JPS6354407A - Production of ethylene/propylene copolymer rubber - Google Patents

Abstract

PURPOSE:To obtain the title rubber excellent in properties when particulated in high yields, by copolymerizing ethylene with propylene in the presence of a specified catalyst. CONSTITUTION:A catalyst is obtained by mixing a catalyst component (a) obtained by contacting a metal oxide which is an oxide of a Group II-IV element of the periodic table (e.g., SiO2) with a magnesium compound (ii) of the formula (wherein R<1> is a 1-20C hydrocarbyl and R<2> is R<1> or a halogen), e.g., butylethylmagnesium, and optionally an alcohol (iii) (e.g., ethanol) and contacting the product with a titanium compound (iv) (e.g., TiCl4) with 1-2,000g.mol, per g.atom of the titanium of component (a), of an organoaluminum (b) (e.g., triethylaluminum) and, optionally, an electron-donating compound. Ethylene is copolymerized with propylene at -80-150 deg.C in the presence of the above catalyst to obtain the title rubber of an ethylene content of 15-90mol%.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a method for producing ethylene/propylene copolymer rubber.

2. Description of the Related Art A method is known in which ethylene and propylene are copolymerized using a highly active titanium-based catalyst in place of the conventional vanadium-based catalyst to produce ethylene-propylene copolymer rubber.

Recently, several methods for producing copolymer rubber using magnesium compound-supported titanium-based catalysts have been attempted.
They are quite complicated. There are problems such as the polymer obtained has a low bulk density, which poses a practical problem.

On the other hand, there is a method of copolymerizing ethylene and propylene, especially gas phase polymerization, using a catalyst component in which a titanium component is supported on a metal oxide such as silica, with the main purpose of obtaining a polymer with particularly good particle properties. It has been reported.

For example, a solid catalyst component formed by contacting (1) a metal oxide, (2) a titanium compound produced by a reaction between magnesium halide and a compound of the formula Me(oR)nx, -n
9-105008), formula MPmTi(OR)nX
o(gD)qc X represents halogen, and gD represents an electron donating compound. ] The catalyst (
A method using Japanese Unexamined Patent Publication No. 59-250011) has been proposed.

Problems to be Solved by the Invention According to the method for producing copolymers using these metal oxide-supported titanium-based catalysts, it has become possible to produce polymers with improved particle properties to some extent, but the polymerization catalyst There is a problem that the amount of polymer produced per unit is low.

Means for Solving ProblemsPurpose of the InventionThe object of the present invention is to produce an ethylene-propylene copolymer rubber with excellent particle properties in a high yield using a metal oxide-supported titanium-based catalyst. As a result of intensive research, the present inventors found that (A) metal oxide and (B) general formula R''M have been proposed for polyethylene production.
Catalyst component obtained by contacting with a magnesium compound of r R'' or further contacting with (C) alcohol and then contacting with (D) a titanium compound (JP-A No. 46-2258, No. 51-47990) , No. 57-90004, No. 5
The present invention was completed based on the discovery that the object of the present invention can be achieved by copolymerizing ethylene and propylene using the following publications: No. 7-85805 and No. 57-200408.

Summary of the Invention That is, the present invention comprises K (A) metal oxide and (B) general formula R1) #R"
C, where L and R1 represent a human carbyl group, and 2 represents a hydrocarbyl group or a halogen atom. A polymerization catalyst consisting of a catalyst component obtained by contacting with a magnesium compound of ] or further contacting with (C') alcohol, and then contacting with (D) a titanium compound, and (b) an organoaluminum compound. In the presence of ethylene and propylene, ethylene/propylene (molar ratio) is α01~1,
The gist of the present invention is a method for producing an ethylene/propylene copolymer rubber having an ethylene content of 15 to 90 mol %, which comprises copolymerizing the rubber to α0 or α03 to α50 in the gas phase.

(A) Metal oxide The metal oxide used in the present invention is an oxide of an element selected from the group of elements from Groups 1 to 2 of the Periodic Table of Elements,
To illustrate them, 731 0g, MfOt
A1503 e 810H6CaO#
T10! t ZnO@Zro, sSnug, B
ad, ThO2, etc. Among these, f%
OB, MfO, person 110g, B101. 'r
iot, Zr01 is preferred, and 5103 is particularly preferred. Furthermore, composite oxides containing these metal oxides, such as BiO, -MfO, SiC, -Al, Os, si
o,-'rtot, 810! -'/, O,.

810g-CrlOl, SiOSlol-TiOl
- etc. may also be used.

The above metal oxides and composite oxides are basically desirably anhydrous, but a trace amount of hydroxide, which is usually mixed, is allowed. In addition, the inclusion of impurities is permitted to the extent that the properties of the metal oxide are not significantly impaired. Acceptable impurities include oxides such as sodium oxide, potassium oxide, lithium oxide, sodium carbonate, potassium carbonate, calcium carbonate, magnesium carbonate, sodium sulfate, aluminum sulfate, barium sulfate, potassium nitrate, magnesium nitrate, and aluminum nitrate; salt, sulfate,
Examples include nitrates.

These metal oxides are usually in the form of powder. The size and shape of the powder often affect the shape of the obtained olefin polymer, so it is desirable to adjust it appropriately. For the purpose of removing poisonous substances before use, it is desirable to sinter metal oxides at the highest possible temperature and handle them in a manner that prevents them from coming into direct contact with the atmosphere.

) Magnesium compound The magnesium compound used in the present invention has the general formula R'M
fR". In the formula, R1 has 1 to 2 carbon atoms.
0 hydrocarbyl groups (alkyl, cycloalkyl,
aryl, aralkyl group), R2 is carbon 'fIi1
~20 hydrocarbyl groups (alkyl, cycloalkyl.

aryl, aralkyl group) or a halogen atom.

Examples of those compounds are shown below. However, M? = Magnesium, Me = Methyl, Et = Ethyl.

Pr=propyl, Eu=butyl, Pe=pentyl.

He-hexyl, ph=phenyl, BZ=benzyl.

Ct=chlorine, Br=bromine, I=diiodine abbreviation.

When 2 is a hydrocarpyl group: M+4MIP.

11e snow Mf, PrIMf, i-Pr
lMP, WtPrMP, BulMP
.

1-BulMP, 36C-BulMP, tert-
BulMP, BuRtMf.

PelMf, i-PelMP, EtPqMf, H
elMP, EtHs) #.

BuHeMP, (2-EtBu)F, tMP, diheptyl MP.

Dioctyl MP, butylcyclohexyl Mf.

Ph! MP, WtPbMf, BuPhMP, Ditril M? .

Dixylyl MW, BZ! MIF, Jihuenech A/M
P.

Examples include ethyl phenethyl MY.

These magnesium compounds may be mixtures or complex compounds with organic compounds of other metals. Organic compounds of other metals have the general formula MRn (where M is boron, beryllium, aluminum or zinc, R is an alkyl, cycloalkyl, aryl or aralkyl group having 1 to 20 carbon atoms, and n is an atom of the metal M). ). Specific examples include triethylaluminum, tributylaluminum, triisobutylalkinium, triphenylaluminum, triethylboron, tributylboron, diethylberyllium, diisobutylberyllium, diethylzinc, dibutylzinc, and the like.

The ratio of the mixture or complex compound of the magnesium compound and the organic compound of the other metal is usually 2 gram atoms or less of the other metal, preferably 1 gram atom or less, per 1 gram atom of magnesium.

When R2 is a halogen atom: PrMfCt, PrM
fCt.

1-PrMPCt, BuMfC6,i-BuMS'C
4, sec-BuMrCA.

tert-Bul#Ct, PeMrC4, HeMfC
t, (2-gtHe)MtCl, octyl Mtct,
Decyl MtC1, cyclohexyl MfC1, PhMPC
6, Tolyl Myct, Xylyl M? C1,BzMrC2
, BtMfBr, BuMPBr, tert-BuM
fBr, HeMfBr, octyl MPBr,
Cyclohexy/I/ MtBr, PhMfBr, E
tMPI, BuMf Eng.

(2-EtHe)) #I, PhMfI, and the like.

(0 alcohol Alcohols include methanol, ethanol/I/, 7
Examples include lovanol, 1-propatol, butanol, 1-butanol, tert-butanol, pentanol, hexanol, 2-ethylhexanol, cyclohexanol, phenol, benzyl alcohol, phenethyl alcohol, and the like.

Furthermore, halogen-containing alcohols in which any hydrogen atom other than the hydroxyl group of these alcohols is substituted with a halogen atom can also be used. Examples of these compounds include 2-chloroethanol, 1-chloro-2-7' lovanol, 4-chloro-1-butanol, 5-chloro-1-pentanol, 6
-Chlor-1-hexanol, 2-chlorocyclohexanol, (m,0.p)-chlorophenol, (m*o
*p)-chlorobenzyl alcohol, 2-7" romethanol, 1-bromo-2-butanol, ("eOep
)-bromophenol, Z, 2-dichloroethanol,
1.5-dichloro-2-propatol, 2.4-sifuromphenol, Z2,2-trichloroethanol, 1.
1.1-) dichloro-2-globanol, 2.44-
) dichlorophenol, etc.

(c) Titanium compounds Titanium compounds are divalent, trivalent, and tetravalent titanium compounds, and examples thereof include titanium tetrachloride, titanium tetrabromide, trichloroethoxytitanium, trichlorobutoxytitanium, and dichlorshed titanium. Titanium, dichlorobutoxytitanium, dichlordiphenoxytitanium, chlortriethoxytitanium, chlortributoxytitanium, tetrabutoxytitanium, titanium trichloride and the like can be mentioned. Among these, tetravalent titanium halides such as titanium tetrachloride, trichlorethoxytitanium, dichlorodibutoxytitanium, and dichlordiphenoxytitanium are preferred, and titanium tetrachloride is particularly preferred.

Preparation method of catalyst component The catalyst component used in the present invention is a metal oxide (hereinafter referred to as A
It is called an ingredient. ) and a magnesium compound (hereinafter referred to as component B) and then a titanium compound (hereinafter referred to as component C), or after bringing component A and component B into contact, alcohol (hereinafter referred to as C ) and then with component C.

Contact between Components A and B Components A and B may be brought into contact by mixing and stirring in the presence or absence of an inert medium, by mechanical co-pulverization, or the like. Inert media include hydrocarbons such as pentane, hexane, hegetane, octane, tecane, cyclohexane, benzene, toluene, xylene, t2-dichloroethane, 1,2-dichloropropane, carbon tetrachloride,
Norogenated hydrocarbons such as butyl chloride, isoamyl chloride, bromobenzene, chlorotoluene, etc. can be used.

The contact between component A and component B is usually carried out at -20°C to +150°C (for 1 to 100 hours, preferably at room temperature to 110°C).
If the time-liquid contact is carried out for 5 to 10 hours and generates heat, a method may be adopted in which the components are first mixed gradually at a low temperature, and then the temperature is raised after the entire amount has been mixed, and the contact is continued.

The contact ratio between A component and B component is A/B=1f/Q, 1~
100 mmol, preferably 12/1 to 10 mmol.

The solid product obtained by contacting component A and component B (hereinafter referred to as product 1) is then contacted with component C, or further with component C, if necessary. Their contact may be preceded by washing with suitable cleaning agents, such as the inert media mentioned above.

The product 1 and component C are brought into contact by mechanically co-pulverizing them, mixing and stirring them in the presence or absence of an inert medium, or the like. Among these, a method in which both are mixed and stirred in the presence of an inert medium is particularly desirable. As inert medium it is possible to use the compounds mentioned above.

Contact between product I and C component is usually between -20°C and +150°C.
for 11 to 100 hours, preferably at room temperature to 110°C.
, for 5 to 10 hours. If contact is accompanied by fever,
It is also possible to adopt a method in which the two are gradually mixed at a low temperature first, and then the temperature is raised once the entire amount has been mixed, and the contact is continued.

The amount of component C used is 105 to 50 per mole of component B.
mol, preferably (11 to 20 mol).

The solid product obtained as described above (hereinafter referred to as product ①) is then contacted with component C, but before contacting with component C, if necessary, the above-mentioned inert medium is added. May be washed.

Contact with component C Contact with product I or product (2) is carried out by mechanically co-pulverizing them in the presence or absence of an inert medium, by mixing and stirring them, or the like. Among these, a method in which both are mixed and stirred in the presence of an inert medium is particularly desirable. As inert medium it is possible to use the compounds mentioned above.

The contact ratio of product 1 or product 2 with component D is per gram atom of magnesium in product 1 or product
The component is 0.01 gmol or more, preferably α1 to 10
Gram moles.

When the two are mixed and stirred in the presence of an inert medium, the contact between the two is carried out at 0 to 200°C for 15 to 20 hours, preferably for 60 to 1
It is carried out at 50° C. for 1 to 5 hours.

The contact between Product I or Product (2) and Component D can be carried out two or more times. The contact method may be the same as described above.

If necessary, the contact material in the first stage may be washed with the medium, and component D (and an inert medium) may be newly added thereto and brought into contact.

The contact reaction product obtained as described above is washed with a hydrocarbon such as hexa/, heptane, octane, cyclohexane, benzene, toluene, or silane, if necessary, and further used in the present invention if necessary. catalytic component.

Polymerization Catalyst The polymerization catalyst used in the present invention consists of a combination of the catalyst component obtained as described above and an organoaluminum compound.

As the organic alk(+cum) compound that can be used, the general formula Rn
AtX3-n (where R is an alkyl group or an aryl group,
X represents a halogen atom, an alkoxy group or a hydrogen atom,
n is an arbitrary number in the range of 1≦n≦3. ), for example, trialkylaluminium, dialkylaluminum monohalide, monoalkylaluminum civalide, alkylaluminum sesquihalide, dialkylaluminium monoalkoxide, and sialium aluminum monohydride having 1 or more carbon atoms. Particularly preferred are alkyl aluminum compounds having 18 carbon atoms, preferably 2 to 6 carbon atoms, or mixtures or complexes thereof. Specifically, trialkylaluminum such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, trihedylaluminum, dimethylaluminum chloride, diethylaluminium chloride, diethylaluminium bromide, diethylaluminium iodide, Dialkylaluminum monohalides such as diisobutylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride, methylaluminum dichloride, ethylaluminum dichloride,
Monoalkylaluminum cibarides such as ethylaluminum diiodide and isobutylaluminum dichloride; alkylaluminum sesquihalides such as ethylaluminum sesquichloride; dimethylaluminum methoxide; diethylaluminum ethoxide; diethylaluminum phenoxide; Examples include dialkyl aluminum monoalkoxides such as aluminum ethoxide and diisobutyl aluminum phenoxide, and dialkyl aluminum hydrides such as dimethyl aluminum hydride, diethylaluminium hydride, diethylalkinium hydride, and dialkyl aluminum hydride. Among these, triple-kylalbanium is preferred, particularly triethylaluminum and triisobutylaluminum. In addition, these triple-kyl albaniums can be used with other organic aluonium compounds,
For example, it can be used in combination with industrially easily available diethylaluminum chloride, ethylaluminum dichloride, ethylaluminum sesquichloride, diethylaluminum ethoxide, diethylaluminium hydride, or a mixture or complex compound thereof.

Furthermore, an organic aluminum compound in which two or more pieces of aluminum are bonded via an oxygen atom or a nitrogen atom can also be used. Examples of such compounds include (C i H1) i A
LOAt(Cs Hs')g eCCnH) x At
OAt(C4Hs)x*(CzHs)xAtNA
Examples include t(CsHs)tI CsHs.

Further, the organometallic compound may be used alone or in combination with an electron-donating compound.

Examples of electron-donating compounds include carboxylic acids, carboxylic anhydrides, carboxylic esters, carboxylic acid halides, alcohols, ethers, ketones, amines,
Examples include amides, nitriles, aldehydes, alcoholates, phosphorus, arsenic and antimony compounds bonded to organic groups via carbon or oxygen, phosphoamides, thioethers, thioesters, carbonic esters and the like.

In addition to these, electron-donating compounds made of organic silicon compounds and electron-donating compounds containing heteroatoms such as nitrogen, sulfur, oxygen, and phosphorus can also be used.

Two or more types of these electron-donating compounds may be used. Further, these electron-donating compounds may be used when an organoaluminum compound is used in combination with a catalyst component, or may be used after being brought into contact with an organoaluminum compound in advance.

The amount of organoaluminum compound used relative to the catalyst component is
Usually 1 to 20 per gram atom of titanium in the catalyst component.
00 gmol, especially 20 to 500 gmol.

The ratio of the organoaluminum compound to the electron-donating compound is selected within the range of 11.1 to 40, preferably 1 to 25, gram atoms of the organoaluminum compound as aluminum per mole of the electron donating compound.

The catalyst component used in the present invention is prepared by prepolymerizing ethylene and/or propylene in the presence of an organoaluminum compound and, if necessary, an electron-donating compound, to obtain ethylene and/or propylene per 1f of catalyst component. Polymer of cL1~1002, preferably 1~so? Incorporated catalyst components can be used. As the prepolymerization method, an ordinary olefin polymerization method using a Ziegler-Natsuta type catalyst can be adopted.

Copolymerization of ethylene and propylene Copolymerization of ethylene and propylene can be carried out by copolymerizing ethylene and propylene according to the usual olefin copolymerization method using a Ziegler-Natsuta type catalyst, but bulk copolymerization using propylene as a medium can be used. Polymerization methods and gas phase polymerization methods are particularly preferred.

The copolymerization temperature is usually in the range of -80°C to +150°C, preferably 0 to 80°C. Copolymerization may be carried out under pressure up to 60 atmospheres. The ethylene/propylene copolymer rubber obtained by the method of the present invention has an ethylene content of 15 to 90 moles. /Flopylene (mole ratio), in the case of bulk polymerization using Flopylene as the medium, by adjusting α01 to 1.0 in the liquid phase, and by adjusting the Q to 03 to 50 in the case of gas phase polymerization.

The copolymerization reaction can be carried out continuously or batchwise, and may be carried out in general or in two or more stages.

Effects of the Invention According to the method of the present invention, ethylene-propylene copolymer rubber with good particle properties can be produced in high yield. Therefore, the decatalyst step can be omitted.

EXAMPLES Next, the present invention will be specifically explained using examples. In addition,
The percentages (%) shown in the examples are vague criteria unless otherwise specified.

Total ethylene in the polymer was determined by infrared spectroscopy. Melt index (M) is ASTM
According to D 1238, the bulk density is ASTM D
1B95-69 method A). Heat of fusion was measured using PerkinElmer MD3cIlc. In addition, true density was measured according to ASTM D 1505.

Example 1 A 200-meter flask equipped with a dropping funnel and a stirrer was purged with nitrogen gas. This flask contains silicon oxide 1 (DA).
Manufactured by VISON, product name G-952. Specific surface area 302m
(5102) (hereinafter referred to as 5102) with a pore volume t 54 nl/9 and an average pore radius 200) was calcined in a nitrogen stream at 200°C for 2 hours and then at 700°C for 5 hours. -Methyl ethyl magnenium (
Hereinafter referred to as BEM. ) in 20% n-heptane solution (manufactured by Texas Alkyls, trade name: LABEM with MA())
)20d (2 & 8 mmol as BEM) was added and stirred for 1 hour.

Contact with titanium tetrachloride After the above suspension was cooled to 0°C, a mixture of 20 cm of titanium tetrachloride and 50 cm of toluene was added to it from the dropping funnel.
It was dripped over 0 minutes. After dropping, heat to 90℃ for 1 hour.
The temperature was raised to 90° C. and stirring was continued for 2 hours. After the reaction is complete,
The supernatant liquid was removed by decantation, and the resulting solid was washed five times with 60-nihexane. Drying was carried out under reduced pressure at room temperature for 1 hour, and the titanium content was 9.
8% catalyst component 6) &0? Obtained.

Into a 1,56 autoclave equipped with an ethylene and propylene copolymerization stirrer and purged with nitrogen, 800-1 ml of liquid propylene component (a) s
A glass ampoule containing rq and tommol of triethyl aluminum (TEAL) were added. Next, the contents were heated to 40° C., and 100 d of hydrogen and ethylene were added so that ethylene/furopylene in the liquid phase was 125 (molar ratio), and the mixture was pressurized to 2 & 5 to 9/a+”. The stirrer was rotated and the glass ampoule was broken to start copolymerization.The ethylene/propylene ratio in the polymerization empty/liquid phase was maintained at α23 by supplying ethylene.After 1 hour, the pressure was lowered and the resulting polymer was taken out. It was dried.Polymerization activity was 2A8.
klil/P・Catalyst component (a)-time. The obtained polymer has a true spherical shape and a bulk density of CL52 f/l.
x", M work 0.75f/1G, true density α875'
l/x”, ethylene content 71 mol%, heat of fusion 1.8
It was cal/j'.

, B) Catalyst components (b) to (d) were prepared in the same manner as in Example 1, except that the magnesium compound shown below was used in place of lfflM.

(%) 2b Zirohexyl MP IC14d
n-BuMPC2&1 Using the catalyst component obtained above and adjusting the copolymerization conditions to the first
Copolymerization of ethylene and propylene was carried out in the same manner as in Example 1, except that the values in the table were changed, and the results are shown in Table 1.

Example 5 Contact between 810mm and BEM was carried out in the same manner as in Example 1. The upper liquid of the resulting suspension was removed by decantation, and washed five times with 50-n-hebutane.

After washing, 20 ml of n-hegetane was added, and a mixed solution of 10 d of ethanol and 10 ml of n-heptane was added dropwise from the dropping funnel at 0° C. over 50 minutes. After the dropwise addition was completed, the temperature was raised to 80°C over 1 hour, and stirring was performed at 80°C for 1 hour. After the reaction was completed, washing was performed five times with 50-g of toluene.

Next, contact with titanium tetrachloride was carried out in the same manner as in Example 1, except that the reaction temperature was 120° C., to prepare a catalyst component (e) having a titanium content of 1.8%.

Copolymerization of ethylene and propylene Copolymerization of ethylene and propylene was carried out in the same manner as in Example 1, except that the catalyst component (e) obtained above was used and the copolymerization conditions were as shown in Table 1. , the result is the first
Shown in the table.

Catalyst component (f) and catalyst component (?) were prepared in the same manner as in Example 5, except that the alcohol shown below was used instead of ethanol.

(%) 6f'n-butanol
z17 r 2,2,2-trichloroethanol 50 Copolymerization of ethylene and propylene Using the catalyst component obtained above and changing the copolymerization conditions to the first
Copolymerization of ethylene and propylene was carried out in the same manner as in Example 1, except that the table was changed, and the results are shown in Table 1. In Example 6, triisobutylaluminum was used instead of TEAL as the organoaluminum compound used during copolymerization.

Example 8 Preparation of catalyst components In the same manner as in Example 4, Sin and n-BuMfCA
were brought into contact with each other to obtain a suspension. This suspension was brought into contact with ethanol-A and then with titanium tetrachloride in the same manner as in Example 5 to prepare a catalyst component (g).

Copolymerization of ethylene and propylene Using the catalyst component obtained above and adjusting the copolymerization conditions to
Copolymerization of ethylene and globin/globin was carried out in the same manner as in Example 1, except for the following changes, and the results are shown in Table 1.

Catalyst component (1) and catalyst component θ) were prepared in the same manner as in Example 8, except that the alcohol shown below was used instead of ethanol.

(%)? tn-butanol 1.11
0jp-Chlorphenol □ Copolymerization of ethylene and propylene Using the catalyst component obtained above and adjusting the copolymerization conditions to the first
Copolymerization of ethylene and propylene was carried out in the same manner as in Example 1, except that the table was changed, and the results were reported in the first
Shown in the table.

5iO1K replaced, 70℃ for 2 hours at 200℃ in a nitrogen stream
A baked at 0℃ for 5 hours! A catalyst component with a titanium content of &7%) and a catalyst component (4) were prepared in the same manner as in Example 1 or Example 9, except that 40s was used.

Co-M copolymerization of ethylene and propylene Using the catalyst component obtained above and adjusting the copolymerization conditions to the first
Copolymerization of ethylene and propylene was carried out in the same manner as in Example 1, except that K was used as shown in the table, and the results are shown in Table 1.

Example 13 A 200-cm flask equipped with a stirrer was sufficiently purged with nitrogen, and 50-cm of heptane was charged. To this, catalyst component (i) (L 5 ) obtained in Example 9 and 5 mmol of TKALα were added, and ethylene was further supplied to start polymerization of ethylene at room temperature and pressure.

After 1.5 hours, the supply of ethylene was stopped and the liquid phase was removed. After washing the in-phase part five times with 50-n-hexane,
Dry at room temperature. 55 f of ethylene was polymerized and incorporated per 12 of catalyst component (1).

Copolymerization of ethylene and propylene Copolymerization of ethylene and propylene was carried out in the same manner as in Example 1, except that the above prepolymerized catalyst components were used and the copolymerization conditions were as shown in Table 1. It is shown in Table 1.

[Brief explanation of the drawing]

FIG. 1 is a flowchart diagram illustrating the method of the present invention.

Claims (1)

[Claims] (a) (A) metal oxide and (B) general formula R^1MgR^
2 [However, R^1 represents a hydrocarbyl group, and R^2 represents a hydrocarbyl group or a halogen atom. ] A polymerization catalyst consisting of a catalyst component obtained by contacting with a magnesium compound or further contacting with (C) alcohol and then contacting with (D) a titanium compound, and (b) an organoaluminium compound. A method for producing an ethylene/propylene copolymer rubber having an ethylene content of 15 to 90 mol%, which comprises copolymerizing ethylene and propylene in the presence of.