogen. Cool to 78°C, add n-butyllithium 1,6N
The temperature of the reaction mixture to which 14.0 ml of hexane solution was added dropwise was raised to room temperature and reacted for 8 hours.

Add 1.95 g of anhydrous yttrium chloride to this at -78°C.
A slurry of 75-1 THF was added at 0°C and refluxed for 8 hours.

After the reaction was completed, the mixture was cooled to 10° C. and the solvent was distilled off under reduced pressure. 120s+1 purified diethyl ether was added to this, extracted, and the solvent was distilled off to obtain 3.34 g of a brown reaction product.

Add purified toluene looml to the obtained product and heat at 0°C.
10.3 ml of bistrimethylsilylmethyllithium 0.53 diethyl ether solution was added and reacted for 8 hours. After distilling off the solvent of the reaction product under reduced pressure, it was extracted with 100 ml of purified toluene, filtered, and polymerized. Served.

The catalyst concentration of this product is 0.067 m5 + oiY / plow 1
) was Luen.

In the same manner as in Example-1, a catalyst solution of 5.0+sl (0,
337 smol) and polymerized with ethylene at 60°C.

As a result, 31.8 g of polyethylene was obtained, the molecular weight of which was 1.48 x 10' for Mn and 4.57 for M w.
X10', Q value was 3.08.

Example 5 In the same manner as in Example 4, ethylene polymerization was carried out in the presence of propylene 151 (liquid equivalent).

As a result, 11.8 g of polymer was obtained, the molecular weight of which was 6.82x 10' for Mn and 2.04x for Mw.
105, and the Q value was 2.99.

Example-6 11511 In the same manner as in Example-4, 8.5 mmol of dimethylsilylene (cyclopentadiene, fluorene) and purified T were placed in a stirred 300 ml flask that had been sufficiently purged with nitrogen.
Pour 150ml of HF, cool to -78°C, and
11.1 ml of a 1.6N hexane solution was added dropwise to the reaction mixture, and the temperature of the reaction mixture was raised to room temperature, followed by a reaction for 8 hours.

Add 1.65 g of anhydrous yttrium chloride to this at -78°C.
Slurry the slurry with 50a+l of THF at 0°C.
and refluxed for 8 hours.

After the reaction was completed, the product was cooled to 10° C. and the solvent was distilled off under reduced pressure. Purified diethyl ether 1001 was added to this, and after stirring, the solvent was distilled off again under reduced pressure. This operation was repeated twice.

Add 100 ml of purified toluene to the obtained product and heat at 0°C.
Bistrimethylsilylmethyllithium 0.67M-
After adding diethyl ether solution 12.6e+I and reacting for 8 hours, the solvent of the reaction product was distilled off under reduced pressure, and purified n-pentane 75s! The mixture was washed with water, extracted with 100 ml of purified toluene, treated with P, and subjected to polymerization.

The catalyst concentration of this product is 0.045 mmol-Y/ml
) was Luen.

In the same manner as in Example-1, a catalyst solution of 5.0 kg (0,2
25-mol) and polymerized with ethylene at 25°C.

As a result, 5.0 g of polyethylene was obtained, and its molecular weight was as follows: Mn: z, tzx: 105, Mw: 5.80x
105, and the Q value was 2.74.

Claims (1)

[Scope of Claims] 1. An olefin polymerization catalyst comprising an yttrium compound having the following constituent elements A and B. A: Two cyclopentadienyl groups have a substituent bonded to each other via a hydrocarbon residue or a silicon atom, B: A substituent selected from a hydrogen atom, an alkyl group, and an aryl group. 2. The method for producing an olefin polymerization catalyst according to item 1, which comprises bringing the following components a, b, and c into contact with each other. Component a: Alkali metal salt or alkaline earth metal salt of a compound having a divalent substituent in which two cyclopentadienyl groups are bonded to each other via a hydrocarbon residue or a silicon atom, Component b: Periodic table Organometallic compound of groups I to III, component c: yttrium halide. 3. In the presence of the catalyst described in item 1, the general formula CH_2=CHR (wherein R is a hydrogen atom or
~8 hydrocarbon residues are shown. ) A method for producing an olefin polymer, which comprises polymerizing an olefin represented by: