JPH09151205A - Reparation of copolymer rubber - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an ethylene/α-olefin copolymer rubber and an ethylene/α- olefin/nonconjugated diene copolymer rubber both having desirable properties by using a catalyst comprising a specific transition metal complex, a borate compd. and an organoaluminum compd. SOLUTION: A catalyst comprising the following components (A) to (C) is used. The component (A) is a transition metal complex of the formula 1 or 2 (wherein M is a transition metal of the Group IVB in the periodic table; CP<1> and CP<2> are each a cyclopentadienyl group π-bonded to M or Hf, or its deriv. group; X<1> and X<2> are each an anionic ligand or a neutral Lewis base ligand; Y is a ligand having a nitrogen atom, a phosphorus atom, an oxygen atom or a sulfur atom; and Z is an oxygen atom, a sulfur atom, a boron atom, or an atom of the Group IVA in the periodic table, provided that Y and Z may be combined to form a condensed ring). The component (B) is a borate compd. The component (C) is methylaluminoxane, or an organoaluminum compd. contg. an alkyl group having at least one branch.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel ethylene-α
The present invention relates to a method for producing an olefin copolymer rubber or an ethylene-α-olefin-non-conjugated diene copolymer rubber. Ethylene-α-olefin copolymer or ethylene-α-olefin-non-conjugated diene copolymer rubber is a rubber material known as EPM or EPDM, respectively, and is a modifier of various resins, a wire coating material, a waterproof sheet. It is widely used as materials, belts, various hoses, and automobile parts materials. If necessary, it is used by being vulcanized with, for example, sulfur or peroxide to increase the rubber properties.

[0002]

2. Description of the Related Art As a conventional method for producing these rubbers, a vanadium-based catalyst has been generally used. In addition, several catalyst systems for olefin polymerization are known. For example, JP-A-58-19309 discloses a method for producing olefins using a metallocene compound of a transition metal and aluminoxane as a catalyst. Although the catalyst has high activity and excellent copolymerizability, it has a problem that a large amount of expensive aluminoxane is required.

Further, JP-A-5-262823 and JP-A-5-43618 disclose a method for polymerizing olefins using a transition metal complex, a boron complex and a small amount of an aluminum compound as a catalyst. This method, however, has a high α-olefin content and a low density,
There is a problem that it is not sufficient for the purpose of producing a binary or ternary high molecular weight copolymer rubber.

Further, EP-A 0,612,768 discloses a method of copolymerizing ethylene and α-olefin using a transition metal complex, a boron complex and an aluminum compound as a catalyst. In this method, However, there is a problem that high-temperature reaction conditions are required to obtain a high-molecular polymer.

[0005]

Accordingly, these EPs are
It is desired to develop a manufacturing method for manufacturing M and EPDM rubbers more efficiently, cheaper, and with even better properties. For example, the development of catalyst systems with higher catalytic activity will reduce the production time and thus provide a more efficient and cost-effective production method. Further, in this case, since the amount of the catalyst used is reduced, the process of decatalyzing or deashing the product can be omitted, which is extremely advantageous in terms of product cost and quality.

Accordingly, the inventors of the present invention have conducted extensive studies as to a novel method for producing a copolymer rubber having desirable properties, and as a result, by using the catalyst system described below, ethylene and α-olefin, Or ethylene, α-
By copolymerizing an olefin and a non-conjugated diene in the presence of a catalyst system containing the following components (A) to (C), an EPM, EPD having a high molecular weight and desirable properties
The present invention has been completed by finding a method for producing the M copolymer rubber under mild conditions.

[0007]

That is, according to the present invention, ethylene and α-olefin are polymerized in the presence of the following catalyst system to give an ethylene content of 30-90% by weight and a density (d) of 0.840-0. A method for producing an ethylene-α-olefin copolymer rubber capable of producing a copolymer rubber having various properties such as 900 g / cm ³ , and polymerizing ethylene, α-olefin, and a non-conjugated diene, Ethylene content 30-90% by weight, density (d) 0.840-0.9
Ethylene-α-which enables the production of a terpolymer rubber having various properties such as 00 g / cm ³ and an iodine value of 0.5-40.
Provided is a method for producing an olefin-non-conjugated diene copolymer rubber.

More specifically, the present invention comprises the following (A).
Min. To (C) in the presence of a catalyst system containing
And α-olefin are polymerized to give an ethylene content of 30-9.
0% by weight, density (d) 0.840-0.900 g / c
m^Three Ethylene characterized in that a copolymer of
It relates to a method for producing an α-olefin copolymer rubber.
The component (A) is represented by the chemical formula (1) or (2).
Transition metal complex(Where M represents a transition metal of Group IVB of the periodic table,
Cp¹ And Cp^Two Is a π bond with M or Hf
Represents a clopentadienyl group or a derivative group thereof, X ¹ as well as
X^Two Represents an anionic ligand or a neutral Lewis base ligand
Y represents a nitrogen atom, a phosphorus atom, an oxygen atom or a sulfur atom.
Represents a ligand having, Z is an oxygen atom, a sulfur atom, a boron atom
Child or atom of Group IVA of the Periodic Table. However, with Y
Z may combine with each other to form a condensed ring), and (B)
The component is a borate compound, and the component (C) is
A methylaluminoxane or at least one branch
An organoaluminum compound containing an alkyl group having
is there.

Further, in the method for producing a copolymer rubber according to the present invention, particularly the component (A) is (tertiary butylamido) dimethyl- (tetramethyl-η ⁵ -cyclopentadienyl).
It is characterized by being silane titanium dichloride or ethylene bis (indenyl) hafnium dichloride. Further, the component (B) is characterized by being triphenylcarbenium tetrakis (pentafluorophenyl) borate or N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate. Further, the organoaluminum compound as the component (C) is particularly preferably methylaluminoxane or triisobutylaluminum.

In the method for producing the copolymer rubber according to the present invention, the ratio (molar ratio) of component (A) / component (B) used is 1
It is characterized by being /(0.01-100). Furthermore, the ratio (molar ratio) of the amount of the component (A) / the component (C) used is 1 / (1-1000).

The present invention also relates to a method for producing a copolymer rubber, which is carried out at a polymerization temperature of -20 ° C or higher and lower than 120 ° C.

The present invention further relates to a method for producing a copolymer rubber, wherein the α-olefin is propylene or 1-butene.

Further, the EPDM terpolymer rubber is produced by polymerizing ethylene, α-olefin and non-conjugated diene in the presence of a catalyst system containing the following components (A) to (C). Ethylene-α-olefin-characterized in that a copolymer having an ethylene content of 30-90% by weight, a density (d) of 0.840-0.900 g / cm ³ , and an iodine value of 0.5-40 is obtained. The present invention relates to a method for producing a non-conjugated diene copolymer rubber.

The component (A) is represented by the chemical formula (1) or (2).
Represented transition metal complex(Where M represents a transition metal of Group IVB of the periodic table,
Cp¹ And Cp^Two Is a π bond with M or Hf
Represents a clopentadienyl group or a derivative group thereof, X ¹ as well as
X^Two Represents an anionic ligand or a neutral Lewis base ligand
Y represents a nitrogen atom, a phosphorus atom, an oxygen atom or a sulfur atom.
Represents a ligand having, Z is an oxygen atom, a sulfur atom, a boron atom
Child or atom of Group IVA of the Periodic Table. However, with Y
Z may combine with each other to form a condensed ring), and (B)
The component is a borate compound, and the component (C) is
A methylaluminoxane or at least one branch
An organoaluminum compound containing an alkyl group having
is there.

Further, in the method for producing a copolymer rubber according to the present invention, particularly the component (A) is (tertiary butylamido) dimethyl- (tetramethyl-η ⁵ -cyclopentadienyl).
It is characterized by being silane titanium dichloride or ethylene bis (indenyl) hafnium dichloride. Further, the component (B) is characterized by being triphenylcarbenium tetrakis (pentafluorophenyl) borate or N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate. Further, the organoaluminum compound as the component (C) is particularly preferably methylaluminoxane or triisobutylaluminum.

In the method for producing the copolymer rubber according to the present invention, the ratio (molar ratio) of the component (A) / the component (B) used is 1
It is characterized by being /(0.01-100). Furthermore, the ratio (molar ratio) of the amount of the component (A) / the component (C) used is 1 / (1-1000).

Further, the present invention relates to a method for producing a copolymer rubber, which is carried out at a polymerization temperature of -20 ° C or higher and lower than 120 ° C.

The present invention further relates to a method for producing a copolymer rubber, wherein the α-olefin is propylene or 1-butene.

Further, as a method for producing a terpolymer rubber,
Ethylene content 30-90% by weight, density (d) 0.84
It is characterized in that a copolymer having an iodine value of 0 to 0.900 g / cm ³ and an iodine value of 0.5 to 40 is obtained. The present invention relates to a method for producing an ethylene, propylene, 5-ethylidene-2-norbornene terpolymer rubber, wherein the component (A) as a catalyst component is (tertiary butylamido) dimethyl- (tetramethyl-η ⁵ -cyclo Pentadienyl) silane titanium dichloride, (B) component is triphenylcarbenium tetrakis (pentafluorophenyl) borate, (C)
The component is triisobutylaluminum, and the polymerization is most effective at a temperature of 20 to 80 ° C. and a pressure of 1 to 300 atm.

Further, as a method for producing a terpolymer rubber,
Ethylene content 30-90% by weight, density (d) 0.84
A method for producing an ethylene, propylene, 5-ethylidene-2-norbornene terpolymer rubber, which comprises obtaining a copolymer having an iodine value of 0 to 0.900 g / cm ³ and an iodine value of 0.5 to 40. As a catalyst component, the component (A) is ethylenebisindenylhafnium dichloride, the component (B) is triphenylcarbenium tetrakis (pentafluorophenyl) borate, and the component (C) is triisobutylaluminum. Is temperature 2
The most effective temperature is 0 to 80 ° C. and the pressure is 1 to 300 atm.

[0021]

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in detail. (Raw material, ethylene, α-olefin) In the present invention, usable α-olefin is not particularly limited,
In particular, a chain having about 3 to 10 carbon atoms can be preferably used. For example, propylene, 1-butene, 3-methyl-1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene and the like can be mentioned. Further, these α-olefins may be used alone or in a mixture of a plurality thereof. The selection of these α-olefins can be appropriately made so as to be the most desirable in terms of the properties of the resulting copolymer rubber. One example of selection is that the physical properties of the copolymer or a mixture containing the copolymer when subjected to vulcanization are desired.

Further, when the above-mentioned various α-olefins are used, generally, the polymerization method according to the present invention does not require substantial change of conditions, and the ratio of the catalyst components, the reaction temperature,
By optimizing the reaction pressure and the like, it is possible to obtain a copolymer rubber having desirable properties, and the slight adjustment of the above reaction conditions can be easily carried out using the knowledge of those skilled in the art. is there. For example, the amount ratio of each catalyst component can be varied within the range disclosed in the present invention to find polymerization conditions for obtaining a copolymer having desired properties.

The non-conjugated diene usable in the present invention is also not particularly limited. Various cyclic or chain diene compounds can be preferably used. Specific examples of the cyclic non-conjugated diene include dicyclopentadiene and 2-methyl-
2,5-norbornadiene, 5-ethylidene-2-norbornene, 5-isopropylidene-2-norbornene,
5-isopropenyl-2-norbornene, 5-methylene-2-norbornene and the like, and specific examples of the chain non-conjugated diene include 1,4-hexadiene, 1,6-octadiene and 6-methyl-1,5. -Heptadiene and the like.

In the production of the ethylene-α-olefin-non-conjugated diene copolymer having the desired properties according to the present invention, the selection of these non-conjugated dienes is the most desirable in view of the properties of the resulting copolymer rubber. Can be selected appropriately. One example of selection is to make the physical properties of the copolymer or a mixture containing the copolymer vulcanized as desired.

Furthermore, when using the various non-conjugated dienes described above, the polymerization process according to the present invention generally does not require substantial modification to the conditions disclosed herein, such as catalyst selection, It is possible to obtain a copolymer rubber having desirable characteristics by optimizing the amount ratio of each component of the catalyst, the reaction temperature, the reaction pressure and the like. A slight adjustment of the above reaction conditions can be understood by those skilled in the art. Can be easily implemented by using. For example, the amount ratio of each catalyst component can be varied within the range disclosed in the present invention to find polymerization conditions for obtaining a copolymer having desired properties.

(Catalyst system) The catalyst system which can be used in the method for producing a copolymer having preferred properties according to the present invention comprises a catalyst component (A), a cocatalyst component (B) and (C). Mandatory.

The component (A) preferably usable in the present invention is a group of transition metal complexes represented by the above chemical formula (1) or (2). Here, in the formula, M is I of the periodic table.
Represents a transition metal of Group VB, Cp ¹ and Cp ² represent a cyclopentadienyl group capable of forming a π bond with M or Hf or a derivative group thereof, and X ¹ and X ² represent an anionic ligand or a neutral Lewis salt Represents a ligand, Y is a nitrogen atom, a phosphorus atom,
It represents a ligand having an oxygen atom or a sulfur atom, and Z represents an oxygen atom, a sulfur atom, a boron atom or an atom of Group IVA of the periodic table. However, Y and Z may combine with each other to form a condensed ring.

Chemical formulas preferably used in the present invention
(1) Specific examples include (tertiary butyl amide) (teto
Lamethyl-η^Five -Cyclopentadienyl) -1,2-d
Tandiyl zirconium dichloride, (tertiary butyryl
Mido) (tetramethyl-η^Five -Cyclopentadienyl)
-1,2-ethanediyl titanium dichloride, (methyl
Mido) (tetramethyl-η^Five -Cyclopentadienyl)
-1,2-ethanediylzirconium dichloride, (meth
Cylamide) (tetramethyl-η^Five -Cyclopentadie
Nyl) -1,2-ethanediyl titanium dichloride, (d
Cylamide) (tetramethyl-η^Five -Cyclopentadie
Nyl) -methylene titanium dichloride, (tertiary butyl
Mido) dimethyl- (tetramethyl-η^Five -Cyclopenta
Dienyl) silane titanium dichloride, (tertiary butyrua
Mid) dimethyl (tetramethyl-η ^Five -Cyclopentadi
(Enyl) silane zirconium dibenzyl, (benzyl
Mid) dimethyl (tetramethyl-η^Five -Cyclopentadi
(Enyl) silane titanium dichloride, and (phenylphosphine
Fido) dimethyl (tetramethyl-η^Five -Cyclopenta
Dienyl) silane Zirconium dibenzyl etc.
An example of such a complex is a coordination complex.

Further, specific examples of the compound represented by the chemical formula (2) include ethylenebis (indenyl) hafnium dichloride, dimethylsilylbis (2,4,5-trimethylcyclopentadienyl) hafnium dichloride,
Dimethylsilylbis (3-methylcyclopentadienyl) hafnium dichloride, dimethylsilylbis (4-
t-Butyl-2-methylcyclopentadienyl) hafnium dichloride, diethylsilylbis (2,4,5-trimethylcyclopentadienyl) hafnium dichloride, diethylsilylbis (2,4-dimethylcyclopentadienyl) hafnium dichloride , Diethylsilylbis (3-methylcyclopentadienyl) hafnium dichloride, diethylsilylbis (4-t-butyl-2-methylcyclopentadienyl) hafnium dichloride, isopropyl (cyclopentadienyl) (fluorenyl)
Hafnium dichloride, diphenylmethylene (cyclopentadienyl) (fluorenyl) hafnium dichloride, methylphenylmethylene (cyclopentadienyl)
(Fluorenyl) hafnium dichloride, isopropyl (cyclopentadienyl) (2,7-di-t-butylfluorenyl) hafnium dichloride, diphenylmethylene (cyclopentadienyl) (2,7-di-t-butylfluorene Nyl) hafnium dichloride, methylphenylmethylene (cyclopentadienyl) (2,7-di-t-
Butylfluorenyl) hafnium dichloride, isopropylidene bis (cyclopentadienyl) hafnium dichloride, diphenylmethylene bis (cyclopentadienyl) hafnium dichloride, methylphenylmethylene bis (cyclopentadienyl) hafnium dichloride, isopropylidene (cyclopentadiene) Dienyl) (tetramethylcyclopentadienyl) hafnium dichloride, diphenylmethylene (cyclopentadienyl) (tetramethylcyclopentadienyl) hafnium dichloride, isopropylidene (indenyl) hafnium dichloride, diphenylmethylenebis (indenyl) hafnium dichloride, Methylphenylmethylene bis (indenyl) hafnium dichloride, dimethylsilylene bis (indenyl) hafnium dichloride Lido, dimethylsilylene bis (4,5,6,7-tetrahydroindenyl) hafnium dichloride, diphenylsilylene bis (indenyl)
Hafnium dichloride, methylphenylsilylene bis (indenyl) hafnium dichloride, ethylene bis (4,5,6,7-tetrahydroindenyl) hafnium dichloride and the like can be mentioned.

Further, in the present invention, the above-mentioned catalysts may be used alone or in combination of two or more kinds.

The cocatalyst (B) component constituting the catalyst system of the present invention is a borate compound which reacts with the transition metal in the above component (A) to form an ionic complex. That is,
The component (B) is a compound capable of making the above-mentioned transition metal complex cationic, and further rather weakly coordinates or interacts with the produced cationic compound, but does not react and does not react with the counter anion. Is a borate compound that provides Specifically, those which can be preferably used in the present invention include tetrakisphenyl borate, tetrakis (pentafluorophenyl) borate ammonium salt, sulfonium salt, phosphonium salt and the like which contain active protons. Further, those which do not contain active protons and have a Lewis acid such as carbonium ion include ionic compounds represented by triphenylcarbenium tetrakis (pentafluorophenyl) borate.

As a more specific example, the following chemical formula (3)
Examples thereof include an ionic compound having an ion pair as shown in and a neutral Lewis acidic compound. [D ⁻ ] [E ⁻ ] (3) Specific examples of [D ⁻ ] represented by the chemical formula (3) include trimethylammonium, triethylammonium, tripropylammonium, tributylammonium, N, N containing active protons. -Dimethylanilinium,
N, N-diethylanilinium, N, N, 2,4,6-
Compounds such as pentamethylanilinium, triphenylphosphonium, tri (o-tolyl) phosphonium, tri (p-tolyl) phosphonium, tri (mesityl) phosphonium, or triphenylcarbenium ion containing no active proton, tropylium ion, etc. Can be given. Further, specific examples of [E ⁻ ] include tetraphenyl borate, tetra (pentafluorophenyl) borate, tetra (o-fluorophenyl) borate, tetra (p-fluorophenyl) borate, tetra (m-).
Fluorophenyl) borate, tetra (3,5-difluorophenyl) borate, tetra (2,5-difluorophenyl) borate, tetra (2,6-difluorophenyl) borate, tetra (o-tolyl) borate, tetra (p- Tolyl) borate, tetra (3,5-dimethylphenyl) borate, tetra (2,5-dimethylphenyl) borate, octadecaborate, dodecaborate,
1-carbaundecaborate, 1-carbadodecaborate and the like can be mentioned.

Further, the co-catalyst (C) component constituting the catalyst system of the present invention is R ₂ AlO (Al (R) -O) _n AlR.
A straight chain such as ₂ or a cyclic methylaluminoxane such as (Al (R) -O) _{n + 2} (R is a methyl group, n is a degree of polymerization 0 to 40, preferably 5 to 40) or at least 1
It is an organoaluminum compound containing an alkyl group having one branch. Further, the organoaluminum compound is usually represented by the chemical formula (4). AlR ^b R ^{b ′} R ^{b ″} (4) Here, R ^b , R ^{b ′} and R ^{b ″} may be the same or different and each is a hydrogen atom, a halogen atom, an amide group, an alkoxy group or a hydrocarbon group. And at least one of them must be a branched hydrocarbon group. Specific examples of the compound represented by the general formula (4) include triisopropyl aluminum, diisopropyl aluminum chloride, isopropyl aluminum dichloride, triisobutyl aluminum, diisobutyl aluminum chloride, isobutyl aluminum dichloride, tri t-butyl aluminum, di t. -Butylaluminum chloride, t-butylaluminum dichloride and the like can be mentioned, with triisobutylaluminum being particularly preferred.

In the present invention, the choice of catalyst system described above does not require substantial modification from the conditions disclosed herein, but to obtain the desired properties of the product copolymer. In addition, the combination of the above catalyst system types can be easily optimized and selected. For example, the optimum catalyst component (A) and the optimum cocatalyst (B), (C) are selected based on the desired characteristics of the product copolymer rubber based on the experimental design method known to those skilled in the art. It is easy to find the optimum manufacturing conditions by selecting the kind and the quantity ratio.

The catalyst system used in the present invention is (A),
(B) and (C) are the main components, and the amount ratio of these is not limited depending on the kind and the desired product characteristics, but in general,
The ratio (molar ratio) of component (A): component (B) is usually 1:
It is preferably 0.01 to 1: 100, more preferably 1: 0.5 to 1:10, and particularly preferably 1: 1 to 1: 5. The component (C) is usually 1 to 1000 with respect to 1 mol of the component (A).
Mol, preferably 1 to 500, particularly preferably 1 to 3
00 mol is used. In particular, methylaluminoxane is expensive, and the smaller the amount used, the more preferable in terms of cost.

The above component ratios are only general ones, and those skilled in the art can determine the optimum production conditions of the copolymer rubber having desirable characteristics by, for example, deciding on the basis of a usual experimental design method or the like. It is possible.

(Polymerization Reaction) The polymerization method for producing the copolymer rubber having the desired properties according to the present invention is not particularly limited. Polymerization conditions such as ethylene or propylene can be preferably used with the Ziegler-Natta catalyst system or the Kaminsky catalyst system. If a copolymer having the preferable properties according to the present invention can be produced, for example, a bulk polymerization method using a monomer as a solvent, a solution polymerization method in a suitable solvent, and a suspension in a suitable inert solvent. Any method such as a turbid polymerization method and a gas phase polymerization method under various pressures may be used. Furthermore, in the batch method,
It may be a continuous method. In the method for producing a copolymer having desirable characteristics according to the present invention, the constitution disclosed in the present invention is not substantially changed, but the specific control conditions required in each polymerization method are not limited to the present invention. Selection of such a catalyst system, and further, if necessary, addition of a suitable supporting agent or the like to the catalyst system of the present invention, adjustment of concentration of polymerized monomer, stirring conditions, adjustment of reaction temperature, separation of produced polymer The equal method can be optimized by a usual method.
("New Polymer Manufacturing Process" by Koji Saeki and Shinzo Omi)

Although the examples of the present invention disclose the polymerization by the solution polymerization method, it goes without saying that the method for producing the copolymer having the desired properties according to the present invention is not limited thereto. is there. The optimization of the control conditions for the various polymerization reactions described above can, of course, utilize the knowledge of the solution polymerization method. Therefore, one optimal embodiment of the present invention by the solution polymerization method will be described below.

(Solution Polymerization Method) Adjustment of Catalyst System In the present invention, the order of contacting the catalyst components is not particularly limited and can be selected depending on the polymerization conditions to be used, the type of monomers to be used, the addition conditions and the like. For example, (A)
The component and the component (B) may be contacted in advance and used as they are, or the contact product obtained by contacting the component (A) and the component (B) may be separated and washed before use. ,
Further, it may be used in contact with the contact product of the component (A) and the component (B) in the polymerization system. Furthermore, the component (C) may be used in contact with the component (A), the component (B), or the contact product of the component (A) and the component (B) in advance.

As a method for bringing the respective components into contact with each other, the contact may be adjusted in advance outside the polymerization reaction system or may be performed inside the polymerization reaction system. Further, the catalyst component may be added in advance to the monomer or the polymerization solvent, or may be added directly into the polymerization system. Further, the catalyst component may be used by supporting it on an inorganic (for example, zeolite type) or organic carrier (for example, polymer beads), if necessary. The inert hydrocarbon solvent used when preparing the catalyst in advance is not particularly limited, but specifically, it is an aliphatic hydrocarbon such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene. Hydrogen or alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclopentane, aromatic hydrocarbons such as benzene, toluene and xylene, and ethylene chloride and chlorobenzene,
It is possible to use halogenated hydrocarbons such as dichloromethane, or mixtures thereof. The preparation temperature is usually preferably in the range of -100 to 250 ° C, and the pressure and the preparation time can be set arbitrarily.

Long preparation times may be required when the preparation temperature is low. Also, when the catalyst component undergoes a decomposition reaction or is reacted at an excessive temperature, the catalytic activity decreases. Preferably, the catalyst is prepared at the temperature of the polymerization reaction conditions. Specifically, 0 to 100 ° C. is more preferable.

The polymerization solvent is not particularly limited in the present invention, and examples thereof include aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene, alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclopentane, and pentane. Aliphatic hydrocarbons such as hexane, heptane and octane, halogenated hydrocarbons such as chloroform and dichloromethane can be used. Further, these solvents may be used alone or in combination of two or more kinds. It is also possible to dissolve or use a monomer such as α-olefin.

The polymerization temperature can be optimized by various methods known to those skilled in the art, for example, experimental design method, in order to optimally produce the copolymer having the desired properties according to the present invention. Generally, in the present invention, -20 ° C or higher 12
It is preferably lower than 0 ° C, more preferably 0 to 100 ° C,
Particularly preferably 0 to 60 ° C., most preferably 20 to 60 ° C.
It is about ° C. When the polymerization reaction temperature is too low, the reaction activity is low and the progress of the reaction actually stops. If the temperature is too high, the catalyst system will be deactivated due to decomposition,
Undesirable side reactions occur in parallel, and the polymerization reaction itself stops. Therefore, the reaction temperature is preferably determined in order to maintain the desired catalyst activity and obtain a practical polymerization reaction rate. The catalyst system according to the present invention is particularly influenced by temperature, and is one of the most influential factors for adjusting the molecular structure, the amount of separation, etc. of the copolymer as a product. Regarding the optimization of the reaction temperature, the desired temperature range can be easily found by changing the reaction temperature.

Various organic chemical analysis methods can be used to monitor the progress of the reaction, and various spectral scans (IR, NMR) can be performed by partial sampling.
Etc.) enables easy monitoring.

Copolymer rubber Separation of the polymerization reaction product from the reaction solution is not particularly limited, and a method of removing the solvent by distillation, a method of removing the solvent by adding steam, or a poor solvent such as methanol is used. A method of precipitating by adding it is possible. The product recovered from the polymerization solution by further separation and recovery can be dried to obtain a solid random copolymer rubber.

The copolymer rubber obtained by the solution polymerization method based on the production method according to the present invention can be generally produced with the following characteristics. That is, the ethylene content is 30 to 90% by weight, preferably 32 to 88% by weight, and particularly preferably 35 to 85% by weight. The glass transition temperature (Tg) is at least -20 ° C.
Or less, preferably at least −30 ° C. or lower, and particularly preferably −40 ° C. or lower. The density (d) as one desirable property of the copolymer rubber according to the present invention is in the range of 0.840 to 0.900 g / cm ³ .
The range is preferably 0.845 to 0.900 g / cm ³ , and particularly preferably 0.850 to 0.898 g / cm 3.
The range is ³ . Furthermore, 1 of the copolymer rubber according to the present invention
One desirable property is that the copolymer rubber be ethylene-α.
In the case of an olefin-non-conjugated diene copolymer rubber, its iodine value is in the range of 0.5-40, preferably 1-30, and particularly preferably 2-25. is there.

Further, the intrinsic viscosity [η] of the random copolymer rubber measured in 70 ° C. xylene is usually
1.0 dl / g <[η] <8 dl / g, preferably 1.0 dl / g <[η] <6 dl / g,
Particularly preferably, it is in the range represented by 1.0 dl / g <[η] <5 dl / g.

Further, if the molecular weight of the copolymer rubber is expressed by the molecular weight measured by gel permeation chromatography (GPC), the weight average molecular weight Mw is 10
It is preferably from 10,000 to 10,000,000, more preferably from 150,000 to 1,000,000, and particularly preferably from 200,000 to 1,000,000. The number average molecular weight Mn is 5
It is preferably 50,000 to 5,000,000, more preferably 80,000 to 500,000, and particularly preferably 100,000 to 500,000.
Of the range. Furthermore, the molecular weight distribution (Mw / Mn =
Aw / An) is preferably 1.3 to 4.5,
The range is more preferably 1.3 to 3.8, and particularly preferably 1.3 to 3.0.

The present invention having the above characteristic parameters
The copolymer rubber obtained by the manufacturing method is a rubber material.
Commonly used EPM or E as a characteristic
Substantially similar properties of PDM are obtained. example
If (1) Mooney viscosity (Ml _{1 + 4} 120 ° C) is 5 or more
Which has an intrinsic viscosity as described herein.
[Η] corresponds to about 1. Furthermore, (2) MFR
It is a positive number of 18 or less at (190 ° C.).

Further, in the production method according to the present invention, control of the molecular weight is particularly important among the preferable characteristics described above, but in the production method according to the present invention, the selection of the catalyst system and the component ratio thereof are important. Can be controlled by optimizing the polymerization temperature and the polymerization temperature. In particular, in selecting the catalyst system, the component (C) which is an essential constituent of the present invention, methylaluminoxane, or an organoaluminum compound containing an alkyl group having at least one branch, particularly an organoaluminum compound having an isobutyl group, is selected. The influence of choice is large.

In the catalyst system according to the present invention, for the purpose of producing the above-mentioned desired copolymer rubber, methylaluminoxane or an organoaluminum having a branched isobutyl group (compared with, for example, triethylaluminum having no branch). For example, the selection of TIBA) is particularly preferable because the organoaluminum coordination maintains a high catalytic activity in the catalytically active center even at a relatively mild polymerization reaction temperature under the production conditions according to the present invention. It is presumed that it accelerates the polymerization of the polymerization product.

[0053]

【Example】

(Measurement Method of Copolymer Rubber Properties) The intrinsic viscosity [η] was measured in xylene at 70 ° C. using an Ubbelohde viscometer. Specifically, the procedure was as follows.

As a sample, 300 mg was dissolved in 100 ml of xylene to prepare a solution of about 3 mg / ml. Further, the solution was diluted to 1/2, 1/3, and 1/5, and each was measured using a Ubbelohde viscometer in a high temperature water bath at 70 ° C (± 0.1 ° C). Each concentration was repeated 3 times, and the obtained values were averaged.

The molecular weight distribution was determined by gel permeation chromatography (GPC) method (Waters, 150-C).
ALC / GPC apparatus).

The elution solution was o-dichlorobenzene, and the measurement temperature was 140 ° C. The column used was Sodex P manufactured by Showa Denko KK
acked Column A-80M, molecular weight standard substance is polystyrene (manufactured by Tosoh Corp., molecular weight 68-8,40).
10,000) was used. The obtained polystyrene-equivalent weight average molecular weight (Mw), number average molecular weight (Mn), and their ratio (Mw / Mn) are used as the molecular weight distribution.

The measurement sample was about 5 mg of the copolymer of 5 m.
It is dissolved in 1 of o-dichlorobenzene to a concentration of about 1 mg / ml. 400 μl of the obtained sample solution was injected. Elution solvent flow rate is 1.0 ml / min
And detected with a refractive index detector. The density (d) was measured using an underwater substitution method. Specifically 25 x 25 x 2 mm
The density of the sample press-molded at 23 ° C. was calculated by an A / (AB) X formula using an automatic hydrometer (manufactured by Toyo Seiki Co., Ltd.) (A: weight in sample air, B: weight in sample water). , X: water temperature correction coefficient) The glass transition temperature Tg was measured by a DSC200 apparatus manufactured by Seiko Instruments Inc.

About 10 mg of each sample was set in a sample cell made of aluminum, and the temperature was raised from -150 ° C to 150 ° C at 10 ° C / min for measurement.

The propylene content of the obtained copolymer rubber was measured by infrared absorption spectrum (IR spectrum) using polypropylene, polyethylene and ethylene-propylene copolymer (50:50) as standard products.
The measurement sample is about 0.1mm using a hot press machine.
The film was measured.

Measurement was carried out using literature values (characterization of polyethylene by infrared absorption spectrum) Takayama, Usami et al., Or Die Makromolekulare.
Chemie, 177 , 461 (1976) Mc R
ae, M .; A. , Madams, W.M. F. Et al.) And the absorption peak (methyl branching) at 1155 cm ⁻¹ was used as a marker to determine the average value of three measurements.

Similarly, the iodine value of EPDM was measured by infrared spectrum using poly-5-ethylidene-2-norbornene as a standard, and the absorption peak at 1688 cm ^-1 (ENB double bond) was used as a marker. .

The catalytic activity was determined based on the reaction conditions described in Example 1 based on the weight (g) of the copolymer rubber produced after the lapse of the polymerization time of 30 minutes, in terms of millimoles of the catalyst (component (A)) used. P- converted to the amount per hour
It was expressed by g / cat-mmol · h.

Example 1 A separable flask reactor having a capacity of 21 equipped with a stirrer, a thermometer, a dropping funnel, and a reflux condenser was decompressed, and then nitrogen gas was introduced to replace the inside with nitrogen gas. 1 L of dried n-hexane was introduced into this flask as a polymerization solvent. Here, mixed gas of ethylene and propylene (flow rate, ethylene:
Propylene = 8: 2 NL / min) was continuously fed at normal pressure, and the temperature of the solvent was set to 30 ° C. using a constant temperature water bath.

Then, triisobutylaluminum (hereinafter abbreviated as TIBA, 1.175 mmol) was added to the polymerization solvent.

(Tertiary butylamido) dimethyl (tetramethyl-η ⁵ -cyclopentadienyl) silane titanium dichloride (synthesized according to the method described in JP-A-3-163088, 0.0047 mmol) was added to a polymerization solvent, and subsequently, Then, a solution of triphenylcarbenium tetrakis (pentafluorophenyl) borate (0.0236 mmol) dissolved in 10 ml of toluene was added, and the mixture was stirred for 30 minutes to carry out a polymerization reaction. Then, the solvent was removed from the reaction mixture by a rotary evaporator to obtain 16 g of ethylene / propylene copolymer rubber. The properties of the obtained copolymer rubber are shown in Table 1.

Example 2 Instead of TIBA in Example 1, a toluene solution having a degree of polymerization of 7 or more methylaluminoxane (2 mol / l toluene solution manufactured by Akzo, Tosoh Corporation, hereinafter abbreviated as MAO) 1.1
The same conditions as in Example 1 were used except that 75 mmol was used, and 11 g of an ethylene / propylene copolymer rubber was obtained. The properties of the obtained copolymer rubber are shown in Table 1.

Example 3 Instead of the triphenylcarbenium tetrakis (pentafluorophenyl) borate used in Example 1, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate (0.0236 mmol)
Was carried out under the same conditions as in Example 1 except that
As a result, an ethylene / propylene copolymer rubber was obtained. The properties of the obtained copolymer rubber are shown in Table 1.

Comparative Example 1 (Tertiary butylamido) dimethyl (tetramethyl-η ⁵ -cyclopentadienyl) silane titanium dichloride (0.0052 mmol) used in Example 1, triphenylcarbenium tetrakis (pentafluorophenyl) Borate (0.026 mmol) was used, and triethyl aluminum (hereinafter abbreviated as TEA, 1.300 mmo) was used instead of TIBA used in Example 1.
Example 1 was repeated except that 1) was used (however, the polymerization time was 1 hour), and 7.6 g of an ethylene / propylene copolymer rubber was obtained. The properties of the obtained copolymer rubber are shown in Table 3.

Example 4 Instead of the (tertiary butylamido) dimethyl (tetramethyl-η ⁵ -cyclopentadienyl) silane titanium dichloride used in Example 1, ethylenebis (indenyl) hafnium dichloride (0.0047 mmo) was used.
l), N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate (0.0236 mmo
l) and TIBA (1.175 mmol) were used, the same procedure as in Example 1 was carried out to obtain 4.3 g of ethylene / propylene copolymer rubber. The properties of the obtained copolymer rubber are shown in Table 1.

Comparative Example 2 In Example 1, 0.0047 mmol of ethylenebis (indenyl) hafnium dichloride and triphenylcarbenium were used instead of (tertiary butylamido) dimethyl (tetramethyl-η ⁵ -cyclopentadienyl) silane titanium dichloride. Tetrakis (pentafluorophenyl)
Porate 0.0236mmol, TEA 1.175mm
Polymerization was carried out for 1 hour in the same manner as in Example 1 except that ol was used. As a result, 5.3 g of ethylene / propylene copolymer rubber was obtained. The properties of the obtained copolymer rubber are shown in Table 3.

Example 5 The same procedure as in Example 1 was repeated except that 5-ethylidene-2-norbornene (hereinafter abbreviated as ENB, 8 mmol) was added in Example 1 before adding the catalyst. A diene copolymer rubber was obtained. The properties of the resulting copolymer rubber are shown in Table 2.

Example 6 In Example 1 ENB (8 mmol) was further added before the catalyst addition and MAO (1 ..
The same procedure as in Example 1 was carried out except that 175 mmol) was used to obtain 20 g of an ethylene / propylene / diene copolymer rubber. The properties of the resulting copolymer rubber are shown in Table 2.

COMPARATIVE EXAMPLE 3 In Example 1, ENB (8 mmol) was further added before the catalyst was added, and TEA (1 ..
The same procedure as in Example 1 was performed except that 175 mmol) was used to obtain 1.8 g of an ethylene / propylene / diene copolymer rubber. The properties of the obtained copolymer rubber are shown in Table 3.

Example 7 Instead of the (tertiary butylamido) dimethyl (tetramethyl-η ⁵ -cyclopentadienyl) silane titanium dichloride used in Example 1, ethylenebis (indenyl) hafnium dichloride (0.0047 mmo) was used.
l), triphenylcarbenium tetrakis (pentafluorophenyl) porate (0.0236 mmol),
TIBA (1.175 mmol) was used, followed by ENB
The same procedure as in Example 1 was carried out except that (8 mmol) was added before the catalyst was added, to obtain 1.1 g of an ethylene / propylene / diene copolymer rubber. The properties of the resulting copolymer rubber are shown in Table 2.

Example 8 Instead of the (tertiary butylamido) dimethyl (tetramethyl-η ⁵ -cyclopentadienyl) silane titanium dichloride used in Example 1, ethylenebis (indenyl) hafnium dichloride (0.0047 mmo) was used.
l), triphenylcarbenium tetrakis (pentafluorophenyl) porate (0.0236 mmol),
MAO (1.175 mmol) was used, followed by ENB
2.1 g of ethylene / propylene / diene copolymer rubber was obtained in the same manner as in Example 1 except that (4 mmol) was added before adding the catalyst. The properties of the resulting copolymer rubber are shown in Table 2.

Comparative Example 4 Instead of the (tertiary butylamido) dimethyl (tetramethyl-η ⁵ -cyclopentadienyl) silane titanium dichloride used in Example 1, ethylenebis (indenyl) hafnium dichloride (0.0047 mmo) was used.
l), triphenylcarbenium tetrakis (pentafluorophenyl) porate (0.022 mmol), T
Using EA (1.100 mmol), ENB (4
(mmol) was added before the catalyst was added, and the same procedure as in Example 1 was carried out to obtain 0.2 g of an ethylene / propylene / diene copolymer rubber. The properties of the obtained copolymer rubber are shown in Table 3.

The following can be seen from the results. The results are clearly shown in Example 1 and Comparative Example 1 in which the catalyst having the structure of the formula (1) was used as the catalyst (A) component. The catalytic activity is increased by using TIBA than when TEA is used. Further, the obtained ethylene / propylene copolymer rubber has an intrinsic viscosity higher than that when TEA is used, and the number average molecular weight is about 10 times higher.

Furthermore, from Example 5 and Comparative Example 3, TIBA
The catalytic activity is several tens of times higher than that when TEA is used, and the obtained ethylene, propylene and diene copolymer rubber has an intrinsic viscosity higher than that when TEA is used, and the number average molecular weight is about The value is 10 times higher.

Similar results were obtained for Example 3 and Comparative Example 2 and Example 7 and Comparative Example 4 using the catalyst having the structure of formula (2) as the catalyst (A) component.

Further, when methylaluminoxane is used, the same effect as when TIBA is used is obtained.
(Examples 1 and 2, Examples 5 and 6, Examples 7 and 8)

[0081]

[Table 1] ------------------ Example 1 2 3 4 Yield g 16 11 69 4.3 Catalytic activity × 10 ³ 6.8 4.7 29.4 1.8 Pg / cat-mmol ・ h P wt% 60 65 62 22 Iodine number [η] dl / g 1.82 2.11 2.18 1.43 Density g / cm ³ 0.857 0.860 0.853 0.889 Tg ℃ -58 -53 -56 -52 Mn 134890 164820 166050 89790 Mw 358750 389910 487490 266090 Mw / Mn 2.6 2.3 2.9 2.9 −−−−−−−−−−−−−−−−−−−−−−−−−−

[0082]

[Table 2] ------------------ Example 5 6 7 8 Yield g 53 20 1.1 2.1 Catalytic activity × 10 ³ 22.5 8.5 0.5 0.9 Pg / cat-mmol ・ h P wt% 65 62 31 32 Iodine value 5.5 9.2 11.6 8.4 (η) dl / g 2.65 3.48 1.82 1.99 Density g / cm ³ 0.858 0.867 0.840 0.897 Tg ℃ -52 -55 -56 -57 Mn 195160 188190 151700 162770 Mw 622790 682650 403030 367360 Mw / Mn 3.1 3.6 2.7 2.3 −−−−−−−−−−−−−−−−−−−−−−−−−−−−

[0083]

[Table 3] ------------------ Comparative example 1 2 3 4 Yield g 7.6 5.3 1.8 0.2 Catalytic activity × 10 ³ 1.5 1.1 0.8 0.07 Pg / cat-mmol ・ h P wt% 62 32 63 21 Iodine value 8.5 9.3 〔η〕 dl / g 0.38 0.69 0.35 0.64 Tg ℃ -56 -58 -56 -50 Mn 11890 38540 16400 43050 Mw 24190 71340 31980 79950 Mw / Mn 2.0 1.8 1.9 1.8 −−−−−−−−−−−−−−−−−−−−−−−−−−−

[0084]

As described above, according to the present invention, the touch
In the presence of a catalyst system containing media components (A), (B), (C),
By polymerizing ethylene and α-olefin, ethylene-containing
30-90% by weight, density (d) 0.840-0.9
00g / cm^Three Manufacture copolymer rubber with various properties such as
Making possible ethylene-α-olefin copolymer rubber
Manufacturing method, and ethylene, α-olefin, and non-copolymer
By polymerizing diene, ethylene content 30-90 weight
%, Density (d) 0.840-0.900 g / cm ^Three ,
Copolymer Go having various characteristics such as iodine value of 0.5-40
Ethylene-α-olefin-nonconjugated
A method for producing a diene copolymer rubber can be provided.
Was.

[Brief description of the drawings]

FIG. 1 is a flowchart showing manufacturing steps of a catalyst.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Atsuko Furusawa 5-1 Anesaki Kaigan, Ichihara, Chiba Sumitomo Chemical Co., Ltd.

Claims (4)

[Claims] 1. The following components (A) to (C) are included.
Polymerize ethylene and α-olephane in the presence of a catalyst system.
The ethylene content is 30-90% by weight and the density (d) is
0.840-0.900 g / cm^Three To obtain a copolymer that is
Ethylene-α-olefin copolymer characterized by being
Rubber manufacturing method. Component (A): Transition gold represented by the chemical formula (1) or (2)
Genus complex(Where M represents a transition metal of Group IVB of the periodic table,
Cp¹ And Cp^Two Is a π bond with M or Hf
Represents a clopentadienyl group or a derivative group thereof, X ¹ as well as
X^Two Represents an anionic ligand or a neutral Lewis base ligand
Y represents a nitrogen atom, a phosphorus atom, an oxygen atom or a sulfur atom.
Represents a ligand having, Z is an oxygen atom, a sulfur atom, a boron atom
Child or atom of Group IVA of the Periodic Table. However, with Y
Z may combine with each other to form a condensed ring. ) Component (B): borate compound (C) component: methylaluminoxane or at least one
-Containing aluminum containing alkyl groups
Compound 2. The component (A) is (tertiary butylamido) dimethyl- (tetramethyl-η ⁵ -cyclopentadienyl) silane titanium dichloride or ethylene bis (indenyl) hafnium dichloride, and the component (B) is It is triphenylcarbenium tetrakis (pentafluorophenyl) borate or N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, and the organoaluminum compound of component (C) is methylaluminoxane or triisobutylaluminum. 1. The manufacturing method according to 1. 3. Containing the following components (A) to (C):
In the presence of a catalyst system, ethylene and α-olefins and
By polymerizing diene, ethylene content 30-90 weight
%, Density (d) 0.840-0.900 g / cm^Three ,
It is special to obtain a copolymer having an iodine value of 0.5-40.
Characteristic ethylene-α-olefin-non-conjugated diene co-weight
Method for producing united rubber. Component (A): Transition gold represented by the chemical formula (1) or (2)
Genus complex(Where M represents a transition metal of Group IVB of the periodic table,
Cp¹ And Cp^Two Is a π bond with M or Hf
Represents a clopentadienyl group or a derivative group thereof, X ¹ as well as
X^Two Represents an anionic ligand or a neutral Lewis base ligand
Y represents a nitrogen atom, a phosphorus atom, an oxygen atom or a sulfur atom.
Represents a ligand having, Z is an oxygen atom, a sulfur atom, a boron atom
Child or atom of Group IVA of the Periodic Table. However, with Y
Z may combine with each other to form a condensed ring. ) Component (B): borate compound (C) component: methylaluminoxane or at least one
-Containing aluminum containing alkyl groups
Compound 4. The component (A) is (tertiary butylamido) dimethyl- (tetramethyl-η ⁵ -cyclopentadienyl) silane titanium dichloride, or ethylenebis (indenyl) hafnium dichloride, and the component (B) is It is triphenylcarbenium tetrakis (pentafluorophenyl) borate or N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, and the organoaluminum compound of component (C) is methylaluminoxane or triisobutylaluminum. 3. The manufacturing method according to 3.