JPH0420002B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a catalyst for the polymerization of olefins and/or conjugated dienes.

As an example of using lanthanum-based rare earth element compounds, Duyang Jun (Proceedings of Japan-China Polymer Science and Technology Symposium, p. 78, The Society of Polymer Science, Tokyo, 1981) used a tribasic lanthanide/EtOH/AlEt _3- based catalyst to produce ethylene and butadiene. The results of each homopolymerization are reported. However, in this case, the catalyst activity shows high activity for butadiene, but for ethylene, 20% of polyethylene per gram of lanthanide metal is used.
It has very low activity, less than 1.5 g.

On the other hand, as an ethylene/butadiene copolymerization catalyst, for example, Ti(OBu) ₄ /
AlEt _3- based catalyst was also published in Japanese Patent Publication No. 1983-26071.
TiCl ₄ /Al(i-Bu) ₃ /carbonyl compound catalysts have been proposed, but these catalyst systems have very low catalytic activity of less than 100 g of polymer per 1 g of Ti atom.

Furthermore, in Japanese Patent Publication No. 49-16784, ethylene and butadiene are co-coated using a solid catalyst component obtained by heat treating MgCl ₂ with titanium tetrachloride in the presence of an electron donor compound and a catalyst consisting of trialkylaluminium. A method of polymerizing is disclosed. This catalytic activity is as high as 30Kg/g・Ti-h,
The conjugated diene content in the copolymer is very low, 2 to 3 mol% or less. Also, in JP-A-51-37984, vanadium compounds - organic aluminum compounds -
A method has been disclosed in which ethylene and butadiene are copolymerized using Bronsted acid-thionyl chloride as a catalyst component, but even this catalyst has a very low diene content.

As described above, in the production of olefin/conjugated diene copolymers, it has been difficult to obtain a polymerization catalyst that has high catalytic activity and can produce a copolymer with a high conjugated diene content.

The present inventors conducted intensive research to solve these problems, and found that a catalyst component consisting of a neodymium or praseodymium compound, a Lewis base, and a titanium halide has high activity in olefin/conjugated diene copolymerization, and can randomly form conjugated dienes. The present invention was achieved by discovering that it can be introduced into a polymer in any amount and that it has high catalytic activity in the homopolymerization of olefins or conjugated dienes.

According to the present invention, the general formula LnY ₃ (where Ln is neodymium or praseodymium, Y is RCOO-, -OR, -
SR, -NR ₂ , or X, where R is 1 carbon number
A catalyst component prepared by adding titanium halide to a reaction product or mixture of a neodymium or praseodymium compound represented by ~20 hydrocarbon groups (X is a halogen atom excluding fluorine) and a Lewis base
(A) and the general formula AlR ¹ nX _3-o (where X is hydrogen or halogen, R ¹ is a hydrocarbon group having 1 to 20 carbon atoms,
n is 1, 1.5, 2 or 3) or the organoaluminum compound and an alcohol represented by the general formula R ² OH (wherein R ² is a hydrocarbon group having 1 to 30 carbon atoms) A catalyst for the polymerization of olefins and/or conjugated dienes is provided, which comprises a catalyst component (B) which is a reaction product of the olefin and/or conjugated diene.

The present invention will be explained in detail below.

Ln of the neodymium or praseodymium compound used in the present invention (catalyst component (A)) is a lanthanum series rare earth element with an atomic number of 57 to 71, and among them, cerium, lanthanum, praseodymium, neodymium, and gadolinium are preferable, and neodymium is particularly preferable because neodymium is industrially available. It is preferred because of its ease of use. A mixture of two or more rare earth elements may be used.

Lanthanum series rare earth element compounds include carboxylates, alkoxides, thioalkoxides,
Halogen and amine forms, particularly carboxylic acid salts, are preferred.

The neodymium or praseodymium carboxylate is represented by the general formula (RCO ₂ ) ₃ Ln, where R represents a hydrocarbon substituent having 1 to 20 carbon atoms, preferably a saturated or unsaturated alkyl group, It is linear, branched, or cyclic, and the carboxyl group is bonded to a primary, secondary, or tertiary carbon atom. Examples include acetic acid, propionic acid, isobutyric acid, n-valeric acid, i-valeric acid, pivalic acid, n-hexanoic acid, 3,3-dimethylbutyric acid,
Examples include n-heptanoic acid, n-octenoic acid, 2-ethylhexanoic acid, cyclohexanoic acid, benzoic acid, naphthenic acid, stearic acid, lauric acid, palmitic acid, and oleic acid. Among them, the number of carbon atoms is 5
The above carboxylic acids are preferred, especially octanoic acid, 2-ethylhexanoic acid, benzoic acid, naphthenic acid, oleic acid and stearic acid.

As an alcohol type compound, the general formula Ln
(OR) ₃ (in the formula, Ln and R are as described above), and specifically preferred alcohols include 2-
Examples include ethyl-hexyl alcohol, oleyl alcohol, stearyl alcohol, phenol, and benzyl alcohol.

As a thioalcohol type compound, the general formula Ln
(SR) ₃ (in the formula, Ln and R are as described above), and a specific preferred thioalcohol is thiophenol.

The amine type compound is represented by the general formula Ln(NR ₂ ) ₃ (wherein Ln and R are as described above), and specifically, dihexylamine and dioctylamine are preferred.

Lewis bases used in catalyst component (A) include the following. Examples of amines include pyridine, picoline, piperidine, triethylamine, N, N,
Examples include N',N'-tetramethylethylenediamine, aniline, N-methylaniline, and N,N-diethylaniline. Examples of ethers include tetrahydrofuran, diethyl ether, dibutyl ether, and diphenyl ether. Examples of ketones include acetone, 2-butanone, acetophenone, and acetylacetone. Alcohols include methyl alcohol, ethyl alcohol, n-propyl alcohol, n-butyl alcohol, t-butyl alcohol, 2-methyl-2-butyl alcohol, n-hexyl alcohol, cyclohexanol, 2-phenyl-2-propanol, 2 -Phenyl-1-
Examples include propanol, 4-t-butyl-cyclohexanol, and the like. Examples of sulfoxides include dimethyl sulfoxide, diethyl sulfoxide, and diphenyl sulfoxide. Among them, acetylacetone, pyridine, dimethyl sulfoxide, tetrahydrofuran, N,N-dimethylformamide, and N,N,N',N'-tetramethylethylenediamine are preferred.

The above neodymium or praseodymium compound and Lewis base may be used as a reaction product, or may be used in the form of a mixture having the following composition ratio. The molar ratio of neodymium or praseodymium compound to Lewis base is 1:0.01 to 1:100, preferably 1:0.05 to 1:50, more preferably 1:
From 0.1 to 1:30.

Examples of the titanium halide used in the catalyst component (A) include titanium tetrachloride, titanium trichloride, and a complex of the aforementioned Lewis base and titanium trichloride. The molar ratio of neodymium or praseodymium compound to titanium halide is 1:0.1 to 50, preferably 1:0.1 to 20, more preferably 1:0.5 to
It is 10.

Examples of the organoaluminum compound represented by AlR ¹ nX _3-o of the catalyst component (B) include trimethylaluminum, triethylaluminum, tri-n-
Propyl aluminum, tri-iso-propyl aluminum, tri-n-butyl aluminum, tri-iso-butyl aluminum, tri-hexyl aluminum, tricyclohexyl aluminum, trioctyl aluminum, diethylaluminium hydride, di-iso-butyl aluminum hydride, dimethyl Aluminum chloride, diethylaluminium chloride, diethylaluminum bromide, di-n-propylaluminum chloride, di-iso-butylaluminum chloride, methylaluminum dibromide, iso-butylaluminum dichloride,
Examples include methylaluminum sesquichloride, ethylaluminum sesquichloride, iso-butylaluminum sesquichloride, and mixtures thereof.

Further, as the catalyst component (B), a reaction product or a mixture of the above organoaluminum compound and an alcohol represented by the general formula R ² OH may be used. As such alcohol, specifically, the alcohols exemplified by the Lewis bases mentioned above are used. The molar ratio of the organic aluminum compound to the alcohol is 1:0.01-2, preferably 1:0.1-1.

In the catalyst of the present invention, the molar ratio of the organoaluminum compound as catalyst component (B) to neodymium or praseodymium as catalyst component (A) is 1:2 to 100, preferably 1:4 to 50.

The catalyst production method begins with LnY ₃ as the catalyst component (A).
and Lewis base. In this case, LnY ₃ is mixed directly with the Lewis base or in the presence of a suitable solvent such as 2-hexane, cyclohexane, benzene, toluene, etc. Usually, LnY ₃ and a Lewis base dissolved in a solvent are mixed in the presence of a solvent. Processing temperature is -50~150℃, preferably 0
~50℃ range.

Next, the solution in the above solvent and the titanium halide are mixed, and the titanium halide may be added to the solution or the solution may be added to the titanium halide. Further, the treatment temperature is in the range of -30°C to +100°C, preferably 0°C to 80°C.

When a solid titanium halide such as titanium trichloride is used, a complex is formed between the titanium halide and one or more compounds exemplified as the Lewis base of the catalyst component (A), and the complex is Preferably, a homogeneous solution or suspension in a solvent is added to the above LnY ₃ /Lewis base solution.

In this case, the Lewis base is preferably ethers or amines, and more preferably tetrahydrofuran or pyridine. The reaction composition ratio of titanium halide and Lewis base is 1:2 to 1:1000, preferably 1:5 to 1:100.

When the catalyst component (A) described above is precipitated as a finely powdered solid, the finely powdered solid may be washed several times with an inert hydrocarbon and then used as a suspension of the inert hydrocarbon. It may be used as is without separation.

When using a reaction product or a mixture of an organoaluminum compound and an alcohol as the catalyst component (B), it is preferable to add the alcohol dropwise to the organoaluminum compound in an inert hydrocarbon. The temperature is between -30°C and 100°C, preferably between 0°C and 80°C.

In the catalyst of the present invention, the composition ratio of component (A) and component (B) is 1:2 to 1:100 in molar ratio, preferably 1:
It ranges from 4 to 1:50.

The catalyst thus obtained can be used for olefin polymerization, conjugated diene polymerization, olefin copolymerization, conjugated diene copolymerization,
Used in olefin/conjugated diene copolymerization. Examples of olefins include ethylene, propylene, 1-butene, 1-hexene, and butylene. Examples of the conjugated diene include butadiene, isoprene, 1,3-pentadiene, and chloroprene.

The polymerization reaction is usually carried out in a hydrocarbon solvent such as n-pentane, isopentane, n-hexane, n-heptane, cyclohexane, cycloheptane, benzene or toluene or mixtures thereof.

Alternatively, polymerization may be carried out by adding a catalyst to the monomer without using a solvent. Polymerization temperature is usually -30℃~150℃
°C, preferably in the range of 0 °C to 100 °C. The polymerization reaction may be carried out either batchwise or continuously.

By using the neodymium or praseodymium compound/Lewis base/titanium halide catalyst component of the present invention, a copolymer with high activity and high randomness can be obtained at any monomer unit composition ratio in olefin/conjugated diene copolymerization. It will be done. It also has high catalytic activity in the homopolymerization of conjugated dienes or olefins.

In the following examples, the copolymer composition of olefin and diene and the microstructure of the diene polymer are determined by nuclear magnetic resonance analysis, and the microstructure of polybutadiene is determined by infrared light analysis using the Morello method.

Example 1 (i) Preparation of polymerization catalyst (1) 0.3 mmol of neodymium octenoate was placed in a Schülenk that had been sufficiently purged with dry nitrogen, and the concentration was 0.5 mol/
1.2 l of acetylacetone in n-hexane solution
ml, and then add 10 ml of n-hexane to make a homogeneous solution. This homogeneous solution has a concentration of
5.1 ml of a 0.5 mol/l n-hexane solution of titanium tetrachloride was added to form a red precipitate, which was used as catalyst component (A-1).

Concentration 0.5 mol/l as catalyst component (B-1)
7.2 ml of a solution of triisobutylaluminum in n-hexane was added dropwise to the catalyst component (A) with stirring to form a suspension to obtain a polymerization catalyst (1).

(ii) Polymerization of butadiene Pour 20 ml of n-hexane as a solvent into a 100 ml pressure-resistant stainless steel autoclave purged with nitrogen, and add 0.030 mmol (Ti
0.225 mmol) of polymerization catalyst (1) was added, and after cooling and degassing under liquid nitrogen temperature, 8.9 g of butadiene was obtained.
(164 mmol) was introduced. The reactor was left for 1 hour while being maintained at 50°C. After the reaction was completed, a large amount of methanol containing an antioxidant was added to wash the polymer, and the polymer was dried under reduced pressure overnight.

The yield of the polybutadiene obtained was 2.79 g (640
g.polymer/g.Nd-h, 230g.polymer/g.Ti-h). The microstructure of the polybutadiene was 27% trans-1.4 structure, 69% cis-1.4 structure, and 4% vinyl structure.

Example 2 (i) Preparation of polymerization catalyst (2) Same as Example 1, neodymium octenoate
A catalyst component (A-2) was prepared using 0.3 mmol of titanium tetrachloride, 0.6 mmol of acetylacetone, 1.95 mmol of titanium tetrachloride, and 10 ml of n-hexane.

Further, 6 mmol of triisobutylaluminum was used as the catalyst component (B-2), and the catalyst component (A
-2) to obtain a polymerization catalyst (2).

(ii) Polymerization of butadiene Same as Example (1), polymerization catalyst (2) (in terms of Nd)
0.030 mmol (0.195 mmol in terms of Ti) was used to polymerize 8.9 g (169 mmol) of butadiene, resulting in 1.59 g of polybutadiene (380 g, polymer/g, Nd,
h, 180 g.polymer/g.Ti.h) was obtained.
The microstructure of the resulting polymer is trans-
The composition was 34% 1.4 structure, 60% cis-1.4 structure, and 6% vinyl structure.

Example 3 (i) Preparation of polymerization catalyst (3) Same as Example 1, neodymium octenoate
After impregnating 0.3 mmol with 0.6 mmol of acetylacetone and dissolving it in 40 ml of n-hexane, titanium tetrachloride
1.35 mmol was added dropwise with stirring to produce a red colored precipitate. This precipitate was washed five times with 40 ml of n-hexane. Thereafter, the precipitate was made into a suspension in 20 ml of n-hexane and used as a catalyst component (A-3). ICP this
Measured with an emission spectrometer JY38P
The Ti/Nd ratio was 1.42.

This catalyst component (A-3) in terms of Ti
0.037 mmol was collected, and 0.6 mmol of triisobutylaluminum was added as a catalyst component (B-3) to obtain a polymerization catalyst (3).

(ii) Polymerization of butadiene Same as Example 1, polymerization catalyst (3) (Nd equivalent)
0.026 mmol (0.037 mmol in terms of Ti) was used to polymerize 8.9 g (164 mmol) of butadiene. The obtained polymer was 1.68g (460g-polymer/g-
Nd·h, 970g-polymer/g-Ti·h). The microstructure is 21% trans-1.4 structure,
The cis-1.4 structure accounted for 66% and the vinyl structure accounted for 14%.

Comparative Example 1 0.05 mmol of titanium tetrachloride and 0.15 mmol of triisobutylaluminum were mixed in 20 ml of n-hexane to prepare a catalyst.

Using this polymerization catalyst, 8.9 g (164 mmol) of butadiene was polymerized in the same manner as in Example 1, and the resulting polybutadiene was 0.01 g (4 g-polymer/g-
It was Ti・h).

Comparative Example 2 0.05 mmol of titanium tetrachloride and 0.20 mmol of triisobutylaluminum were mixed in 20 ml of n-hexane to prepare a polymerization catalyst. Furthermore, using this polymerization catalyst, 8.9 g (164 mmol) of butadiene was produced in the same manner as in Example 1.
When polymerized, the obtained polybutadiene was
It was 0.08g (32g-polymer/g-Ti.h).

Comparative Example 3 0.05 mmol of titanium tetrachloride and 0.50 mmol of triisobutylaluminum were mixed in 20 ml of n-hexane to prepare a polymerization catalyst. Furthermore, using this polymerization catalyst, 8.9 g (164 mmol) of butadiene was produced in the same manner as in Example 1.
When polymerized, no polymer was obtained.

Comparative Example 4 0.03 mmol of neodymium octenoate was impregnated with 0.06 mmol of acetylacetone, then dissolved in 20 ml of n-hexane, and 1.2 mmol of triisobutylaluminum was added to prepare a polymerization catalyst.

When 8.9 g (164 mmol) of butadiene was polymerized using this polymerization catalyst in the same manner as in Example 1, no polymer was obtained.

Comparative Example 5 0.03 mmol of neodymium octate was impregnated with 0.06 mmol of acetylacetone, then dissolved in 20 ml of n-hexane, and diethylaluminium monochloride was added.
1.2 mmol was added to serve as a polymerization catalyst. Using this polymerization catalyst, 8.9 g of butadiene was prepared in the same manner as in Example 1.
(164 mmol), no polymer was obtained.

Example 4 Polymerization catalyst (3) of Example 3 (0.026 mmol in terms of Nd,
Ethylene was polymerized in the same manner as in Example 3 using 4.6 g (164 mmol) of ethylene instead of butadiene in Example 3. The obtained polymer was 2.17 g (580 g-polymer/g-
Nd·h, 1230g-polymer/g-Ti·h). The melting point of the obtained polyethylene was 139°C.

Example 5 Polymerization catalyst (3) of Example 3 (0.026 mmol in terms of Nd,
Propylene was polymerized in the same manner as in Example 3 using 6.9 g (164 mmol) of propylene instead of butadiene in Example 3. The obtained polypropylene was 2.09g (570g polymer/g
-Nd·h, 1210 g polymer/g-Ti·h).

Example 6 (i) Preparation of polymerization catalyst (6) Same as Example 1, neodymium octenoate
A catalyst component (A-6) was prepared using 0.3 mmol of titanium tetrachloride, 0.6 mmol of acetylacetone, 2.55 mmol of titanium tetrachloride, and 10 ml of n-hexane.

Furthermore, 3.6 mmol of triisobutylaluminum was added as the catalyst component (B-6).
6) was added dropwise with stirring to obtain a polymerization catalyst (6).

(ii) Ethylene/butadiene copolymerization 20 ml of n-hexane was placed as a solvent in a 100 ml pressure-resistant stainless steel autoclave purged with nitrogen, and 0.03 mmol (Ti
0.255 mmol) of polymerization catalyst (6) was added, and after cooling and degassing under liquid nitrogen temperature, 8.92 mmol of butadiene was added.
(164 mmol) and 4.6 g (164 mmol) of ethylene were introduced. While keeping this reaction vessel at 50℃,
The mixture was left stirring for an hour. After the reaction was completed, a large amount of methanol containing an antiaging agent was added to wash the polymer, and the polymer was dried under reduced pressure overnight. The obtained white polymer weighed 5.80g (480g polymer/g・Ti・h,
The composition of ethylene and butadiene units in the polymer was 60 mmol% ethylene and 40 mol% butadiene.
The microstructure of the butadiene unit is trans-
1.4 structure was 54%, -cis-1.4 structure was 38%, and vinyl structure was 8%.

Example 7 (i) Preparation of polymerization catalyst (7) Same as Example 1, neodymium octenoate
A catalyst component (A-7) was prepared using 0.3 mmol of acetylacetone, 0.6 mmol of acetylacetone, 0.75 mmol of titanium tetrachloride, and 10 ml of n-hexane.

Furthermore, 6 mmol of triisobutylaluminum was added as the catalyst component (B-7) to the catalyst component (A-7).
was added dropwise with stirring to obtain a polymerization catalyst (7).

(ii) Copolymerization of ethylene and butadiene As in Example 6, the polymerization catalyst (7) was
Copolymerization of ethylene and butadiene was carried out using 0.03 mmol (0.075 mmol in terms of Ti). The obtained polymer was 4.69g (1.08Kg polymer/g Nd
hr, 1.30Kg polymer/g Ti hr), and the proportions of ethylene and butadiene units are respectively
They were 83 mol% and 170 mol%.

Comparative Example 6 0.03 mmol of neodymium octate was impregnated with 0.06 mmol of acetylacetone, then dissolved in 20 ml of n-hexane to prepare diethylaluminium monochloride.
0.12 mmol was added, and further 1.08 mmol of triisobutylaluminum was added to serve as a polymerization catalyst.

4.8 g of ethylene in the same manner as in Example 6
(164 mmol) and 8.9 g (164 mmol) of butadiene were polymerized. The resulting polymer weighed 0.25g (60g polymer/gNdh) and was a homopolymer of polybutadiene. The microstructure of this polymer is cis-
1.4 structure was over 98%.

Example 8 Using the polymerization catalyst (3) of Example 3, copolymerization of ethylene and butadiene was carried out in the same manner as in Example 6. The obtained polymer was 4.96g (1300g polymer/g
Nd h, 2800 g polymer/g Ti h). The ethylene and butadiene units in the polymer are 78 mol% and 22 mol%, respectively, and the microstructure of the butadiene unit is trans-1.4.
37%, 48% cis-1.4 structure, and 15% vinyl structure.

Example 9 2.3 g (82 mmol) of ethylene, 3.4 g (82 mmol) of propylene, and 4.4 g of butadiene were produced in the same manner as in Example 6 using the polymerization catalyst (3) of Example 3.
(82 mmol) was copolymerized.

The obtained polymer was 3.74g (2000g polymer/
gNdh, 2100g polymer/gTih). Ethylene, propylene, and butadiene units in the polymer are 32 mol%, 15 mol%, and 53 mol%, respectively.
It was hot.

Example 10 (i) Preparation of polymerization catalyst (10) 2.55 mmol of titanium trichloride and 10 mmol of pyridine
is added, and after the complex is formed, it is dried under reduced pressure to remove excess pyridine. A polymerization catalyst (10) was prepared in the same manner as in Example 1, except that this complex was made into a suspension in 10 ml of n-hexane and used in place of titanium tetrachloride in Example 1.

(ii) Copolymerization of ethylene and butadiene Ethylene and butadiene were polymerized in the same manner as in Example 6 except that the above catalyst components were used. The obtained polymer was 1.58g (440g/g・Ti・h, 370
g/g・Nd・h), and the composition of each unit was 58 mol% ethylene and 42 mol% butadiene.

Example 11 (i) Preparation of polymerization catalyst (11) Precipitation was produced in the same manner as in Example 1 from neodymium octenoate, titanium tetrachloride, and n-hexane using 0.6 mmol of pyridine instead of acetylacetone in Example 1. . Thereafter, it was washed five times with 40 ml of n-hexane to obtain a catalyst component (A-11).

Ti atoms in this suspension were determined using an atomic absorption spectrometer.

Catalyst component (A-11) in terms of Ti atoms
0.030 mmol was collected and diisobutylaluminum chloride was used as the catalyst component (B-11).
0.48 mmol was added to form a polymerization catalyst (11).

(ii) Copolymerization of ethylene and butadiene Ethylene and butadiene were copolymerized in the same manner as in Example 6 except that the reaction was carried out for 15 minutes instead of 1 hour in the method of Example 6. The obtained polymer is 3.54
g (9900 g polymer/g Ti h).
The ethylene and butadiene units in the polymer were 54 mol% and 45 mol%, respectively.

Example 12 (i) Preparation of polymerization catalyst (12) Precipitation was produced in the same manner as in Example 1 from neodymium octenoate, titanium tetrachloride, and n-hexane, using 0.6 mmol of dimethyl sulfoxide instead of acetylacetone in Example 1. I let it happen. Then n-
Wash with 40ml of hexane 5 times and catalyst component (A-12)
And so.

Ti atoms in this suspension were determined using an atomic absorption spectrometer.

Catalyst component (A-12) in terms of Ti atoms
0.03 mmol was collected, and 0.9 mmol of diisobutylaluminum chloride was used as the catalyst component (B-12).
was added to obtain a polymerization catalyst (12).

(ii) Copolymerization of ethylene and butadiene Ethylene and butadiene were copolymerized in the same manner as in Example 6 except that the reaction was carried out for 15 minutes instead of 1 hour in the method of Example 6. The obtained polymer is 3.65
g (10000g polymer/g Ti h),
The ethylene and butadiene units in the polymer were 35 mol% and 65 mol%, respectively.

Example 13 (i) Preparation of polymerization catalyst (13) Using a reaction product obtained by adding 0.12 mmol of t-butanol dropwise with stirring to 0.60 mmol of diisobutylaluminum chloride as the catalyst component (B-13), the catalyst component (A-3) of Example 3 was prepared. ) in terms of Ti
0.037 mmol was collected and catalyst component (13) was prepared in the same manner as in Example 3.

(ii) Copolymerization of ethylene and butadiene Ethylene and butadiene were copolymerized in the same manner as in Example 6 except that the reaction was carried out for 15 minutes instead of 1 hour in the method of Example 6. The obtained polymer is 4.82
g (5100 g polymer g Nd h, 10900 polymer/g Ti h), and the ethylene and butadiene units in the polymer are each 42 mol%.
It was 58 mol%.

Example 14 (i) Preparation of polymerization catalyst (14) Acetylacetone, titanium tetrachloride, n-
A catalyst component (A-14) was prepared from hexane.

3.6 mmol of diisobutylaluminum chloride was used as the catalyst component (B-14).
14) was added dropwise with stirring to obtain a polymerization catalyst (14).

(ii) Copolymerization of ethylene and butadiene Same as Example 6, polymerization catalyst (14) (in terms of Pr)
0.03 mmol (0.255 mmol in terms of Ti) was used to copolymerize ethylene and butadiene.

The obtained polymer was 3.64 g (860 g polymer/g Pr h, 300 g polymer/g Ti h)
The ethylene and butadiene units in the polymer were 32 mol% and 68 mol%, respectively.

[Brief explanation of drawings]

FIG. 1 is a flowchart showing the steps for preparing a catalyst used in the method of the present invention.

Claims (1)

[Claims] 1. General formula LnY ₃ (Ln is neodymium or praseodymium, Y is RCOO-, -OR, -SR, -NR ₂ or X, where R is a carbonized compound having 1 to 20 carbon atoms) A catalyst component (A) prepared by adding titanium halide to a reaction product or mixture of a neodymium or praseodymium compound represented by a hydrogen group (X is a halogen atom excluding fluorine) and a Lewis base, and a catalyst component (A) with the general formula AlR ¹ _o X _3-o (X is hydrogen or halogen,
R ¹ is a hydrocarbon group having 1 to 20 carbon atoms, n is 1,
1.5, 2 or 3) or the reaction product of the organoaluminum compound and an alcohol represented by the general formula R ² OH (wherein R ² is a hydrocarbon group having 1 to 30 carbon atoms) A catalyst for the polymerization of olefins and/or conjugated dienes, which comprises a catalyst component (B) which is a substance.