JP6713759B2 - Method for producing multi-component copolymer and multi-component copolymer - Google Patents

Description

The present invention relates to a method for producing a multicomponent copolymer and a multicomponent copolymer.

Generally, rubber products (tires, conveyor belts, anti-vibration rubber, seismic isolation rubber, etc.) are required to have high durability (breakdown resistance, abrasion resistance, crack growth resistance, etc.) and weather resistance. Various rubber components and rubber compositions have been developed to meet the requirements. For example, Patent Document 1 discloses that a conjugated diene compound (a part derived from a conjugated diene compound) has a cis-1,4 bond content of more than 70.5 mol% and a non-conjugated olefin content of 10 mol% or more. A copolymer with a conjugated olefin is disclosed, and it is also disclosed that the copolymer is used for producing a rubber having good crack growth resistance and weather resistance.

Such a copolymer is a binary copolymer obtained by polymerizing one kind of conjugated diene compound and one kind of non-conjugated olefin compound, and is increased by increasing the content of the non-conjugated olefin moiety contributing to the improvement of weather resistance. Crystallinity tends to increase. Due to such increase in crystallinity of the copolymer, the physical properties as an elastomer may be deteriorated, and when a rubber composition, a rubber product or the like is produced using the same (particularly at the time of kneading in the production of a rubber composition). Workability may deteriorate.

International Publication No. 2012/014455

In order to solve the problems of the binary copolymer as described above and contribute to the improvement of the durability and weather resistance of the rubber composition or the rubber product, a polymer having low crystallinity and excellent workability, a conjugated diene A terpolymer having both a compound-derived portion, a non-conjugated olefin compound-derived portion, and an aromatic vinyl compound-derived portion is considered. However, a method capable of producing such a terpolymer by polymerizing a conjugated diene compound, a non-conjugated olefin compound and an aromatic vinyl compound has not been reported so far. Therefore, such a ternary copolymer is, for example, a binary copolymer of a conjugated diene compound and an aromatic vinyl compound is synthesized, and a hydrogenation reaction is performed on the obtained binary copolymer to obtain a binary copolymer. It is produced by a method in which hydrogen is randomly added to unsaturated double bonds in the main chain of the copolymer.

However, such a manufacturing method has high cost and low manufacturing efficiency. Therefore, the present invention provides a method for producing a multicomponent copolymer capable of efficiently producing a multicomponent copolymer of a conjugated diene compound, a non-conjugated olefin compound, and an aromatic vinyl compound at low cost. The purpose is to do.

The method for producing the multi-component copolymer of the present invention is
It is characterized by comprising a step of polymerizing a conjugated diene compound, a non-conjugated olefin compound and an aromatic vinyl compound in the presence of a catalyst composition containing a rare earth element compound represented by the following formula (I).
M-(AQ ¹ )(AQ ² )(AQ ³ )...(I)
(In the formula, M is scandium, yttrium or a lanthanoid element; AQ ¹ , AQ ² and AQ ³ are functional groups which may be the same or different; A is nitrogen, oxygen or sulfur. Yes; provided that it has at least one M-A bond.)
According to the method for producing a multicomponent copolymer of the present invention, a multicomponent copolymer of a conjugated diene compound, a non-conjugated olefin compound, and an aromatic vinyl compound can be produced at low cost and efficiently.

In the method for producing a multicomponent copolymer of the present invention, it is preferable that the catalyst composition further includes a coordination compound that can serve as a ligand, and more preferably, the coordination compound has a cyclopentadiene skeleton. More preferably, the compound having a cyclopentadiene skeleton is a compound selected from substituted or unsubstituted cyclopentadiene, substituted or unsubstituted indene, and substituted or unsubstituted fluorene, and particularly preferably The compound having the indenyl group is a substituted phenylindenyl compound. By adopting these constitutions, it becomes possible to synthesize a multicomponent copolymer having a higher cis-1,4 bond content in a high yield.

In the method for producing a multi-component copolymer of the present invention, the catalyst composition further comprises at least one compound selected from the group consisting of ionic compounds and halogen compounds, and a compound represented by the following formula (II). It is preferable to include.
YR ¹ _a R ² _b R ³ _c ... (II)
(In the formula, Y is a metal selected from Group 1, Group 2, Group 12 and Group 13 of the periodic table, and R ¹ and R ² are hydrocarbon groups having 1 to 10 carbon atoms or hydrogen. And R ³ is a hydrocarbon group having 1 to 10 carbon atoms, R ¹ , R ² and R ³ may be the same or different from each other, and Y is selected from Group 1 of the periodic table. A is 1 and b and c are 0, and when Y is a metal selected from Groups 2 and 12 of the Periodic Table, a and b are 1 And c is 0 and a, b and c are 1 when Y is a metal selected from Group 13 of the Periodic Table.)
With this configuration, it is possible to more efficiently produce a multicomponent copolymer containing a conjugated diene compound, a non-conjugated olefin compound, and an aromatic vinyl compound.

In the method for producing a multicomponent copolymer of the present invention, the non-conjugated olefin compound is preferably ethylene. With this configuration, it is possible to efficiently polymerize with the conjugated diene compound, and at the same time, it is possible to produce a multicomponent copolymer having further reduced crystallinity and improved weather resistance.

In the method for producing a multi-component copolymer according to the present invention, the aromatic vinyl compound is preferably styrene. With this configuration, it is possible to efficiently polymerize with the conjugated diene compound, and at the same time, it is possible to produce a multicomponent copolymer having further reduced crystallinity and improved weather resistance.

In the method for producing a multicomponent copolymer of the present invention, the conjugated diene compound is preferably 1,3-butadiene. With this structure, it is possible to produce a multi-component copolymer with effectively improved durability.

The multi-component copolymer of the present invention is characterized by being manufactured by the above-mentioned manufacturing method. Such a multi-component copolymer has a long conjugated diene block and has a sufficiently reduced crystallinity, so that it can be used with high workability, and a rubber composition and tire having high durability and weather resistance are provided. can do.

According to the present invention, a conjugated diene compound, a non-conjugated olefin compound, a multicomponent copolymer of an aromatic vinyl compound, a method for producing a multicomponent copolymer that can be efficiently produced at low cost, and A multi-component copolymer produced by the production method can be provided.

Hereinafter, the present invention will be described in detail based on its embodiments.

(Method for producing multi-component copolymer)
The method for producing the multi-component copolymer of the present invention is
It is characterized by comprising a step of polymerizing a conjugated diene compound, a non-conjugated olefin compound and an aromatic vinyl compound in the presence of a catalyst composition containing a rare earth element compound represented by the following formula (I).
M-(AQ ¹ )(AQ ² )(AQ ³ )...(I)
(In the formula, M is scandium, yttrium or a lanthanoid element; AQ ¹ , AQ ² and AQ ³ are functional groups which may be the same or different; A is nitrogen, oxygen or sulfur. Yes; provided that it has at least one M-A bond.)
In the prior art, for example, there has not been a method for producing a multicomponent copolymer by polymerizing a conjugated diene compound, a non-conjugated olefin compound and an aromatic vinyl compound. Therefore, such a multicomponent copolymer has been produced by subjecting a binary copolymer obtained by polymerizing a conjugated diene compound and an aromatic vinyl compound to a hydrogenation reaction. On the other hand, by using the catalyst composition of the present invention, a conjugated diene compound, a non-conjugated olefin compound, and an aromatic vinyl compound were polymerized to produce a multicomponent copolymer. In addition, the production method of the present invention is different from the conventional method of subjecting the binary copolymer to a hydrogenation reaction, in which cis-1,4 in the whole unit derived from the conjugated diene in the produced multicomponent copolymer. The bond content can be significantly increased and long conjugated diene blocks can be formed.

<Conjugated diene compound>
In the present specification, the conjugated diene compound refers to a conjugated diene compound. The conjugated diene compound used as a monomer in the production method of the present invention is not particularly limited, but preferably has 4 to 8 carbon atoms. Specific examples of the conjugated diene compound include 1,3-butadiene, isoprene, 1,3-pentadiene, and 2,3-dimethylbutadiene. Of these, 1,3-butadiene is preferable. This is because it is possible to effectively improve the durability of the rubber composition, tire, etc. using the produced multi-component copolymer.

<Non-conjugated olefin compound>
In the present specification, the olefin compound refers to a compound that is an aliphatic unsaturated hydrocarbon and has one or more carbon-carbon double bonds, and the non-conjugated olefin compound does not include an aromatic vinyl compound. The non-conjugated olefin compound used as a monomer in the production method of the present invention is not particularly limited, but preferably has 2 to 10 carbon atoms. Examples of the non-conjugated olefin compound include α-olefins such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, and 1-octene; vinyl pivalate, 1-phenylthioethene, or N. And hetero atom-substituted alkene compounds such as vinylpyrrolidone. The non-conjugated olefin compound is not particularly limited, and the above-mentioned non-conjugated olefin compounds can be used. Among these, a non-cyclic non-conjugated olefin compound is preferable, and α-olefin. Is more preferable, and ethylene is particularly preferable. An acyclic non-conjugated olefin compound such as α-olefin, particularly ethylene, has a double bond at the α-position of the olefin, and therefore can be efficiently polymerized with a conjugated diene compound, and also the produced multi-component terpolymer This is because it is possible to further reduce the crystallinity of the coalescence and further improve the weather resistance of the rubber composition, tire, etc. using such a multi-component copolymer.

<Aromatic vinyl compound>
In the present specification, the aromatic vinyl compound refers to an aromatic compound substituted with at least a vinyl group. The aromatic vinyl compound used as a monomer in the production method of the present invention is not particularly limited, but preferably has 8 to 10 carbon atoms. Examples of the aromatic vinyl compound include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o,p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene and p-ethylstyrene. .. The aromatic vinyl compound is not particularly limited, and the above-mentioned aromatic vinyl compounds can be used, but among these, styrene is more preferable. This is because the copolymer can be efficiently polymerized with the conjugated diene compound, the crystallinity of the produced copolymer can be further reduced, and the weather resistance can be further improved.

<Catalyst composition>
The catalyst composition used in the production method of the present invention,
Component (A): Rare earth element compound represented by the following formula (I) M-(AQ ¹ )(AQ ² )(AQ ³ )...(I)
(In the formula, M is scandium, yttrium or a lanthanoid element; AQ ¹ , AQ ² and AQ ³ are functional groups which may be the same or different; A is nitrogen, oxygen or sulfur. Yes; provided that it has at least one M-A bond.)
including.
Here, the lanthanoid element is specifically lanthanium, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium. The component (A) has at least one M-A bond. Further, the component (A) is a component capable of improving the catalytic activity in the reaction system, shortening the reaction time, and increasing the reaction temperature.
Further, with respect to the M, gadolinium is particularly preferable from the viewpoint of enhancing catalyst activity and reaction controllability.
In addition, the said (A) component may be used individually by 1 type, and may be used in combination of 2 or more type.

That is, the compound represented by the above formula (I) has at least one MA bond. By having one or more M-A bonds, each bond is chemically equivalent, so that the structure is stable, and therefore, the structure is easy to handle, and the multi-component copolymer can be efficiently produced at low cost. You can do it. In addition, the compound represented by the above formula (I) may include a bond other than M-A, for example, a bond between the metal other than M and a hetero atom such as O or S.

In the above formula (I), when A is nitrogen, examples of the functional group represented by AQ ¹ , AQ ² and AQ ³ (that is, NQ ¹ , NQ ² and NQ ³ ) include an amide group and the like.
Examples of the amide group include an aliphatic amide group such as a dimethylamide group, a diethylamide group and a diisopropylamide group; a phenylamide group, a 2,6-di-tert-butylphenylamide group, a 2,6-diisopropylphenylamide group, 2,6-Dineobenzylphenylamide group, 2-tert-butyl-6-isopropylphenylamide group, 2-tert-butyl-6-neobentylphenylamide group, 2-isopropyl-6-neobentylphenyl Examples thereof include amide groups, arylamide groups such as 2,4,6-tert-butylphenylamide group; and bistrialkylsilylamide groups such as bistrimethylsilylamide group. Particularly, from the viewpoint of solubility in aliphatic hydrocarbons, A trimethylsilylamide group is preferred.
The above functional groups may be used alone or in combination of two or more.

In the formula (I), when A is oxygen, examples of the functional group represented by AQ ¹ , AQ ² and AQ ³ (that is, OQ ¹ , OQ ² and OQ ³ ) include, for example, an alkoxy group and an alkoxycarboxyl group. Etc. As the alkoxy group, a methoxy group, an ethoxy group, an isopropoxy group and the like are preferable. Further, as the acyloxy group, an acetoxy group, a valeroyl group, a pivaloxy group and the like are preferable.

In the above formula (I), when A is sulfur, the functional groups represented by AQ ¹ , AQ ² and AQ ³ (that is, SQ ¹ , SQ ² and SQ ³ ) include, for example, an alkylthio group and an alkylsulfonyl group. Etc. As the alkylthio group, a methylthio group, an isopropylthio group and the like are preferable. Moreover, as the alkylsulfonyl group, a phenylsulfonyl group, an isopropanesulfonyl group, a hexanesulfonyl group and the like are preferable.

Specific examples of the lanthanoid include lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium. In addition, the said (A) component may be used individually by 1 type, and may be used in combination of 2 or more type.

In the polymerization reaction system, the concentration of component (A) contained in the catalyst composition is preferably in the range of 0.1 to 0.0001 mol/l.

Further, the catalyst composition used in the production method of the present invention further comprises
Component (B): at least one selected from the group consisting of a specific ionic compound (B-1) and a specific halogen compound (B-2),
Component (C): Formula (II) below:
YR ¹ _a R ² _b R ³ _c ... (II)
(In the formula, Y is a metal selected from Group 1, Group 2, Group 12 and Group 13 of the periodic table, and R ¹ and R ² are hydrocarbon groups having 1 to 10 carbon atoms or hydrogen. And R ³ is a hydrocarbon group having 1 to 10 carbon atoms, R ¹ , R ² and R ³ may be the same or different from each other, and Y is selected from Group 1 of the periodic table. A is 1 and b and c are 0, and when Y is a metal selected from Groups 2 and 12 of the Periodic Table, a and b are 1 And c is 0, and when Y is a metal selected from Group 13 of the periodic table, a, b and c are preferably 1).
This is because it is possible to more efficiently produce a multicomponent copolymer of a conjugated diene compound, a non-conjugated olefin compound, and an aromatic vinyl compound.

Since the ionic compound (B-1) and the halogen compound (B-2) do not have carbon atoms for supplying to the component (A), the above-mentioned ionic compound (B-1) and the halogen compound (B-2) are used as carbon sources for the component (A). Component (C) is required. In addition, the catalyst composition may include other components contained in a usual rare earth element compound-based catalyst composition, for example, a cocatalyst.
The total content of the component (B) in the catalyst composition is preferably 0.1 to 50 times the mol of the component (A).

The ionic compound represented by the above (B-1) is an ionic compound composed of a non-coordinating anion and a cation, and reacts with the rare earth element compound of the component (A) to form a cationic transition metal compound. Examples thereof include ionic compounds that can be generated.
Here, examples of the non-coordinating anion include tetraphenylborate, tetrakis(monofluorophenyl)borate, tetrakis(difluorophenyl)borate, tetrakis(trifluorophenyl)borate, tetrakis(tetrafluorophenyl)borate, tetrakis( Pentafluorophenyl)borate, tetrakis(tetrafluoromethylphenyl)borate, tetra(tolyl)borate, tetra(xylyl)borate, (triphenyl, pentafluorophenyl)borate, [tris(pentafluorophenyl),phenyl]borate, tri Decahydride-7,8-dicarbaundecaborate and the like can be mentioned. On the other hand, examples of the cation include a carbonium cation, an oxonium cation, an ammonium cation, a phosphonium cation, a cycloheptatrienyl cation, and a ferrocenium cation having a transition metal. Specific examples of the carbonium cation include tri-substituted carbonium cations such as triphenylcarbonium cation and tri(substituted phenyl)carbonium cation, and more specifically, as tri(substituted phenyl)carbonium cation, , Tri(methylphenyl)carbonium cation, tri(dimethylphenyl)carbonium cation, and the like. Specific examples of ammonium cations include trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tripropylammonium cation, and tributylammonium cation (eg, tri(n-butyl)ammonium cation); N,N-dimethylanilinium. Cations, N,N-dialkylanilinium cations, N,N-dialkylanilinium cations such as N,N-2,4,6-pentamethylanilinium cations; dialkylammonium cations such as diisopropylammonium cations and dicyclohexylammonium cations Are listed. Specific examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tri(methylphenyl)phosphonium cation, and tri(dimethylphenyl)phosphonium cation. Therefore, the ionic compound is preferably a compound selected and combined from the above-mentioned non-coordinating anion and cation, specifically, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, triphenylcarboate. Preference is given to titanium tetrakis(pentafluorophenyl)borate and the like. Moreover, these ionic compounds can be used individually by 1 type or in mixture of 2 or more types.
The content of the ionic compound (B-1) in the catalyst composition is 0.1 to 10 times mol, preferably about 1 times mol of the component (A). Is more preferable.

The halogen compound represented by (B-2) is at least one of a Lewis acid, a complex compound of a metal halide and a Lewis base, and an organic compound containing active halogen. By reacting with the rare earth element compound of the component (A), a cationic transition metal compound, a halogenated transition metal compound, or a compound having a transition metal center with insufficient charge can be produced.
The total content of the halogen compound (B-2) in the catalyst composition is preferably 1 to 5 times the mol of the component (A).

As the Lewis acid, B (C ₆ F ₅₎ boron-containing halogen compounds such as _{3, Al (C 6 F 5} ) except that the aluminum-containing halogen compounds such as ₃ can be used, the third group in the periodic table, the A halogen compound containing an element belonging to Group 4, Group 5, Group 6, or Group 8 can also be used. Preferably, an aluminum halide or an organic metal halide is used. Further, chlorine or bromine is preferable as the halogen element. As the Lewis acid, specifically, methyl aluminum dibromide, methyl aluminum dichloride, ethyl aluminum dibromide, ethyl aluminum dichloride, butyl aluminum dibromide, butyl aluminum dichloride, dimethyl aluminum bromide, dimethyl aluminum chloride, diethyl aluminum bromide, diethyl Aluminum chloride, dibutyl aluminum bromide, dibutyl aluminum chloride, methyl aluminum sesquibromide, methyl aluminum sesquichloride, ethyl aluminum sesquibromide, ethyl aluminum sesquichloride, dibutyltin dichloride, aluminum tribromide, antimony trichloride, antimony pentachloride, phosphorus trichloride , Phosphorus pentachloride, tin tetrachloride, titanium tetrachloride, tungsten hexachloride and the like. Among these, diethyl aluminum chloride, ethyl aluminum sesquichloride, ethyl aluminum dichloride, diethyl aluminum bromide, ethyl aluminum sesquibromide, ethyl aluminum dichloride. Bromide is particularly preferred.

Examples of the metal halide forming the complex compound of the metal halide and the Lewis base include beryllium chloride, beryllium bromide, beryllium iodide, magnesium chloride, magnesium bromide, magnesium iodide, calcium chloride, calcium bromide, and iodine. Calcium iodide, barium chloride, barium bromide, barium iodide, zinc chloride, zinc bromide, zinc iodide, cadmium chloride, cadmium bromide, cadmium iodide, mercury chloride, mercury bromide, mercury iodide, manganese chloride, Manganese bromide, manganese iodide, rhenium chloride, rhenium bromide, rhenium iodide, copper chloride, copper bromide, copper iodide, silver chloride, silver bromide, silver iodide, gold chloride, gold iodide, bromide Examples thereof include gold. Of these, magnesium chloride, calcium chloride, barium chloride, manganese chloride, zinc chloride, and copper chloride are preferable, and magnesium chloride, manganese chloride, zinc chloride, and copper chloride are particularly preferable.

Further, as the Lewis base constituting the complex compound of the metal halide and the Lewis base, phosphorus compounds, carbonyl compounds, nitrogen compounds, ether compounds, alcohols and the like are preferable. Specifically, tributyl phosphate, tri-2-ethylhexyl phosphate, triphenyl phosphate, tricresyl phosphate, triethylphosphine, tributylphosphine, triphenylphosphine, diethylphosphinoethane, diphenylphosphinoethane, acetylacetone, benzoylacetone , Propionitrile acetone, valeryl acetone, ethyl acetylacetone, methyl acetoacetate, ethyl acetoacetate, phenyl acetoacetate, dimethyl malonate, diethyl malonate, diphenyl malonate, acetic acid, octanoic acid, 2-ethylhexanoic acid, oleic acid , Stearic acid, benzoic acid, naphthenic acid, versatic acid, triethylamine, N,N-dimethylacetamide, tetrahydrofuran, diphenyl ether, 2-ethylhexyl alcohol, oleyl alcohol, stearyl alcohol, phenol, benzyl alcohol, 1-decanol, lauryl alcohol, etc. Among these, tri-2-ethylhexyl phosphate, tricresyl phosphate, acetylacetone, 2-ethylhexanoic acid, versatic acid, 2-ethylhexyl alcohol, 1-decanol and lauryl alcohol are preferable.

The Lewis base is reacted in a proportion of 0.01 to 30 mol, preferably 0.5 to 10 mol, per 1 mol of the metal halide. The use of the reaction product with this Lewis base can reduce the amount of metal remaining in the polymer.

Examples of the organic compound containing active halogen include benzyl chloride.

The component (C) that can be used in the catalyst composition is represented by the following formula (II):
YR ¹ _a R ² _b R ³ _c ... (II)
(In the formula, Y is a metal selected from Group 1, Group 2, Group 12 and Group 13 of the periodic table, and R ¹ and R ² are hydrocarbon groups having 1 to 10 carbon atoms or hydrogen. And R ³ is a hydrocarbon group having 1 to 10 carbon atoms, R ¹ , R ² and R ³ may be the same or different from each other, and Y is selected from Group 1 of the periodic table. A is 1 and b and c are 0, and when Y is a metal selected from Groups 2 and 12 of the Periodic Table, a and b are 1 And c is 0, and Y is a metal selected from Group 13 of the periodic table, a, b and c are 1), and a compound represented by the following formula (III): :
AlR ¹ R ² R ³ ... (III)
(In the formula, R ¹ and R ² are a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom, R ³ is a hydrocarbon group having 1 to 10 carbon atoms, and R ¹ , R ² , and R ³ are respectively It may be the same or different from each other). Examples of the organoaluminum compound of the formula (III) include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-t-butylaluminum, tripentylaluminum, Trihexyl aluminum, tricyclohexyl aluminum, trioctyl aluminum; diethyl aluminum hydride, di-n-propyl aluminum hydride, di-n-butyl aluminum hydride, diisobutyl aluminum hydride, dihexyl aluminum hydride, diisohexyl hydride Aluminum, dioctylaluminum hydride, diisooctylaluminum hydride; ethylaluminum dihydride, n-propylaluminium dihydride, isobutylaluminum dihydride, and the like can be mentioned, and among these, triethylaluminum, triisobutylaluminum, diethylaluminum hydride. Preferred is diisobutylaluminum hydride. The organoaluminum compound as the component (C) described above may be used alone or in combination of two or more. The content of the organoaluminum compound in the catalyst composition is preferably 1 to 50 times mol, and more preferably about 10 times mol, of the component (A).

Further, the catalyst composition used in the production method of the present invention makes it possible to synthesize a copolymer having a higher cis-1,4 bond content in a high yield.
Component (D): It is preferable to further include a coordination compound that can serve as a ligand.
The component (D) is not particularly limited as long as it can be exchanged with the amide group of the component (A), and examples thereof include those having any of an OH group, an NH group and an SH group. ..

Specific compounds having an OH group include aliphatic alcohols and aromatic alcohols. Specifically, 2-ethyl-1-hexanol, dibutylhydroxytoluene, alkylated phenol, 4,4′-thiobis-(6-t-butyl-3-methylphenol), 4,4′-butylidenebis-(6- t-butyl-3-methylphenol), 2,2'-methylenebis-(4-methyl-6-t-butylphenol), 2,2'-methylenebis-(4-ethyl-6-t-butylphenol), 2, 6-di-t-4-ethylphenol, 1,1,3-tris-(2-methyl-4-hydroxy-5-t-butylphenyl)butane, n-octadecyl-3-(4-hydroxy-3, 5-di-t-butylphenyl)propionate, tetrakis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane, dilaurylthiodipropionate, distearylthiodipropionate , Dimyristyl thiopropionate and the like, but are not limited thereto. For example, as a hindered phenol type, triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,3 5-di-t-butyl-4-hydroxyphenyl)propionate], 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3 5-triazine, pentaerythryl-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,2-thio-diethylenebis[3-(3,5-di-t] -Butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, N,N'-hexamethylenebis(3,5-di-t- Butyl-4-hydroxy-hydrocinnamamide), 3,5-t-butyl-4-hydroxybenzylphosphonate-diethyl ester, 1,3,5-trimethyl-2,4,6-tris(3,5-di) -T-butyl-4-hydroxybenzyl)benzene, tris-(3,5-di-t-butyl-4-hydroxybenzyl)-isocyanurate, octylated diphenylamine, 2,4-bis[(octylthio)methyl]- Examples thereof include o-cresol. Examples of the hydrazine-based compound include N,N'-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyl]hydrazine.

Examples of those having an NH group include primary amines or secondary amines such as alkylamines and arylamines. Specific examples thereof include dimethylamine, diethylamine, pyrrole, ethanolamine, diethanolamine, dicyclohexylamine, N,N'-dibenzylethylenediamine, bis(2-diphenylphosphinophenyl)amine and the like.

（式中、Ｒ¹、Ｒ²及びＲ³はそれぞれ独立して−Ｏ−Ｃ_jＨ_2j+1、−（Ｏ−Ｃ_kＨ_2k−）_a −Ｏ−Ｃ_mＨ_2m+1又は−Ｃ_nＨ_2n+1 で表され、Ｒ¹、Ｒ²及びＲ³の少なくとも１つが−（Ｏ−Ｃ_kＨ_2k−）_a−Ｏ−Ｃ_mＨ_2m+1であり、ｊ、ｍ及びｎはそれぞれ独立して０〜１２であり、ｋ及びａはそれぞれ独立して１〜１２であり、Ｒ⁴は炭素数１〜１２であって、直鎖、分岐、もしくは環状の、飽和もしくは不飽和の、アルキレン基、シクロアルキレン基、シクロアルキルアルキレン基、シクロアルケニルアルキレン基、アルケニレン基、シクロアルケニレン基、シクロアルキルアルケニレン基、シクロアルケニルアルケニレン基、アリーレン基又はアラルキレン基である。）
上記式（ＶＩ）で示されるものの具体例として、３−メルカプトプロピルトリメトキシシラン、３−メルカプトプロピルトリエトキシシラン、３−メルカプトプロピルメチルジメトキシシラン、（メルカプトメチル）ジメチルエトキシシラン、メルカプトメチルトリメトキシシラン等が挙げられる。

（式中、Ｗは−ＮＲ⁸−、−Ｏ−又は−ＣＲ⁹Ｒ¹⁰−（ここで、Ｒ⁸及びＲ⁹は−Ｃ_pＨ_2p+1であり、Ｒ¹⁰は−Ｃ_qＨ_2q+1であり、ｐ及びｑはそれぞれ独立して０〜２０である。）で表され、Ｒ⁵及びＲ⁶はそれぞれ独立して−Ｍ−Ｃ_rＨ_2r−（ここで、Ｍは−Ｏ−又は−ＣＨ₂−であり、ｒは１〜２０である。）で表され、Ｒ⁷は−Ｏ−Ｃ_jＨ_2j+1、−（Ｏ−Ｃ_kＨ_2k−）_a−Ｏ−Ｃ_mＨ_2m+1又は−Ｃ_nＨ_2n+1 で表され、ｊ、ｍ及びｎはそれぞれ独立して０〜１２であり、ｋ及びａはそれぞれ独立して１〜１２であり、Ｒ⁴は炭素数１〜１２であって、直鎖、分岐、もしくは環状の、飽和もしくは不飽和の、アルキレン基、シクロアルキレン基、シクロアルキルアルキレン基、シクロアルケニルアルキレン基、アルケニレン基、シクロアルケニレン基、シクロアルキルアルケニレン基、シクロアルケニルアルケニレン基、アリーレン基又はアラルキレン基である。）
式（ＶＩＩ）で示されるものの具体例として、３−メルカプトプロピル（エトキシ）−１，３−ジオキサ−６−メチルアザ−２−シラシクロオクタン、３−メルカプトプロピル（エトキシ）−１，３−ジオキサ−６−ブチルアザ−２−シラシクロオクタン、３−メルカプトプロピル（エトキシ）−１，３−ジオキサ−６−ドデシルアザ−２−シラシクロオクタンなどが挙げられる。 Examples of compounds having an SH group include compounds represented by the following formulas (VI) and (VII) in addition to aliphatic thiols and aromatic thiols.

(In the formula, R ¹ , R ² and R ³ are each independently —O—C _j H _2j+1 , —(O—C _k H _2k −) _a —O—C _m H _2m+1 or —C. _n H _2n+1 , at least one of R ¹ , R ² and R ³ is —(O—C _k H _2k −) _a —O—C _m H _2m+1 , and j, m and n are Each independently 0 to 12, k and a each independently 1 to 12, R ⁴ has 1 to 12 carbon atoms, and is linear, branched, or cyclic, saturated or unsaturated. , An alkylene group, a cycloalkylene group, a cycloalkylalkylene group, a cycloalkenylalkylene group, an alkenylene group, a cycloalkenylene group, a cycloalkylalkenylene group, a cycloalkenylalkenylene group, an arylene group or an aralkylene group.)
Specific examples of those represented by the above formula (VI) include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, (mercaptomethyl)dimethylethoxysilane, and mercaptomethyltrimethoxysilane. Etc.

(Wherein, W is -NR ⁸ -, - O- or -CR ⁹ R ¹⁰ - (wherein, R ⁸ and R ⁹ are _{-C p H 2p + 1, R} 10 is -C _q H _{2q + 1} and p and q are each independently 0 to 20), and R ⁵ and R ⁶ are each independently —M—C _r H _2r — (where M is —O—. Or —CH ₂ —, r is 1 to 20), and R ⁷ is —O—C _j H _2j+1 , —(O—C _k H _2k —) _a —O—C _m. H _2m+1 or —C _n H _2n+1 , j, m and n each independently represent 0 to 12, k and a each independently represent 1 to 12, and R ⁴ represents carbon. Number 1 to 12 and is a linear, branched, or cyclic, saturated or unsaturated alkylene group, cycloalkylene group, cycloalkylalkylene group, cycloalkenylalkylene group, alkenylene group, cycloalkenylene group, cycloalkylalkenylene. Group, a cycloalkenylalkenylene group, an arylene group or an aralkylene group.)
Specific examples of those represented by the formula (VII) include 3-mercaptopropyl(ethoxy)-1,3-dioxa-6-methylaza-2-silacyclooctane and 3-mercaptopropyl(ethoxy)-1,3-dioxa-. 6-butylaza-2-silacyclooctane, 3-mercaptopropyl(ethoxy)-1,3-dioxa-6-dodecylaza-2-silacyclooctane and the like can be mentioned.

Further, the coordination compound of the component (D) is preferably a compound having a cyclopentadiene skeleton.
Further, the compound having a cyclopentadiene skeleton is not particularly limited as long as it has a cyclopentadiene skeleton, but a compound having an indenyl group is more preferable from the viewpoint that higher catalytic activity can be obtained. This is because the activity can be enhanced without using toluene as a solvent at the time of polymerization.

Here, as the compound having an indenyl group, for example, indene, 1-methylindene, 1-ethylindene, 1-benzylindene, 2-phenylindene, 2-methylindene, 2-ethylindene, 2-benzylindene , 3-methylindene, 3-ethylindene, 3-benzylindene and the like can be mentioned, and among them, it is preferable to use a substituted phenylindenyl compound.

The component (D) is preferably added in an amount of 0.01 to 10 mol, particularly 0.1 to 1.2 mol, relative to 1 mol of the rare earth element compound of the component (A). If the amount added is less than 0.01 mol, the polymerization of the monomer may not proceed sufficiently. The addition amount is preferably the same as the rare earth element compound (1.0 mol), but an excessive amount may be added. However, if the addition amount exceeds 10 mol, the loss of the reagent is large, which is not preferable.

<Polymerization process>
The production method of the present invention comprises a step of polymerizing a conjugated diene compound, a non-conjugated olefin compound and an aromatic vinyl compound in the presence of the catalyst composition (hereinafter, also referred to as a polymerization step), and further requires According to the requirements, a coupling step, a washing step, and other steps can be appropriately provided.

As the polymerization method in the polymerization step, any method such as a solution polymerization method, a suspension polymerization method, a liquid phase bulk polymerization method, an emulsion polymerization method, a gas phase polymerization method or a solid phase polymerization method can be used. When a solvent is used in the polymerization reaction, such a solvent may be one that is inactive in the polymerization reaction, and examples thereof include toluene, cyclohexane, and normal hexane.

In the production method of the present invention, the polymerization step may be performed in one stage or in multiple stages of two or more stages. The one-step polymerization step is a step of simultaneously reacting all three kinds of monomers to be polymerized, that is, a conjugated diene compound, a non-conjugated olefin compound, and an aromatic vinyl compound to perform polymerization. In the multi-step polymerization step, a part or all of one or two kinds of monomers are first reacted to form a polymer (first polymerization step), and then the remaining kinds of monomers or It is a step of polymerizing by performing one or more steps (second polymerization step to final polymerization step) of adding and polymerizing the rest of the one or two kinds of monomers.

In the presence of the catalyst composition, since the reactivity of the conjugated diene compound is higher than that of the non-conjugated olefin compound and the aromatic vinyl compound, the multicomponent compound produced by controlling the order of introducing the conjugated diene compound. Bond content (cis-1,4 bond content, trans-1,4 bond content, 3,4 vinyl bond content and 1,2 vinyl bond content) and each monomer in the unit derived from the conjugated diene compound in the polymer The content of the derived unit (that is, the copolymerization ratio of each monomer) can be controlled. For example, when the conjugated diene compound is added from the first polymerization stage to perform the polymerization process in multiple stages, the block length of the conjugated diene compound-derived portion becomes long, and a multi-component copolymer having a block sequence is obtained. To be On the other hand, when the conjugated diene compound is added after the second polymerization step and the polymerization step is performed in multiple stages, the block length of the conjugated diene compound-derived portion is shortened, and a multicomponent copolymer having a more random arrangement is obtained.

In the production method of the present invention, the polymerization step is preferably performed in an atmosphere of an inert gas, preferably nitrogen gas or argon gas. The polymerization temperature in the polymerization step is not particularly limited, but is preferably in the range of −100 to 200° C., and may be about room temperature. In addition, if the polymerization temperature is raised, the cis-1,4 selectivity of the polymerization reaction may decrease. The pressure in the polymerization step is preferably in the range of 0.1 to 10.0 MPa in order to sufficiently incorporate the non-conjugated olefin compound into the polymerization reaction system. The reaction time of the polymerization step is not particularly limited, but is, for example, in the range of 1 second to 10 days, and the desired microstructure of the obtained multicomponent copolymer, the type of each monomer, the input amount and the addition order, the catalyst It can be appropriately selected depending on the conditions such as the type of the compound and the polymerization temperature. In the polymerization step, the polymerization may be stopped by using a polymerization terminator such as methanol, ethanol or isopropanol.

<Coupling process>
The coupling step is a step of carrying out a reaction (coupling reaction) for modifying at least a part (for example, a terminal) of the polymer chain of the multicomponent copolymer obtained in the above-mentioned polymerization step. In the coupling step, it is preferable to perform the coupling reaction when the polymerization reaction reaches 100%.
The coupling agent used in the coupling reaction is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include tin-containing compounds such as bis(-1-octadecyl maleate dioctyltin): 4,4 Examples thereof include isocyanate compounds such as'-diphenylmethane diisocyanate; alkoxysilane compounds such as glycidylpropyltrimethoxysilane. These may be used alone or in combination of two or more. Among these, bis(-1-octadecyl maleate-1-octadecyl)dioctyltin is preferable in terms of reaction efficiency and low gel formation.
The number average molecular weight (Mn) can be increased by performing the coupling reaction.

<Washing process>
The washing step is a step of washing the multicomponent copolymer obtained in the polymerization step. The medium used for washing is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include methanol, ethanol and isopropanol. When a Lewis acid-derived catalyst is used as a polymerization catalyst, Can be used by adding an acid (for example, hydrochloric acid, sulfuric acid, nitric acid) to these solvents. The amount of acid added is preferably 15 mol% or less based on the solvent. If the amount is higher than this, the acid may remain in the copolymer, which may adversely affect the reaction during kneading and vulcanization.
By this washing step, the amount of catalyst residue in the copolymer can be suitably reduced.

<Identification of multi-component copolymer>
Whether a multi-component copolymer is obtained by the production method of the present invention is determined by using a technique such as gel permeation chromatography (GPC), ¹ H-NMR, ¹³ C-NMR, etc. for the polymerization product. Can be confirmed by. Specifically, based on gel permeation chromatography-refractive index curve (GPC-RI curve) and gel permeation chromatography-ultraviolet absorption curve (GPC-UV curve), aromatics such as benzene ring in the copolymer The presence of the skeleton derived from the aromatic vinyl compound can be confirmed by confirming the UV absorption by the ring. The presence of units derived from each monomer component can be confirmed based on the ¹ H-NMR spectrum and ¹³ C-NMR spectrum.

(Multi-component copolymer)
The multi-component copolymer of the present invention produced by the above production method contains a conjugated diene compound, a non-conjugated olefin compound and an aromatic vinyl compound, and therefore has high durability derived from a conjugated diene compound and a non-conjugated olefin. Both the compound and the aromatic vinyl compound intervene to improve the weather resistance by reducing the ratio of double bonds.
Further, since the multi-component copolymer of the present invention is obtained by polymerizing using a conjugated diene compound, for example, a known non-conjugated diene compound such as ethylene-propylene-non-conjugated diene copolymer (EPDM) is used. It has excellent cross-linking properties as compared with the copolymer obtained by polymerization. Therefore, the multi-component copolymer of the present invention also has an advantage that the mechanical properties of a rubber composition or a rubber product produced by using the multi-component copolymer can be further improved.
The multi-component polymer of the present invention may be a multi-component polymer containing a conjugated diene compound, a non-conjugated olefin compound, and an aromatic vinyl compound, and may be a terpolymer, It may be a multi-component polymer (such as a quaternary copolymer) described above.

The physical properties and microstructure of the multi-component copolymer of the present invention should be identified by using techniques such as differential scanning calorimetry (DSC), ¹ H-NMR, ¹³ C-NMR, gel permeation chromatography (GPC) and the like. You can Specifically, the melting point (°C) can be determined by DSC. The content and ratio of each monomer component-derived unit and the cis-1,4 bond content, trans-1,4 bond content, and 1,2-vinyl bond content in the entire unit derived from the conjugated diene compound are ¹ H-NMR and It can be determined by ¹³ C-NMR. The weight average molecular weight and the molecular weight distribution can be determined by gel permeation chromatography (GPC) using polystyrene as a standard substance. The chain structure can be identified based on the physical properties and microstructure identified using DSC, ¹ H-NMR, ¹³ C-NMR, and GPC.

In addition, the multicomponent copolymer of the present invention preferably has a cis-1,4 bond content of 50% or more, and more preferably 70% or more, in the entire unit derived from the conjugated diene compound. If the content of cis-1,4 bonds in the entire unit derived from the conjugated diene compound is 50% or more, the glass transition temperature becomes low, and thus crack resistance growth of rubber compositions and tires using the obtained multi-component copolymer. It is possible to effectively improve physical properties such as properties and abrasion resistance. On the other hand, the trans-1,4 bond content and the 1,2 vinyl bond content in the entire unit derived from the conjugated diene compound are not particularly limited, but are preferably 50% or less, and 30% or less. Is more preferable.

The multicomponent copolymer of the present invention has a melting point (T _m ) of the conjugated diene compound used for the multicomponent copolymer, the non-conjugated olefin compound and the aromatic vinyl compound used for the multicomponent copolymer. It is preferably lower than the melting point (T _m ) of the binary copolymer formed by polymerizing any one kind. More specifically, the multicomponent copolymer of the present invention has a melting point (T _m ) of preferably 100° C. or lower, more preferably 80° C. or lower, and particularly preferably 50° C. or lower. preferable. It is also preferable that the melting point (T _m ) of the multicomponent copolymer of the present invention disappears. In these cases, it can be said that the crystallinity was reduced only by newly adding the non-conjugated olefin compound or the aromatic vinyl compound to the conventional binary copolymer. The advantages of the invention of polymerizing with can be more enjoyed. That is, in these cases, a rubber composition or tire or the like using such a multi-component copolymer can be produced with high workability, and durability and weather resistance of the rubber composition or tire and the like can be obtained. It can be expensive.
When the above-mentioned copolymer has a plurality of melting points, the highest melting point among them has to be used for the above comparison.

In the multicomponent copolymer of the present invention, the content of the unit derived from the conjugated diene compound is preferably 1 to 99 mol%, more preferably 5 to 95 mol%, and particularly preferably 10 to 90 mol%. .. When the content of the unit derived from the conjugated diene compound is 1 mol% or more, the obtained multi-component copolymer can behave uniformly as an elastomer, which can bring higher durability, while 99 mol% or less can be obtained. If so, the effect of using the non-conjugated olefin compound and the aromatic vinyl compound can be sufficiently obtained.

Further, in the multicomponent copolymer of the present invention, the total content of the unit derived from the non-conjugated olefin compound and the unit derived from the aromatic vinyl compound is preferably 1 to 99 mol%, and more preferably 5 to 95 mol%. Is more preferable and 10 to 90 mol% is particularly preferable. When the total content of the units derived from the non-conjugated olefin compound and the units derived from the aromatic vinyl compound is 1 mol% or more, higher weather resistance can be brought to the obtained multicomponent copolymer, while, If it is 99 mol% or less, the effect of using the conjugated diene compound can be sufficiently obtained. In the conventional binary copolymers (polymers of a conjugated diene compound and a non-conjugated olefin compound, and polymers of a conjugated diene compound and an aromatic vinyl compound), a unit or an aromatic compound derived from the non-conjugated olefin compound is generally used. When the content of the group-derived vinyl compound-derived unit is 50 mol% or more, that is, when the content of the conjugated diene compound-derived unit is 50 mol% or less, sufficient physical properties as an elastomer are lost. Since the crystallinity can be suppressed low by using the conjugated olefin compound and the aromatic vinyl compound, even when the total content of the units derived from the non-conjugated olefin compound or the units derived from the aromatic vinyl compound is about 90 mol%, Physical properties can be secured.

Furthermore, in the multi-component copolymer of the present invention, the proportion of one unit in the total units derived from the non-conjugated olefin compound and the aromatic vinyl compound is preferably 1 to 99 mol%, and preferably 3 to 97 mol%. Is more preferable, and 10 to 90 mol% is particularly preferable. Thus, the crystallinity can be effectively reduced by containing at least 1 mol% of each of the units derived from the two types of non-conjugated olefin compounds.

The polystyrene copolymerized weight average molecular weight (Mw) of the multi-component copolymer of the present invention is preferably 10,000 to 10,000,000, more preferably 100,000 to 9,000,000, and 150 Particularly preferably, it is 8,000 to 8,000,000. When the Mw of the multi-component copolymer is 10,000 or more, the mechanical strength as a rubber product material can be sufficiently secured, and when the Mw is 10,000,000 or less, it is high. Workability can be retained.

Furthermore, the multi-component copolymer of the present invention preferably has a molecular weight distribution (Mw/Mn) represented by the ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of 10.0 or less, It is more preferably 9.0 or less, and particularly preferably 8.0 or less. When the molecular weight distribution of the multicomponent copolymer is 10.0 or less, sufficient homogeneity can be brought about in the physical properties of the multicomponent copolymer.

The chain structure of the multi-component copolymer of the present invention is not particularly limited and may be appropriately selected depending on the purpose. For example, a unit derived from a conjugated diene compound is A, a unit derived from a non-conjugated olefin compound is B, in case where the unit derived from the aromatic vinyl compound and _{C, a x -B y -C z} (x, y, z is a is an integer of 1 or more) the block copolymer employing a configuration such as, a, B, A random copolymer in which C is randomly arranged, a taper copolymer in which the random copolymer and the block copolymer are mixed, (ABC) _w (w is an integer of 1 or more) It is possible to obtain an alternating copolymer having a constitution such as

(Rubber composition)
A rubber composition can be produced using the multi-component copolymer of the present invention. The rubber composition contains at least the multi-component copolymer of the present invention as a rubber component, and may further contain other rubber components, fillers, cross-linking agents, and other components as necessary.

The other rubber components are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include polyisoprene, butadiene rubber (BR), acrylonitrile-butadiene rubber (NBR), chloroprene rubber, ethylene-propylene. Examples thereof include rubber (EPM), ethylene-propylene-non-conjugated diene rubber (EPDM), polysulfide rubber, silicone rubber, fluororubber and urethane rubber. These may be used alone or in combination of two or more.

In addition, a filler can be used in the rubber composition, if necessary, for the purpose of improving its reinforcing property. The blending amount of the filler is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 10 to 100 parts by mass, and more preferably 20 to 80 parts by mass with respect to 100 parts by mass of the rubber component. , 30 to 60 parts by mass are particularly preferable. When the compounding amount of the filler is 10 parts by mass or more, the effect of improving the reinforcing property due to the compounding of the filler is obtained, and when it is 100 parts by mass or less, the low loss property is significantly reduced. It is possible to maintain good workability while avoiding the above.

The filler is not particularly limited, and carbon black, silica, aluminum hydroxide, clay, alumina, talc, mica, kaolin, glass balloon, glass beads, calcium carbonate, magnesium carbonate, magnesium hydroxide, magnesium oxide. Examples thereof include titanium oxide, potassium titanate, barium sulfate, and the like. Among these, it is preferable to use carbon black. These may be used alone or in combination of two or more.

The carbon black is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include FEF, GPF, SRF, HAF, N339, IISAF, ISAF and SAF. These may be used alone or in combination of two or more.
The nitrogen adsorption specific surface area (measured in accordance with N ₂ SA, JIS K 6217-2:2001) of the carbon black is not particularly limited and may be appropriately selected according to the purpose. -100 m< ² >/g is preferable and 35-80 m< ² >/g is more preferable. When the nitrogen adsorption specific surface area (N ₂ SA) of the carbon black is 20 m ² /g or more, the durability of the obtained rubber composition is improved, sufficient crack growth resistance is obtained, and 100 m ² When it is at most /g, good workability can be maintained while avoiding a significant decrease in low loss property.

A crosslinking agent can be used in the rubber composition, if necessary. The cross-linking agent is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include sulfur-based cross-linking agents, organic peroxide-based cross-linking agents, inorganic cross-linking agents, polyamine cross-linking agents, resin cross-linking agents, and sulfur. Examples thereof include compound-based crosslinking agents and oxime-nitrosamine-based crosslinking agents. Among these, as the rubber composition for tires, a sulfur-based crosslinking agent (vulcanizing agent) is more preferable.

The content of the crosslinking agent is appropriately selected depending on the intended purpose without any limitation, but it is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the rubber component. If the content of the cross-linking agent is less than 0.1 parts by mass, the crosslinking may hardly progress, while if it exceeds 20 parts by mass, some of the cross-linking agents cause the crosslinking to proceed during kneading. There is a tendency, and the physical properties of the vulcanizate may be impaired.

When the above vulcanizing agent is used, a vulcanization accelerator can also be used in combination. Examples of the vulcanization accelerator include guadinine-based, aldehyde-amine-based, aldehyde-ammonia-based, thiazole-based, sulfenamide-based, thiourea-based, thiuram-based, dithiocarbamate-based, and xanthate-based compounds. Further, the rubber composition of the present invention, if necessary, a softening agent, a vulcanization aid, a colorant, a flame retardant, a lubricant, a foaming agent, a plasticizer, a processing aid, an antioxidant, an antioxidant, Known compounds such as anti-scorch agents, anti-UV agents, antistatic agents, anti-coloring agents, and other compounding agents can be used according to the purpose of use.

(Crosslinked rubber composition)
Further, a crosslinked rubber composition can be obtained by crosslinking the rubber composition containing the multi-component copolymer of the present invention. The conditions for the cross-linking are not particularly limited and may be appropriately selected depending on the intended purpose, but are preferably a temperature of 120 to 200° C. and a heating time of 1 to 900 minutes. Since such a crosslinked rubber composition uses a conjugated diene compound as one of the monomers of the rubber component, compared to the case of using a polymer having a non-conjugated diene compound such as EPDM as one of the monomers. , Good cross-linking properties and therefore higher mechanical properties.

(tire)
A tire can be manufactured using the rubber composition containing the multi-component copolymer of the present invention. The tire is not particularly limited as long as it uses the rubber composition containing the multi-component copolymer of the present invention, and can be appropriately selected according to the purpose. Since such a tire uses the rubber composition containing the multi-component copolymer of the present invention, it can be manufactured with high workability and has high durability and weather resistance. The application site of the rubber composition of the present invention in the tire is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include a tread, a base tread, a sidewall, a side reinforcing rubber and a bead filler. .. Among these, the use of the rubber composition of the present invention in the tread is advantageous from the viewpoint of durability.
As a method for producing the tire, a conventional method can be used. For example, a carcass layer composed of an unvulcanized rubber composition and/or cord, a belt layer, a tread layer, and the like, which are commonly used in tire production, are sequentially laminated on a tire molding drum, and the drum is removed to obtain a green tire. To do. Then, a desired tire (for example, a pneumatic tire) can be manufactured by heating and vulcanizing this green tire according to a conventional method.

(Applications other than tires)
The rubber composition containing the multi-component copolymer of the present invention can be used for anti-vibration rubber, seismic isolation rubber, belts such as conveyor belts, rubber crawlers, various hoses, etc., as well as tire applications.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples.

(Synthesis Example 1: Terpolymer A)
250 g of a toluene solution containing 50 g (0.48 mol) of styrene was added to a sufficiently dried 2 L stainless steel reactor. On the other hand, in a glove box under a nitrogen atmosphere, gadolinium tris(bis(trimethylsilyl)amide) [ G dN(SiMe ₃ ) ₃ ]231 μmol, 1-methyl-2-phenylindene [1-Me-2- PhC ₉ H ₆ ]462 μmol Dimethylanilinium tetrakis(pentafluorophenyl)borate [Me ₂ NHPhB(C ₆ F ₅ ) ₄ ] 254 μmol and 3.00 mmol of diisobutylaluminum hydride were charged and dissolved in 40 ml of toluene, then the catalyst solution was added. And After that, the catalyst solution was taken out from the glove box, and after adding the catalyst solution in an amount of 210 μmol in terms of gadolinium to the monomer solution, 400 g of a monomer solution containing 100 g (1.85 mol) of 1,3-butadiene was introduced, and ethylene pressure was reduced (1.5 Polymerization was carried out at 80° C. for 540 minutes in MPa). After the polymerization, the reaction was stopped by adding 1 ml of an isopropanol solution containing 5% by mass of 2,2'-methylene-bis(4-ethyl-6-t-butylphenol) (NS-5), and co-existing with a large amount of 2-propanol. The polymer was separated and vacuum dried at 60° C. to obtain a terpolymer A. The yield of the obtained terpolymer A was 104 g.

(Synthesis Example 2: Terpolymer B)
250 g of a toluene solution containing 50 g (0.48 mol) of styrene was added to a sufficiently dried 2 L stainless steel reactor. On the other hand, in a glove box under a nitrogen atmosphere, gadolinium tris(bis(dimethylsilylamide)) [ G dN(SiMe ₃ ) ₃ ] 231 μmol, 1-methyl-2-phenylindenine [1-Me- 2-PhC ₉ H ₆ ]462 μmol, dimethylanilinium tetrakis(pentafluorophenyl)borate [Me ₂ NHPhB(C ₆ F ₅ ) ₄ ] 254 μmol, and diisobutylaluminum hydride 3.00 mmol were charged and dissolved in toluene 40 ml to prepare a catalyst solution. And After that, the catalyst solution was taken out from the glove box, and after adding the catalyst solution in an amount of 210 μmol in terms of gadolinium to the monomer solution, 600 g of a monomer solution containing 1,3-butadiene 150 g (2.78 mol) was introduced, and ethylene pressure was reduced (1.5 Polymerization was carried out at 80° C. for 540 minutes in MPa). After the polymerization, the reaction was stopped by adding 1 ml of an isopropanol solution containing 5% by mass of 2,2'-methylene-bis(4-ethyl-6-t-butylphenol) (NS-5), and co-existing with a large amount of 2-propanol. The polymer was separated and vacuum dried at 60° C. to obtain a terpolymer B. The yield of the obtained terpolymer B was 139 g.

(Synthesis Example 3: terpolymer C)
250 g of a toluene solution containing 50 g (0.48 mol) of styrene was added to a sufficiently dried 2 L stainless steel reactor. On the other hand, in a glove box under a nitrogen atmosphere, gadolinium tris(bis(dimethylsilylamide)) [ G dN(SiMe ₃ ) ₃ ] 231 μmol, 1-ethyl-2-phenylindenin [1-Et- 2-PhC ₉ H ₆ ]462 μmol, dimethylanilinium tetrakis(pentafluorophenyl)borate [Me ₂ NHPhB(C ₆ F ₅ ) ₄ ] 254 μmol, and diisobutylaluminum hydride 3.00 mmol were charged and dissolved in toluene 40 ml to prepare a catalyst solution. And After that, the catalyst solution was taken out from the glove box, and after adding the catalyst solution in an amount of 210 μmol in terms of gadolinium to the monomer solution, 600 g of a monomer solution containing 1,3-butadiene 150 g (2.78 mol) was introduced, and ethylene pressure was reduced (1.5 Polymerization was carried out at 80° C. for 540 minutes in MPa). After the polymerization, the reaction was stopped by adding 1 ml of an isopropanol solution containing 5% by mass of 2,2'-methylene-bis(4-ethyl-6-t-butylphenol) (NS-5), and co-existing with a large amount of 2-propanol. The polymer was separated and vacuum dried at 60° C. to obtain a terpolymer C. The yield of the obtained terpolymer C was 142 g.

(Synthesis example 4: terpolymer D)
375 g of a hexane solution containing 75 g (0.72 mol) of styrene was added to a sufficiently dried 2 L stainless steel reactor. On the other hand, in a glove box under a nitrogen atmosphere, gadolinium tris(bis(dimethylsilylamide)) [ G dN(SiMe ₃ ) ₃ ] 231 μmol, 1-trimethylsilyl-2-phenylindenine [1-TMS- 2-PhC ₉ H ₆ ]462 μmol, MMAO (“MMAO-3A” manufactured by Tosoh Line Chemical Co., Ltd.) 12 mmol, and diisobutylaluminum hydride 3.00 mmol were charged and dissolved in 90 ml of hexane to prepare a catalyst solution. After that, the catalyst solution was taken out from the glove box, and after adding the catalyst solution in an amount of 210 μmol in terms of gadolinium to the monomer solution, 600 g of a monomer solution containing 1,3-butadiene 150 g (2.78 mol) was introduced, and ethylene pressure was reduced (1.5 Polymerization was carried out at 80° C. for 540 minutes in MPa). After the polymerization, the reaction was stopped by adding 1 ml of an isopropanol solution containing 5% by mass of 2,2'-methylene-bis(4-ethyl-6-t-butylphenol) (NS-5), and co-existing with a large amount of 2-propanol. The polymer was separated and vacuum dried at 60° C. to obtain a terpolymer D. The yield of the obtained terpolymer D was 193 g.

(Confirmation of terpolymer)
For the polymers A to D obtained as described above, ¹ H-NMR spectrum and ¹³ C-NMR spectrum were measured to confirm characteristic peaks derived from each monomer, and gel permeation chromatography was performed. -Refractive index curve (GPC-RI curve) and gel permeation chromatography-UV absorption curve (GPC-UV curve) was measured to confirm the aromatic ring skeleton derived from the aromatic vinyl compound, and ternary copoly As a result of checking whether or not they are united, it was found that the polymers A to D were terpolymers.

(Identification of copolymer)
The weight average molecular weight (Mw), molecular weight distribution (Mw/Mn), microstructure, and melting point (T _m ) of the copolymers A to D were measured and evaluated by the following methods. The results are shown in Table 1.

(1) Weight average molecular weight (Mw) and molecular weight distribution (Mw/Mn)
Gel permeation chromatography [GPC: Tosoh HLC-8220GPC/HT, column: Tosoh GMH _HR- H(S)HT x 2, detector: differential refractometer (RI)] based on monodisperse polystyrene The polystyrene-reduced weight average molecular weight (Mw) and molecular weight distribution (Mw/Mn) of the copolymers A to C were determined. The measurement temperature is 40°C.

(2) Microstructure The microstructures in the polymers A to D were analyzed by ¹ H-NMR spectrum (content of 1,2-vinyl bond) and ¹³ C-NMR spectrum (cis-1,4 bond and trans-1, It was determined by the integration ratio of the content ratio of 4 bonds). Table 1 shows the cis-1,4 bond content (%), trans-1,4 bond content (%), and 1,2 vinyl bond content (%), the conjugated diene compound in the whole unit derived from the conjugated diene compound. Content of unit derived from (mol%), content of unit derived from non-conjugated olefin compound (mol%), content of unit derived from aromatic vinyl compound (mol%), and content of unit derived from non-conjugated olefin The ratio (molar ratio) is shown.
For example, regarding the content ratio of the ethylene-derived unit of the copolymer A, the molar ratio of butadiene (Bd)/ethylene (Et) is 27.0 to 28.5 ppm and 32.0 to 38.0 of the measured ¹³ C-NMR spectrum. It was calculated as follows from the sum of the peak integrated values of 34.0 ppm and the peak integrated value of 29.5-31.0 ppm.
Bd:Et=(96.3+3.7):13.3=100:13.3
As for the content ratio of the styrene-derived units in the copolymer A, butadiene (Bd) / the molar ratio of styrene (St), 4.75~5.10ppm and 5.20～ of ¹ H-NMR spectrum was measured It was calculated as follows from the sum of the peak integrated values of 5.50 ppm and the peak integrated value of 6.75 to 7.50 ppm.
Bd:St=(8.27+0.08)/2:1.33/5=4.18:0.27

From the results shown in Table 1, it was found that the terpolymers of each example had various weight average molecular weights and various copolymerization ratios.
As a result, the method for producing a terpolymer of the present invention efficiently polymerizes a terpolymer having various microstructures by polymerizing a conjugated diene compound, a non-conjugated olefin compound, and an aromatic vinyl compound. It can be said that it can be manufactured well.

The method for producing a terpolymer of the present invention can be used for producing a terpolymer composed of a conjugated diene compound, a non-conjugated olefin compound and an aromatic vinyl compound. Further, the terpolymer of the present invention can be used for a rubber composition as a raw material of a rubber product such as a tire, a vibration proof rubber, a seismic isolation rubber, a belt such as a conveyor belt, a rubber crawler and various hoses.

Claims (10)

A step of polymerizing a conjugated diene compound, a non-conjugated olefin compound and an aromatic vinyl compound in the presence of a catalyst composition containing a rare earth element compound represented by the following formula (I): Method for producing multi-component copolymer.
M-(AQ ¹ )(AQ ² )(AQ ³ )...(I)
(In the formula, M is scandium, yttrium, or a lanthanoid element; AQ ¹ , AQ ^2, and AQ ³ are aliphatic amide groups, arylamide groups or bistrialkylsilylamide groups; provided that at least one M- It has an A bond.) The method for producing a multi-component copolymer according to claim 1, wherein the catalyst composition further comprises a coordination compound that can serve as a ligand. The catalyst composition further comprises at least one compound selected from the group consisting of ionic compounds and halogen compounds, and an organoaluminum compound represented by the following formula (III): Or the method for producing the multi-component copolymer according to item 2.
AlR ¹ R ² R ³ (III)
(In the formula, R ¹ and R ² are a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom, R ³ is a hydrocarbon group having 1 to 10 carbon atoms, and R ¹ , R ² , and R ³ are respectively May be the same or different from each other) The method for producing a multi-component copolymer according to claim 2, wherein the coordination compound is a compound having a cyclopentadiene skeleton. The compound according to claim 4, wherein the compound having a cyclopentadiene skeleton is selected from substituted or unsubstituted cyclopentadiene, substituted or unsubstituted indene, and substituted or unsubstituted fluorene. Method for producing polymer. The method for producing a multi-component copolymer according to claim 5, wherein the substituted or unsubstituted indene is a substituted phenylindenyl compound. The method for producing a multicomponent copolymer according to any one of claims 1 to 6, wherein the non-conjugated olefin compound is ethylene. The method for producing a multi-component copolymer according to any one of claims 1 to 7, wherein the aromatic vinyl compound is styrene. The method for producing a multicomponent copolymer according to any one of claims 1 to 8, wherein the conjugated diene compound is 1,3-butadiene. It is manufactured by the method for manufacturing a multicomponent copolymer according to any one of claims 1 to 9, and the content of cis-1,4 bonds in the entire unit derived from the conjugated diene compound is 70% or more. , Multi-component copolymers.