JPS648009B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing ethylene copolymer rubber with good processability, high tensile strength, and excellent randomness in a high yield using a Ziegler catalyst soluble in a solvent. It is.

As a catalyst for producing a rubber-like copolymer by randomly copolymerizing two or more types of olefins, a combination catalyst of a homogeneous vanadium compound and an organoaluminum compound has conventionally been widely used.

However, these homogeneous vanadium catalysts are generally very easily deactivated during polymerization, and their activity is not very high at practical polymerization temperatures of 30 to 60°C.

On the other hand, a combination catalyst of a titanium compound and an organoaluminum compound is generally known as a catalyst that is relatively less deactivated during polymerization. However, when this titanium compound is used as a catalyst, each olefin is likely to be homopolymerized, forming a mixture of individual homopolymers, or copolymerizing into a block shape. Therefore, the production of rubber-like elastic copolymers using titanium-based catalysts has not been successful so far.

Recently, several patents have been filed for producing ethylene/α-olefin elastic copolymers using titanium-based catalysts. An example of this is JP-A-Sho.
Examples include JP-A No. 49-51381, JP-A-50-117886, and JP-A-53-104687. These attempts to randomly copolymerize ethylene and α-olefin using a combination catalyst of a solid catalyst component supporting a titanium compound on a carrier and an organoaluminium compound component, but the randomness of the resulting copolymer is Because it is not good, it partially precipitates in the hydrocarbon solvent during polymerization. Therefore, it is difficult to perform solution polymerization using these catalysts.

Furthermore, the produced polymer is plastic-like and difficult to use in the rubber field. Therefore, the present inventors thought that it would be difficult to produce a random copolymer of olefin using a solid titanium-based catalyst, and attempted to research a method using a titanium compound in a solution state. However, titanium compounds that are soluble in organic solvents and have olefin polymerization activity include titanium tetrachloride, titanium triacetylacetonate, and tetrabutoxytitanium. When these olefins are copolymerized, a mixture of each homopolymer or a block copolymer is likely to be produced, and a rubber-like copolymer cannot be obtained.

The present inventors thought that in order to perform random copolymerization, it would be necessary to reduce titanium tetrachloride in advance while keeping it in a liquid state.

Conventionally, various methods are known for producing solid titanium trichloride. For example, there is a method in which titanium tetrachloride is reduced with metallic titanium, metallic aluminum, an organoaluminum compound, an organomagnesium compound, hydrogen, or the like. Among these, titanium trichloride obtained by reducing titanium tetrachloride with hydrogen has a high utility value because it contains few impurities and can be added with the required amount of other metal compounds depending on the purpose.

A method to obtain solid titanium trichloride by reducing titanium tetrachloride with hydrogen is to reduce titanium tetrachloride and hydrogen.
A method of contacting titanium tetrachloride and hydrogen at a high temperature of 800°C under high pressure, and a method of contacting titanium tetrachloride with hydrogen under high voltage without static discharge are known. However, using these known methods, it is impossible to reduce titanium tetrachloride while keeping it in a liquid state.

In a short period of time under mild conditions, the present inventors
Moreover, for many years, we have been intensively researching a method for producing a liquid material containing titanium trihalide by reducing titanium tetrahalide with hydrogen at low cost.

As a result, a liquid obtained by treating titanium tetrahalide with (1) hydrogen in the presence of ether and at least one Group B, B, B, metal of the periodic table or its compound in an organic solvent. thing or (2)
A surprising thing happened when copolymerization of ethylene and propylene or/and butene-1 was carried out using a combination of a liquid obtained by treating hydrogen with an organomagnesium compound and/or an organoaluminum compound and an organoaluminum compound as a catalyst. The present inventors have discovered that it is possible to obtain a substantially amorphous rubber-like elastic copolymer that exhibits extremely high activity, excellent randomness, good processability, and high tensile strength.

That is, the present invention provides (A) an ether and at least one type of periodic table B in an organic solvent.
B. A liquid obtained by treating titanium tetrahalide in the presence of a group metal or its compound with (1) hydrogen or (2) hydrogen and an organomagnesium compound and/or an organoaluminum compound. Ethylene and propylene or/and
The present invention provides a method for producing an ethylene copolymer rubber, which comprises copolymerizing ethylene copolymer rubber and butene-1.

The present invention will be explained in more detail below.

The catalyst component (A) that can be used in the present invention comprises titanium tetrahalide (1 ) a liquid obtained by treatment with hydrogen; or (2) a liquid obtained by treatment with hydrogen and an organomagnesium compound and/or an organoaluminum compound.

Titanium tetrahalides that can be used in the present invention include titanium tetrachloride, titanium tetrabromide, and titanium tetraiodide, and mixtures thereof can also be used.

High purity hydrogen is preferred. Oxygen or oxygen-containing compounds (CO, CO ₂ ) contained in hydrogen
Up to 50 ppm, preferably up to 20 ppm of hydrogen is used.

The ether used in the present invention has the general formula R ¹ OR ² (2) (wherein R ¹ and R ² are the same or different alkyl groups or alkenyl groups having 1 to 20 carbon atoms, preferably 2 to 12 carbon atoms, Ethers represented by aryl or aralkyl groups are used, and specific examples thereof include the following ethers.

(1) Dialkyl ether diethyl ether, di-n-propyl ether, di-n-butyl ether, di-n-hexyl ether, di-n-octyl ether, di-
n-decyl ether, di-n-dodecyl ether, hexyl octyl ether, dicyclohexyl ether, etc. (2) Dialkenyl ether bis(1-octenyl) ether, bis(1-octenyl) ether,
-decynyl)ether, 1-octenyl-9-
Decynyl ether, etc. (3) Diarakyl ether Bis(benzyl) ether, etc. (4) Alkyl alkenyl ether n-octyl-1-decynyl ether, n-
Decyl-1-decynyl ether, etc. (5) Alkyl aralkyl ether n-octyl benzyl ether, n-decyl benzyl ether, etc. (6) Aralkyl alkenyl ether 1-octenyl benzyl ether, etc. (7) Alkylaryl ether Anisole, etc. (8) Diaryl ether, diphenyl ether, etc. These ethers can be used in combination of two or more. Among these ethers, ethers in which R ₁ and R ₂ of formula (1) are alkyl groups are preferred.

Periodic table B, B, which can be used in the present invention
Examples of Group B metals or compounds thereof include the following. Examples of metals include copper,
Metals such as silver, zinc, titanium, zirconium, iron, cobalt, nickel, ruthenium, rhodium, palladium, iridium, platinum, alloys of these metals, powders, granules, solids such as sponge, or carbon, alumina, silica, etc. Powders, granules, granules, pellets, etc. supporting these metals can be used. Compounds of these metals include chlorides, oxides, hydrides, sulfides, sulfates, and nitrates. For example, cuprous chloride,
Zirconium hydride, titanium hydride, primary chloride
Iron, cobalt chloride, nickel chloride, palladium chloride, platinum chloride, rhodium chloride, iridium chloride,
These include ferrous oxide, palladium oxide, platinum oxide, palladium sulfide, platinum sulfide, palladium sulfate, platinum sulfate, palladium nitrate, cobalt nitrate, rhodium nitrate, and platinum nitrate. Compounds modified by adding small amounts of organic or inorganic substances to these metals or these metal compounds also essentially fall within the scope of the present invention. A mixture of two or more of these compounds can also be used. Among these metals or compounds, preferred are metals or compounds listed in Periodic Table B,
B, B and group metals or compounds of group metals or hydrides of cuprous chloride, titanium or zircon; particularly preferred are group metals and their compounds. Most preferably palladium,
Platinum metal or its compounds.

Organic solvents that can be used in preparing the catalyst component (A) are hydrocarbons or halogenated hydrocarbons.

Hydrocarbons include n-bentane, n-hexane, n-heptane, n-octane, n-decane,
Carbon number 5-20 like kerosene and liquid paraffin
Saturated aliphatic hydrocarbons having 5 to 12 carbon atoms such as cyclohexane and methylcyclohexane are most suitable.
Saturated alicyclic hydrogen, benzene, toluene, and other aromatic hydrocarbons having 6 to 9 carbon atoms may also be used.

Examples of halogenated hydrocarbons include halides of saturated aliphatic hydrocarbons having 1 to 12 carbon atoms, and
Examples include halides of 12 saturated alicyclic hydrocarbons and halides of aromatic hydrocarbons having 6 to 9 carbon atoms, and specific examples thereof are shown below.

Halides of saturated aliphatic hydrocarbons Methylene chloride, chloroform, carbon tetrachloride, monochloroethane, ethyl iodide, 1,2-
dichloroethane, 1,1-dichloroethane, 1,
1,2-trichloroethane, 1,1,2,2-tetrachloroethylene, n-butyl chloride, n-iodide
- Halides of saturated alicyclic hydrocarbons such as butyl, halides of aromatic hydrocarbons such as chlorocyclohexane, chlorobenzene, benzene bromide, benzene iodide, orthodichlorobenzene, etc. Among these halogenated hydrocarbon solvents, preferred are A halide of a saturated aliphatic hydrocarbon having 1 to 12 carbon atoms is used. These hydrocarbon solvents,
Two or more halogenated hydrocarbon solvents may be used as a mixture.

Among these organic solvents, when using a hydrocarbon solvent, R ¹ of the ether represented by formula (1),
It is preferable to use an ether in which R ² has 6 to 20 carbon atoms.

The organomagnesium compound used in the present invention has the general formula RMgX...(2) (wherein R has 1 to 20 carbon atoms, preferably 1 carbon number)
~12 hydrocarbon groups, X is the same hydrocarbon group as R,
1 to 1 carbon atoms bonded via N, O or S atoms
20, preferably 1 to 12 hydrocarbon groups or halogen atoms. ), and
Particularly preferred are compounds in which R in the formula is a linear alkyl group or alkenyl group.

Examples of organomagnesium compounds used include, for example, diethylmagnesium, dibutylmagnesium, ethylmagnesium chloride, butylmagnesium chloride, octylmagnesium chloride, ethylmagnesium bromide, butylmagnesium bromide, ethylmagnesium iodide, butylmagnesium iodide, octylmagnesium iodide,
Ethyl n-butoxymagnesium, n-butyl n
-butoxymagnesium, diethylaminoethylmagnesium, diethylamino n-butylmagnesium, di-n-butylamino n-butylmagnesium, ethyl n-butylthiomagnesium, n
-butyl n-butylthiomagnesium and the like. Two or more types of organomagnesium compounds can also be used in combination.

Further, a small amount of an organometallic compound of Groups 1 to 10 of the periodic table other than magnesium may also be used.

Examples of organoaluminum compounds that can be used in preparing the catalyst component (A) in the present invention include compounds represented by the general formula (2) of the catalyst component (B) described below.

In the present invention, the method for preparing the catalyst component (A) is not particularly limited. For example, (1) in an organic solvent, ether and periodic table B, B, B,
A method in which titanium tetrahalide is added in the presence of a group metal or its compound and hydrogen gas is blown under atmospheric pressure. A method of adding a metal or its compound, titanium tetrahalide, and contacting it by pressurizing hydrogen gas, (3) periodic table B, B,
B. A method of contacting an organic solvent solution of titanium tetrahalide and ether with hydrogen gas in a countercurrent manner under atmospheric pressure or under pressure in the presence of a group metal or its compound; A method in which titanium tetrahalide is added in the presence of a group B, B, B metal of the periodic table or a compound thereof, hydrogen gas is blown under atmospheric pressure, and then an organomagnesium compound is added, (5) organic After contacting the titanium tetrahalide and the organomagnesium compound in the presence of ether in a solvent,
A method of adding B, B, group metal or its compound and blowing hydrogen gas under atmospheric pressure, (6) a method of adding an organic solvent, ether, periodic table B, B, to a pressurized reactor,
After adding B, group metal or its compound, and titanium tetrahalide and reacting by injecting hydrogen gas,
A method of adding an organomagnesium compound, (7) an organic solvent solution of titanium tetrahalide and ether in the presence of a metal of Group B, B, B of the periodic table or a compound thereof, at atmospheric pressure or under pressure. A method is used in which an organomagnesium compound is added after contacting hydrogen gas in a countercurrent manner.
This liquid material may be used as it is, or metals of groups B, B, and B of the periodic table or compounds thereof may be separated and used as necessary.

Hydrogen can be used in combination with an inert gas such as nitrogen, argon, helium, etc. The pressure used when contacting with hydrogen is preferably in the range of atmospheric pressure to 100 kg/cm ² . The temperature when contacting with hydrogen is -50°C to 200°C, preferably -30°C to 150°C.

Further, when the catalyst component (A) is prepared by contacting titanium tetrahalide with hydrogen gas, it is also possible to have a small amount of α-olefin, such as propylene, 1-butene, 1-hexyl, etc., present.

The molar ratio of titanium tetrahalide and ether used in these methods is preferably from 1:0.2 to
The ratio is 1:20, particularly preferably in the range of 1:0.5 to 1:5. It is sufficient that metals of groups B, B, B of the periodic table or their compounds are present in catalytic amounts, and it is uneconomical if they are used in large amounts. That is, the molar ratio with titanium tetrahalide is preferably 0.00001 to 10.
It is 0.0001 to 1. The molar ratio of the organomagnesium compound or organoaluminium compound to titanium tetrahalide is in the range of 0.05 to 0.9, preferably 0.1 to 0.75. When an organomagnesium compound and an organoaluminum compound are used together, the sum of the moles of both is 0.05 to 0.9 (molar ratio) to the titanium compound, preferably 0.1 to 0.75.

The organoaluminum compound of the catalyst component (B) used in the present invention has the general formula _{A1R n}
is a halogen or an alkoxy group having 1 to 12 carbon atoms,
Organoaluminum compounds with the formula 1≦m≦3) are generally suitable. Two or more types of compounds may be combined. Specific examples of organoaluminum compounds include triethylaluminum, trinium
-propyl aluminum, tri-i-butyl aluminum, tri-n-octyl aluminum, tri(2-methylpentyl) aluminum, di-i
-butylaluminum hydride, ethylaluminum sesquichloride, diethylaluminum chloride, ethylaluminum dichloride, diethylaluminum ethoxide, diethylaluminium iodide, and the like. Among these organoaluminum compounds, trialkylaluminum compounds are particularly preferred. catalyst component
The ratio of (A) to catalyst component (B) is expressed as the atomic ratio of titanium to aluminum, and is usually in the range of 1:0.2 to 1:200, preferably in the range of 1:1 to 1:50. It will be done.

As monomers for polymerization, ethylene, propylene, and α-olefins of butene-1 can be used. A rubber-like copolymer can be obtained by copolymerizing a combination of ethylene and the above α-olefin.

Furthermore, in order to facilitate the vulcanization of the copolymer rubber, a non-conjugated polyene monomer can be copolymerized with the olefin monomer. The non-conjugated polyene is selected from arbitrary types such as cross-linked hydrocarbon compounds, monocyclic compounds, heterocyclic compounds, chain compounds, and spiro-type compounds. Specifically, dicyclopentadiene, tricyclopentadiene, 5-methyl-2,5-norbornadiene, 5
-methylene-2-norbornene, 5-ethylidene-2-norbornene, 5-isopropylidene-2
-norbornene, 5-isopropenyl-2-norbornene, 5-(1-butenyl)-2-norbornene, 5-(2'-butenyl)-2-norbornene, cyclooctadiene, vinylcyclohexene, 1,
5,9-cyclododecatriene, 6-methyl-
4,7,8,9-tetrahydroindene, 2,
2'-dicyclopentenyl, trans-1,2-divinylcyclobutane, 1,4-hexadiene,
Examples include 1,6-octadiene and 6-methyl-1,5-heptadiene.

Polymerization temperature is usually 0~120℃, preferably 20~80℃
It is ℃. Polymerization pressure usually ranges from normal pressure to 50 kg/cm ² . In general, a solution polymerization method in which copolymerization is carried out in a good solvent for the copolymer is suitable for the copolymerization. As the solvent at that time, hydrocarbon solvents such as n-hexane and n-heptane are often used. Copolymerization may be batch polymerization or continuous polymerization. The molecular weight of the copolymer can be arbitrarily adjusted by using hydrogen as necessary.

Next, the present invention will be explained in more detail with reference to Examples. In addition, the measured values of various physical properties of the copolymer in the examples are as follows: Mooney viscosity: preheating for 1 minute, measurement for 4 minutes, temperature: 100℃
The propylene content was determined by infrared absorption spectrum, the iodine number was determined by titration, and the 100% modulus, tensile strength, elongation at break, and Shore A hardness were determined by a measurement method based on JIS K6301. .

In the following Examples and Comparative Examples, the infrared absorption spectra of 730 cm ^-1 (absorption due to crystallinity of polyethylene) and 720 cm ^-1 ((-CH ₂ - ) _o
The intensity ratio (absorption due to skeletal vibration) was expressed as shown in Figure 2, and the area of each was determined and calculated using the following formula to determine the random index (RI).

RI (%) (Area of B) / (Area of A + B) x 10
0 Example 1 (1) Preparation of catalyst component (A) 50 mg of dried powdered platinum black and 1.2 mg of dried powdered platinum black were placed in a 100 ml flask that had been thoroughly dried and purged with nitrogen.
-50 ml of dichloroethane and 10 mmol of titanium tetrachloride
and then add n-butyl ether while stirring.
3.4 ml was added over 5 minutes [Ether/Ti=2.0
(molar ratio)]. Keep the flask at 20℃ and add 0.2 hydrogen
The air was blown at a speed of /min for 2 hours. A yellow-black solution formed. The solution was filtered under nitrogen to separate the powdered platinum black. The liquid was a homogeneous yellow-black solution.

(2) Copolymerization A stirring blade, a three-way pot, a gas blowing tube, and a thermometer were attached to the separable flask in Step 3, and the flask was sufficiently purged with nitrogen and dried. N-hexane 2, which had been dried with molecular sieves and degassed, was placed in the flask. A mixed gas of 4/min of ethylene, 6/min of propylene, and 0.1/min of hydrogen, which had been dried through a molecular sieve, was bubbled through a gas blowing tube into a flask whose temperature was controlled at 35° C. for 10 minutes. After this, 7.0 mmol of tri-i-butylaluminum (B) and the aforementioned catalyst component were added.
0.7 mmol of (A) was added in terms of titanium, and copolymerization was started while passing the mixed gas at the above flow rate. The temperature inside the flask was maintained at 35°C and copolymerization was carried out for 30 minutes. Copolymerization was stopped by adding 50 ml of methanol to the polymerization solution. During the copolymerization, the solution was homogeneous, and no copolymer precipitation was observed during the copolymerization. After adding a small amount of anti-aging agent and 1 part of water and stirring well, a solid rubber was obtained by steam stripping. The copolymer yield was 62g. The RI value determined from the infrared absorption spectrum of the copolymer was 0.4%. The physical properties of the copolymer obtained in this example are as follows.

Propylene content = 30wt% ML ¹⁰⁰ ℃ ₁₊₄ = 74 100% modulus = 12Kg/cm ² Tensile strength = 50Kg/cm ² Elongation at break = 3000% Shore A hardness = 52 Comparative example 1 Copolymerization was carried out in the same manner as in Example 1, except that titanium chloride was used as it was as a catalyst. A large amount of copolymer precipitated during copolymerization, and copolymerization proceeded in a slurry state. The copolymer yield is 8g, and the propylene content in the copolymer is
It was 38wt%. Furthermore, the RI value determined from the infrared absorption spectrum of the copolymer was 3.1%.

Comparative Example 2 A compound was prepared in the same manner as in Example 1 except that a 1,2-dichloroethane solution of a complex of titanium tetrachloride and di-n-butyl ether (titanium and ether are equimolar) was used instead of the catalyst component (A). Polymerization was carried out.
A large amount of copolymer precipitated during copolymerization, and copolymerization proceeded in a slurry state. The copolymer yield was 6 g, and the propylene content in the copolymer was 36 wt%. In addition, the infrared absorption spectrum of the copolymer determined
The RI value was 2.9%.

Comparative Example 3 Copolymerization was carried out in the same manner as in Example 1, except that a 1,2-dichloroethane slurry of solid titanium trichloride (hydrogen-reduced product) was used in place of the catalyst component (A). During the copolymerization, a large amount of copolymer was precipitated, and the copolymerization proceeded in a slurry state. Copolymer yield is 11
g, propylene content in the copolymer is 37wt%, RI is
It was 3.3%.

Example 2 A hexane solution of 5-ethylidene-2-norbornene was supplied at a rate of 8 ml/min (2.09 mmol/min of 5-ethylidene-2-norbornene) for 25 minutes from the start of copolymerization to 5 minutes before the end. Copolymerization was carried out in the same manner as in Example 1 except for this. The solution during copolymerization was homogeneous, and no precipitation of copolymer was observed during polymerization. Copolymer yield is 55
It was hot at g. The RI value determined from the infrared absorption spectrum of the copolymer was 0.6%.

The physical properties of the copolymer obtained in this example are as follows.

Propylene content = 32wt% Yoso value = 18 ML ¹⁰⁰ ₁₊₄ = 73 100% modulus = 13Kg/cm ² Tensile strength = 68Kg/cm ² Elongation at break = 3060% Shore A hardness = 53 Example 3 5-ethylidene-2- Copolymerization was carried out in the same manner as in Example 2 except that dicyclopentadiene was supplied at a rate of 2.09 mmol/min instead of norbornene. The solution during polymerization was homogeneous, and no precipitation of copolymer was observed during copolymerization. The yield of the copolymer was 53 g, the propylene content in the polymer was 33 wt%, and the iodine number was 19. The RI value determined from the infrared absorption spectrum of the copolymer was 0.7%.

Example 4 Catalyst component (A) was prepared in the same manner as in Example 1, except that 100 mg of palladium carbon powder (palladium content 5%) was used instead of powdered platinum black. A yellow-black homogeneous solution was obtained.

Copolymerization was carried out in the same manner as in Example 1. The solution during copolymerization was homogeneous, and no precipitation of copolymer was observed during copolymerization. The copolymer yield was 64 g, and the propylene content in the copolymer was 35 wt%. The RI value determined from the infrared absorption spectrum of the copolymer was 0.4%.

Example 5 Catalyst component (A) was prepared in the same manner as in Example 1 except that powdered platinum black was replaced with powdered palladium nitrate. A yellow-black homogeneous solution was obtained.

Copolymerization was carried out in the same manner as in Example 1. The solution during polymerization was homogeneous, and no precipitation of copolymer was observed during copolymerization. The copolymer yield was 56 g, and the propylene content in the copolymer was 32 wt%. The RI value determined from the infrared absorption spectrum of the copolymer was 0.4%.

Example 6 Catalyst component (A) was prepared in the same manner as in Example 1 except that 50 mg of powdered palladium oxide was used instead of powdered platinum black. A yellow-black homogeneous solution was obtained.

Copolymerization was carried out in the same manner as in Example 1. The solution during polymerization was homogeneous, and no precipitation of copolymer was observed during copolymerization. The copolymer yield was 66 g, and the propylene content in the copolymer was 36 wt%. The RI value determined from the infrared absorption spectrum of the copolymer was 0.4%.

Example 7 (1) Preparation of catalyst component (A) 1 g of dried powdered Raney cobalt, 50 ml of 1,2-dichloroethane, and 10 mmol of titanium tetrachloride were charged into a 100 ml stainless steel autoclave that had been sufficiently dried and purged with nitrogen. While stirring, 3.4 ml of n-butyl ether was added over 5 minutes [ether/Ti=20 (molar ratio)]. Next, add 8 hydrogen
The mixture was pressurized to Kg/cm ² and reacted at 100°C for 10 hours.
After the reaction, the mixture was filtered under nitrogen to separate powdered Raney cobalt. The liquid was a homogeneous yellow-black solution.

(2) Copolymerization Copolymerization was carried out in the same manner as in Example 1. The solution during polymerization was homogeneous, and no precipitation of copolymer was observed during copolymerization. Copolymer yield is 45g
and the propylene content in the copolymer is 29wt
It was %. The RI value determined from the infrared absorption spectrum of the copolymer was 0.7%.

Example 8 Catalyst component (A) was prepared in the same manner as in Example 1 except that 700 mg of powdered copper was used instead of powdered platinum black.
was prepared. A yellow-black homogeneous solution was obtained.

Copolymerization was carried out in the same manner as in Example 1. The solution during copolymerization was homogeneous, and no precipitation of the copolymer was observed during copolymerization. The yield of copolymer is 55g
The propylene content of the copolymer was 32 wt%. The RI value determined from the infrared absorption spectrum of the copolymer was 0.5%.

Example 9 Catalyst components were prepared in the same manner as in Example 1, except that 700 mg of powdered zinc was used instead of powdered platinum black.
(A) was prepared. A yellow-black homogeneous solution was obtained.

Copolymerization was carried out in the same manner as in Example 1. The solution during copolymerization was homogeneous, and no precipitation of copolymer was observed during copolymerization. The copolymer yield was 58 g, and the propylene content in the copolymer was 34 wt%. The RI value determined from the infrared absorption spectrum of the copolymer was 0.5%.

Example 10 Catalyst component (A) was prepared in the same manner as in Example 1 except that powdered platinum black was replaced with powdered titanium.
was prepared. A yellow-black homogeneous solution was obtained.

Copolymerization was carried out in the same manner as in Example 1. The solution during polymerization was homogeneous, and no precipitation of copolymer was observed during copolymerization. The copolymer yield was 56 g, and the propylene content in the copolymer was 33 wt%. The RI value determined from the infrared absorption spectrum of the copolymer was 0.5%.

Example 11 1,2-dichloroethane to n-hexane, n
-3.4 ml of butyl ether to n-octyl ether
Catalyst component (A) was prepared in the same manner as in Example 1 except that the amount was changed to 7.6 ml. A yellow-black homogeneous solution was obtained.

Copolymerization was carried out in the same manner as in Example 1. The solution during copolymerization was homogeneous, and no precipitation of copolymer was observed during copolymerization. The copolymer yield was 60 g, and the propylene content in the copolymer was 32 wt%. The RI value determined from the infrared absorption spectrum of the copolymer was 0.5%.

Example 12 (1) Preparation of catalyst component (A) Dry powdered palladium-carbon in a 100 ml flask that has been thoroughly dried and purged with nitrogen.
100mg of titanium tetrachloride, 50ml of 1,2-dichloroethane, and 10mmol of titanium tetrachloride were added, and then n-
3.4 ml of butyl ether was added over 5 minutes. Keep the inside of the flask at 10℃ and add hydrogen gas at 0.2/
It was blown for 2 hours at a speed of min. A yellow-black solution formed. It was filtered under nitrogen to separate the powdered palladium on carbon (Pd content 5%).
This liquid was cooled to 0° C., and while stirring, 2 mmol of n-butylmagnesium iodide was added as a solution in n-butyl ether over 10 minutes (the molar ratio of n-butyl ether and titanium tetrachloride was 2.6). A dark brown homogeneous solution was obtained.

(2) Copolymerization Copolymerization was carried out in the same manner as in Example 1. The solution during copolymerization was homogeneous, and no precipitation of copolymer was observed during polymerization. The yield of copolymer is 113g
and the propylene content in the polymer is 37wt
It was %. The RI value determined from the infrared absorption spectrum of the copolymer was 0.3%.

Example 13 (1) Preparation of catalyst component (A) Powdered palladium carbon (Pd content 5%) was placed in a 100 ml flask that had been thoroughly dried and purged with nitrogen.
100 mg of purified 1,2-dichloroethane and mmol of titanium tetrachloride were added, and then 2.8 ml of n-butyl ether was added over 5 minutes with stirring. The inside of the flask was cooled to 0°C, and 3 mmol of n-butylmagnesium iodide was added under stirring.
was added over a period of 10 minutes (the molar ratio of n-butyl ether to titanium tetrachloride was 2.0). A brown solution was obtained.

Next, hydrogen gas was blown in at a rate of 0.2/min for 2 hours. It was filtered under nitrogen to separate the powdered palladium on carbon. A dark brown homogeneous solution was obtained.

(2) Copolymerization Copolymerization was carried out in the same manner as in Example 1. The solution during the copolymerization was homogeneous, and no precipitation of the copolymer was observed during the polymerization. The yield of copolymer is 120
g, and the propylene content in the polymer is 39wt.
It was %. The RI value determined from the infrared absorption spectrum of the copolymer was 0.2%.

Example 14 Using the catalyst of Example 13, butene-1 instead of propylene of Example 1, ethylene 2/
Copolymerization was carried out in the same manner as in Example 1 except that a mixed gas of 10 min and butene-1/min was used. The yield of the copolymer was 49 g, and the content of butene-1 in the copolymer was 21 wt%.

[Brief explanation of the drawing]

FIG. 1 is a flow chart that organically combines the catalyst components and preparation steps of the present invention. Figure 2 shows the infrared absorption spectra at 720 cm ^-1 and 730 cm ^- of the copolymer produced in Example 1 in order to determine the random index (RI) showing the randomness of ethylene and propylene, which is a feature of the present invention. This is an enlarged view of the absorption part of ¹ .

Claims (1)

[Claims] 1 (A) In an organic solvent, an ether and at least one
A liquid obtained by treating titanium tetrahalide with (1) hydrogen in the presence of a Group B, B, B, metal of the periodic table, or a compound thereof; or
(2) Copolymerizing ethylene and propylene or/and butene-1 using a liquid obtained by treating hydrogen with an organomagnesium compound and/or an organoaluminum compound, and (B) a catalyst consisting of an organoaluminum compound. A method for producing ethylene copolymer rubber, characterized by: