JP2011127035A - Modified conjugated diene polymer and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a modified conjugated diene polymer having little change in molecular weight distribution before and after the modification, and the polymer. <P>SOLUTION: The method for producing a modified conjugated diene polymer is provided, which includes (1) addition of water or 5C or less alcohol as a reaction terminator immediately after polymerization of a conjugated diene polymer, (2) subsequent cooling of the reaction system, and (3) subsequent hydrosilylation of the modified conjugated diene polymer by an organosilane compound. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

The present invention relates to a method for producing a modified conjugated diene polymer having almost no change in molecular weight distribution before and after modification and the polymer.

Silica has become a very important inorganic filler since it has been applied to various uses, mainly rubber, as an environmentally friendly material for the past 10 years. This is because it is superior to carbon black in terms of mechanical properties such as tear strength, abrasion resistance, and aging resistance, as well as the most important balance of performance related to wettability and low rolling resistance. .

However, since there are silanol groups on the polar surface of the silica particles, interactions due to hydrogen bonds are likely to occur. Therefore, silica tends to have poor compatibility or affinity with a rubber matrix, particularly a hydrocarbon structure such as polybutadiene. This causes the silica particles to easily aggregate in the silica-rubber compound, resulting in poor dispersibility.

As a result, the silica aggregate breaks down, that is, Payne Effect (Non-Patent Document 1) causes a large hysteresis loss, that is, a significant energy loss due to heat, an increase in heat generation, and an increase in rolling resistance.

The hysteresis characteristic of a rubber compound is generally said to be a difference between energy when the rubber compound is deformed and energy released when the rubber compound returns to the initial state. Accordingly, in order to achieve low rolling resistance, low heat generation, and low fuel consumption during use, it is desirable that the hysteresis loss is low or the energy loss is low with respect to heat.

As a binder for improving the affinity and interaction between the polar silica surface and the nonpolar rubber matrix, it is possible to use a silane coupling agent having a dual function to make a silica-rubber compound. It has become. Further, surface-treated silica having a low surface polarity combined with a silane coupling agent is an effective method even on an industrial scale for producing a silica compound.

Nevertheless, the use of very expensive silane coupling agents is economically disadvantageous. Moreover, it is known that a silane coupling agent inhibits a crosslinking reaction in a vulcanization process of a rubber compound, thereby lowering a crosslinking density, resulting in poor mechanical properties.

Therefore, chemical modification of the rubber of the silica-rubber compound is an alternative technique for improving the silica-rubber interaction and is a method for reducing the cost due to the expensive silane coupling agent. However, it is usually desirable for rubber chemical modification techniques to have a high cis 1,4-structure in order to maintain good rubber performance. Therefore, there has been a limit to the application of rubber such as polybutadiene.

Many of the chemically modified rubbers such as high cis-polybutadiene are functionalized by molecular polymerization using various effective alkoxysilane coupling agents after living polymerization of 1,3-butadiene using a rare earth catalyst. The method of making it is reported. The alkoxysilane compound having a modified molecular end has an epoxy group, an isocyanate group, a urethane group, an amino group, a carboxyl group, and the like. In order to collect these functional groups at the ends of living molecules, reaction accelerators such as Bi compounds, Zn compounds, Sn compounds or Al compounds are required (Patent Documents 1 to 6).

The use of living anionic polymerization of 1,3-polybutadiene in the presence of an organolithium initiator can be selectively used to produce molecular end-modified low cis polybutadiene using a bifunctional alkoxysilane coupling agent Therefore, a low cis structure is not necessarily required (Patent Documents 7 and 8).

However, the molecular end-modification technology of rubber is still not satisfactory for reducing silica-silica interaction, silica aggregation, hysteresis loss due to silica aggregation (payne effect) and consequently heat generation. Absent. Addition of a functional group only at the terminal end is insufficient in effect, and in order to further enhance the affinity with silica, it is desirable to have a physical property with a polymer having a functional group inside the polymer chain (Non-patent Document 2).

Known methods for hydrosilylating unsaturated monomers in the presence of platinum (Pt) or rhodium (Rh) catalysts widely used in the silicone industry for the commercial production of various silane compounds instead of molecular end modification Another strategy similar to the concept of grafting a polybutadiene main chain using (Patent Document 9, Non-Patent Document 3) has become one of the interests for introducing functional groups into a polybutadiene rubber matrix.

To date, in silicone coating applications, there have been few examples of using hydrosilylation techniques to introduce functional groups into the molecular backbone of high vinyl content, low cis polybutadiene.
In the US patents (Patent Documents 10-12), efforts to prepare silicones for coating applications with improved mechanical strength have been found in the presence of platinum or rhodium catalysts in the presence of high vinyl content (vinyl content 90% or higher) polybutadiene. It is stated that it has succeeded in becoming.

WO03-046020 JP 2005-08870 A European Patent No. 071385 European Patent No. 0267675 US Pat. No. 7,247,695 EP 1860136 U.S. Pat. No. 7,335,706 European Patent No. 1939220 US Pat. No. 5,550,272 US Pat. No. 5,703,163 US Patent No. 5811193 U.S. Pat. No. 6,482,891

Payne AR., J.Apply.Polym.Scl.1962,6,57. Hsu, B .; Halasa, A .; Bates, k .; Zhou, J .; Hua, k .; Ogata, N .; Nippon Gomu Kyokaishi, 79, 117 (2006). Larry N. Lewis, Platlnum Metals Rev., 1997, 41, 66.

Provided are a production method in which the molecular weight distribution of a modified conjugated diene polymer hardly changes before and after modification, and a conjugated diene polymer having a narrow molecular weight distribution produced by the method.

In the method for producing a modified conjugated diene polymer,
(1) Immediately after polymerizing the conjugated diene polymer, water or an alcohol having 5 or less carbon atoms is added as a reaction terminator,
(2) Next, the reaction system is cooled,
(3) Next, the present invention relates to a method for producing a modified conjugated diene polymer, wherein the unmodified conjugated diene polymer is hydrosilylated with an organosilane compound.

  The conjugated diene polymer has a 1,4-cis structure of 80 to 95% and a 1,2-vinyl structure of 4 to 19 mol%, and relates to a method for producing the modified conjugated diene polymer.

The modified conjugate as described above, wherein the conjugated diene polymer is produced by polymerization using a metallocene vanadium complex compound, an ionic compound of a non-coordinating anion and a cation, and a catalyst comprising an organometallic compound. The present invention relates to a method for producing a diene polymer.

  In the above production method, the reaction terminator used in (1) is isopropyl alcohol. The present invention relates to a method for producing the modified conjugated diene polymer.

  The organic silane compound is diethylaminodimethylsilane, and relates to a method for producing the modified conjugated diene polymer.

The present invention relates to a modified conjugated diene polymer produced by the above method.

  The modified conjugated diene polymer obtained in the present invention can suppress an increase in molecular weight distribution due to modification, and provides a method capable of reducing the adverse effects of physical properties due to modification as much as possible, and the modification obtained by the method. Provided is a conjugated diene polymer.

The modification method performed in the steps (I) to (IV) as the characteristics of the present invention will be described below.
(I) A conjugated diene monomer is polymerized. The catalyst system used in the polymerization is a half vanadocene (V) catalyst represented by (a) the chemical formula (C5R5) VOX2. Here, R = H and X = Cl.
(b) An aluminium compound represented by the chemical formula AlR ₃ . Here, R = alkyl group.
(c) Organoboric acid compound Ph3CB (C6F5) 4
(II) A reaction terminator is charged immediately after the polymerization. As the reaction terminator, water or alcohol having 5 or less carbon atoms is used.
(III) Next, the reaction system is rapidly cooled.
(IV) Subsequently, the hydrosilylation reaction of the conjugated diene polymer is carried out by releasing the unreacted 1,3-polybutadiene monomer, and then the Speier catalyst in isopropanol together with the silane compound represented by the chemical formula SiH (R ′) (R ″) 2. Obtained from (I) which is readily soluble in cyclohexane at 40-80 ° C., more preferably 50-60 ° C. in the presence of (H 2 PtCl 6), where R ′ is preferably ethoxy, methyl, diethylamino, R "Is preferably ethoxy, methyl, hexamethyltrisiloxane.
(V) Dry the hydrosilylated cis-polybutadiene solution in cyclohexane at 100 ° C. for 1 hour under vacuum.

  In the present invention, it is important to use water or alcohol having 5 or less carbon atoms in the operation of (II) as a reaction terminator immediately after the polymerization of (I). That is, by using these reaction terminators, the polymerization reaction can be almost completely stopped.

The reaction terminator used here is water or a lower alcohol having 5 or less carbon atoms. Examples of the lower alcohol having 5 or less carbon atoms are methanol, ethanol, 1-propanol, 2-propanol (isopropyl alcohol), 1 -Butanol (n-butanol), 2-methyl-1-propanol (isobutanol), 2-butanol (sec-butanol), 2-methyl-2-propanol (tert-butanol), 1-pentanol (n-amyl) Alcohol), 2-pentanol (sec-amyl alcohol), 3-pentanol, 2-methyl-1-butanol,
3-methyl-1-butanol (isoamyl alcohol), 2-methyl-2-butanol (tert-amyl alcohol), 3-methyl-2-butanol, 2,2-dimethyl-1-propanol (neopentyl alcohol) can give. These may be used alone or in combination. Of these, the use of isopropyl alcohol is particularly preferred.

  Use of a higher alcohol having 6 or more carbon atoms is not preferable because the effect as a reaction terminator is reduced.

  The amount of the reaction terminator used is preferably from 0.1 to 15 ml, more preferably from 0.2 to 10 ml, particularly preferably from 0.3 to 2 ml per 100 g of the polymer rubber.

If the amount of the reaction terminator used is less than 0.1 ml, the effect of terminating the reaction is lowered, which is not preferable. Moreover, when 15 ml or more is used, use is not preferable from a side reaction and economical viewpoint.

  Furthermore, in the operation (III), it is important to completely stop the polymerization reaction by cooling the reaction system. In particular, when the temperature is 30 ° C. or lower, the polymerization reaction can be completely stopped.

  In the operation of the present invention, if the order of (II) and (III) is reversed, no effect is obtained. The premise is that the polymerization reaction is terminated due to the deactivation of the catalytically active species by the reaction terminator.

Conjugated Diene Polymer In the modified conjugated diene polymer according to the present invention, the hydrosilylation is preferably such that the vinyl group of the conjugated diene polymer is hydrosilylated.
The idea of the present invention is that high cis polybutadiene (1,4-cis structure 80 to 80) having a vinyl group content of only about 10% because hydrosilylation tends to react with the vinyl side chain of the conjugated diene polymer. In order to modify the vinyl side chain of 95 mol%, 1,2-vinyl structure 4-19 mol%), the hydrosilylation technique is applied. According to the modified conjugated diene polymer according to the present invention, by applying hydrosilylation technology to high cis polybutadiene (1,4-cis structure 80-95 mol%, 1,2-vinyl structure 4-19 mol%), By modifying the vinyl side chain, the silica-rubber interaction can be improved and the balance between the high performance of the high cis structure and the degree of modification to the polybutadiene main chain can be maintained compared to the molecular end modification.

In the polybutadiene used in the modified conjugated diene polymer according to the present invention, the 1,4-cis structure in the polymer main chain is 80 mol% or more, preferably 80 to 95%, more preferably 87 to 92%, The 1,2-vinyl structure is 20 mol% or less, preferably 4 to 19%, more preferably 8 to 13%, and the 1,4-trans structure is 1% or less.
Since the reaction proceeds efficiently when the range of the microstructure is not within the above range, it is desirable that the 1,2-vinyl structure in the above range is included. Further, if the 1,4-cis structure is not more than the above range, the abrasion resistance and mechanical properties are remarkably inferior.

The polybutadiene has a Mooney viscosity (ML _{1 + 4} , 100 ° C.) of 20 to 50, preferably 30 to 40, particularly preferably 33 to 35. If the Mooney viscosity is too lower than the above range, there will be a problem of deterioration of mechanical properties. Conversely, if it is too high, the filler dispersibility at the time of kneading will deteriorate, and sufficient performance will not be exhibited, and there will be a problem in workability. It is not preferable because it occurs.

  The number average molecular weight (Mn) of the polybutadiene is 180,000 to 380,000 g / mol, and particularly preferably 220,000 to 350,000 g / mol. The molecular weight distribution (Mw / Mn) is preferably 1.0 to 2.4, more preferably 1.0 to 2.35.

  This polybutadiene (hereinafter referred to as MBR) is preferably produced by polymerization using a metallocene complex of a transition metal compound, an ionic compound of a non-coordinating anion and a cation, and a catalyst comprising an organometallic compound. .

This polymerization method is not particularly limited, and bulk polymerization, solution polymerization and the like can be applied. As the polymerization apparatus, an autoclave is generally used, but there is no particular limitation. Solvents for solution polymerization include aromatic hydrocarbons such as toluene, benzene and xylene, aliphatic hydrocarbons such as n-hexane, butane, heptane and pentane, alicyclic hydrocarbons such as cyclopentane and cyclohexane, -Olefin hydrocarbons such as butene, cis-2-butene, trans-2-butene, hydrocarbon solvents such as mineral spirit, solvent naphtha, kerosene, halogenated hydrocarbon solvents such as methylene chloride, etc. . Further, 1,3-butadiene itself may be used as a polymerization solvent. The solvent is preferably a non-aromatic hydrocarbon, particularly cyclohexane.
Polymerization catalyst

The catalyst component used to polymerize the polybutadiene includes a metallocene complex of a transition metal of Group 4 transition metal such as titanium and zirconium (for example, CpTiCl ₃ ), vanadium, niobium, tantalum and the like. Examples include metallocene complexes of group 5 transition metals, group 6 transition metal metallocene complexes such as chromium, and metallocene complexes of group 8 transition metals such as cobalt and nickel. Among these, metallocene type complexes of group 5 transition metals of the periodic table are preferably used.

Examples of the metallocene complex of the Group 5 transition metal compound in the periodic table include (1) RM · La, (2) Rn MX _2-n · La, (3) Rn MX _3-n · La, (4) Examples include compounds represented by general formulas such as RMX ₃ · La, (5) RM (O) X ₂ · La, and (6) Rn MX _3-n (NR ′) (wherein n is 1 or 2, a is 0, 1 or 2). Among these, RM · La, RMX ₃ · La, RM (O) X ₂ · La, and the like are preferable. In the formula, M is preferably a Group 5 transition metal compound in the periodic table. Specifically, it is vanadium (V), niobium (Nb), or tantalum (Ta), and a preferred metal is vanadium. R represents a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a fluorenyl group, or a substituted fluorenyl group.

  Examples of the substituent in the substituted cyclopentadienyl group, substituted indenyl group or substituted fluorenyl group include methyl, ethyl, propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, t-butyl, hexyl and the like. Examples thereof include chain aliphatic hydrocarbon groups or branched aliphatic hydrocarbon groups, aromatic hydrocarbon groups such as phenyl, tolyl, naphthyl, and benzyl, and hydrocarbon groups containing silicon atoms such as trimethylsilyl. In addition, those in which a cyclopentadienyl ring and a part of X are bonded to each other by a bridging group such as dimethylsilyl, dimethylmethylene, methylphenylmethylene, diphenylmethylene, ethylene, substituted ethylene are also included.

  Specific examples of the substituted cyclopentadienyl group include methylcyclopentadienyl group, 1,2-dimethylcyclopentadienyl group, 1,3-dimethylcyclopentadienyl group, 1,3-di (t-butyl). ) Cyclopentadienyl group, 1,2,3-trimethylcyclopentadienyl group, 1,2,3,4-tetramethylcyclopentadienyl group, pentamethylcyclopentadienyl group, 1-ethyl-2, 3,4,5-tetramethylcyclopentadienyl group, 1-benzyl-2,3,4,5-tetramethylcyclopentadienyl group, 1-phenyl-2,3,4,5-tetramethylcyclopenta Dienyl group, 1-trimethylsilyl-2,3,4,5-tetramethylcyclopentadienyl group, 1-trifluoromethyl-2,3,4,5-tetramethylcyclope Such as Tajieniru group, and the like.

  Specific examples of the substituted indenyl group include 1,2,3-trimethylindenyl group, heptamethylindenyl group, 1,2,4,5,6,7-hexamethylindenyl group and the like. Specific examples of the substituted fluorenyl group include a methyl fluorenyl group. Among these, R is preferably a cyclopentadienyl group, a methylcyclopentadienyl group, a pentamethylcyclopentadienyl group, an indenyl group, a 1,2,3-trimethylindenyl group, or the like.

  In the formula, X represents hydrogen, halogen, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group, or an amino group. All Xs may be the same or different from each other. Specific examples of the halogen include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

  Specific examples of the hydrocarbon group having 1 to 20 carbon atoms include linear aliphatic carbonization such as methyl, ethyl, propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, t-butyl and hexyl. Examples thereof include a hydrogen group or a branched aliphatic hydrocarbon group, and an aromatic hydrocarbon group such as phenyl, tolyl, naphthyl, and benzyl. Further, a hydrocarbon group containing a silicon atom such as trimethylsilyl is also included. Of these, methyl, benzyl, trimethylsilylmethyl and the like are preferable.

  Specific examples of the alkoxy group include methoxy, ethoxy, phenoxy, propoxy, butoxy and the like. Furthermore, amyloxy, hexyloxy, octyloxy, 2-ethylhexyloxy, thiomethoxy and the like may be used. Specific examples of the amino group include dimethylamino, diethylamino, diisopropylamino and the like. Among these, as X, hydrogen, fluorine atom, chlorine atom, bromine atom, methyl, ethyl, butyl, methoxy, ethoxy, dimethylamino, diethylamino and the like are preferable.

  In the formula, L is a Lewis base and is a Lewis basic general inorganic or organic compound capable of coordinating to a metal. Of these, compounds having no active hydrogen are particularly preferred. Specific examples include ethers, esters, ketones, amines, phosphines, silyloxy compounds, olefins, dienes, aromatic compounds, alkynes, and the like.

NR ′ is an imide group, and R ′ is a hydrocarbon substituent having 1 to 25 carbon atoms. Specific examples of R ′ include linear aliphatic hydrocarbon groups such as methyl, ethyl, propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, t-butyl, hexyl, octyl and neopentyl, Branched aliphatic hydrocarbon groups, aromatic hydrocarbon groups such as phenyl, tolyl, naphthyl, benzyl, 1-phenylethyl, 2-phenyl-2-propyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, etc. Is mentioned. Further, a hydrocarbon group containing a silicon atom such as trimethylsilyl is also included.

As the metallocene complex of the Group 5 transition metal compound of the periodic table, a vanadium compound in which M is vanadium is particularly preferable. For example, RV · La, RVX · La, R ₂ V · La, RVX ₂ · La, R ₂ VX · La, RVX ₃ · La, RV (O) X ₂ · La and the like are preferable. In particular, RV · La and RVX ₃ · La are preferable.

  RM.La, that is, a group 5 transition metal compound with an oxidation number of +1 having a cycloalkadienyl group ligand includes cyclopentadienyl (benzene) vanadium, cyclopentadienyl (toluene) vanadium. , Cyclopentadienyl (xylene) vanadium, cyclopentadienyl (trimethylbenzene) vanadium, cyclopentadienyl (hexamethylbenzene) vanadium, cyclopentadienyl (naphthalene) vanadium, cyclopentadienyl (anthracene) vanadium, cyclo Pentadienyl (ferrocene) vanadium, methylcyclopentadienyl (benzene) vanadium, 1,3-dimethylcyclopentadienyl (benzene) vanadium, 1-butyl-3-methylcyclopetadienyl (benzene) vanadium, te Tramethylcyclopentadienyl (benzene) vanadium, pentamethylcyclopentadienyl (benzene) vanadium, trimethylsilylcyclopentadienyl (benzene) vanadium, 1,2-bis (trimethylsilyl) cyclopentadienyl (benzene) vanadium, 1 , 3-bis (trimethylsilyl) cyclopentadienyl (benzene) vanadium, indenyl (benzene) vanadium, 2-methylindenyl (benzene) vanadium, 2-trimethylsilyl indenyl (benzene) vanadium, fluorenyl (benzene) vanadium, cyclopenta Dienyl (ethylene) (trimethylphosphine) vanadium, cyclopentadienyl (butadiene) (trimethylphosphine) vanadium, cyclopentadienyl (1,4-diphenyl) Butadiene) (trimethylphosphine) vanadium, cyclopentadienyl (1,1,4,4-tetraphenylbutadiene) (trimethylphosphine) vanadium, cyclopentadienyl (2,3-dimethylbutadiene) (trimethylphosphine) vanadium, cyclo Examples thereof include pentadienyl (2,4-hexadiene) (trimethylphosphine) vanadium, cyclopentadienyl tetracarbonyl vanadium, and indenyl tetracarbonyl vanadium.

Among the compounds represented by Rn MX _2-n · La, when n = 1, that is, when having one cycloalkadienyl group as a ligand, a hydrogen atom, chlorine Halogen atoms such as bromine and iodine, hydrocarbon groups such as methyl group, phenyl group, benzyl group, neopentyl group, trimethylsilyl group and bistrimethylsilylmethyl group, hydrocarbon oxy groups such as methoxy group, ethoxy group and isopropoxy group, It can have a hydrocarbon amino group such as a dimethylamino group, a diethylamino group, a diisopropylamino group, or a dioctylamino group.

  Further, the other ligand may have a neutral Lewis base such as amine, amide, phosphine, ether, ketone, ester, olefin, diene, aromatic hydrocarbon, alkyne and the like. Lewis bases without active hydrogen are preferred.

Among the compounds represented by Rn MX _2-n · La, when n = 2, that is, when having two cycloalkadienyl groups as ligands, each cycloalkadienyl ring is a Me ₂ Si group. , A dimethylmethylene group, a methylphenylmethylene group, a diphenylmethylene group, an ethylene group, a substituted ethylene group or the like bonded together.

Of the compounds represented by RnMX _2-n · La of the present invention, n = 1, that is, specific examples of Group 5 transition metal compounds having an oxidation number of +2 having one cycloalkadienyl group as a ligand As chlorocyclopentadienyl (tetrahydrofuran) vanadium, chlorocyclopentadienyl (trimethylphosphine) vanadium, chlorocyclopentadienyl bis (trimethylphosphine) vanadium, chlorocyclopentadienyl (1,2-bisdimethylphosphino) Ethane) vanadium, chlorocyclopentadienyl (1,2-bisdiphenylphosphinoethane) vanadium, chlorocyclopentadienyl (triphenylphosphine) vanadium, chlorocyclopentadienyl (tetrahydrothiophene) vanadium, bromocyclopen Tadienyl (tetrahydrofuran) vanadium, iodocyclopentadienyl (tetrahydrofuran) vanadium, chloro (methylcyclopentadienyl) (tetrahydrofuran) vanadium, chloro (1,3-dimethylcyclopentadienyl) (tetrahydrofuran) vanadium, chloro ( 1-butyl-3-methylcyclopetadienyl) (tetrahydrofuran) vanadium, chloro (tetramethylcyclopentadienyl) (tetrahydrofuran) vanadium, chloro (pentamethylcyclopentadienyl) (tetrahydrofuran) vanadium, chloro (trimethylsilylcyclopenta) Dienyl) (tetrahydrofuran) vanadium, chloro (1,2-bis (trimethylsilyl) cyclopentadienyl) (tetrahydrofuran) vanadium, Rolo (1,3-bis (trimethylsilyl) cyclopentadienyl) (tetrahydrofuran) vanadium, chloroindenyl (tetrahydrofuran) vanadium, chloro (2-methylindenyl) (tetrahydrofuran) vanadium, chloro (2-trimethylsilylindenyl) ( Tetrahydrofuran) vanadium, chlorofluorenyl (tetrahydrofuran) vanadium, dimethylsilyl (cyclopentadienyl) (t-butylamino) vanadium, dimethylsilyl (tetramethylcyclopentadienyl) (t-butylamino) vanadium, etc. .

Among the compounds represented by Rn MX _2-n · La of the present invention, n = 2, that is, specific examples of Group 5 transition metal compounds in the periodic table having an oxidation number of +2 having two cycloalkadienyl groups as ligands Examples include biscyclopentadienyl vanadium, bis (methylcyclopentadienyl) vanadium, bis (1,2-dimethylcyclopentadienyl) vanadium, bis (1,3-dimethylcyclopentadienyl) vanadium, bis (1-methyl-3-butylcyclopentadienyl) vanadium, bis (tetramethylcyclopentadienyl) vanadium, bis (pentamethylcyclopentadienyl) vanadium, bis (ethylcyclopentadienyl) vanadium, bis (n -Propylcyclopentadienyl) vanadium, bis (i-propylcyclopentadiene) L) Vanadium, bis (n-butylcyclopentadienyl) vanadium, bis (iso-butylcyclopentadienyl) vanadium, bis (sec-butylcyclopentadienyl) vanadium, bis (t-butylcyclopentadienyl) Vanadium, bis (1-methoxyethylcyclopentadienyl) vanadium, bis (1-dimethylaminoethylcyclopentadienyl) vanadium, bis (1-diethylaminoethylcyclopentadienyl) vanadium, bis (trimethylsilylcyclopentadienyl) Vanadium, bis (1-dimethylphosphinoethylcyclopentadienyl) vanadium, bis (1,2-bis (trimethylsilyl) cyclopentadienyl) vanadium, bis (1,3-bis (trimethylsilyl) cyclopentadienyl) Vanadium, indenylcyclopentadienyl vanadium, (2-methylindenyl) cyclopentadienyl vanadium, (2-trimethylsilylindenyl) cyclopentadienyl vanadium, bisindenyl vanadium, bisfluorenyl vanadium, indenyl full Orenyl vanadium, cyclopentadienylfluorenyl vanadium, dimethylsilyl (cyclopentadienyl) (t-butylamino) vanadium, dimethylsilyl (tetramethylcyclopentadienyl) (t-butylamino) vanadium, dimethylsilylbis (Cyclopentadienyl) vanadium, dimethylsilylbis (indenyl) vanadium, dimethylsilylbis (fluorenyl) vanadium, and the like.

Among the specific compounds represented by Rn MX _3-n · La, the compounds with n = 1 include cyclopentadienyl vanadium dichloride, methylcyclopentadienyl vanadium dichloride, (1,3-dimethylcyclopentadiene). Enyl) vanadium dichloride, (1-butyl-3-methylcyclopentadienyl) vanadium dichloride, (pentamethylcyclopentadienyl) vanadium dichloride, (trimethylsilylcyclopentadienyl) vanadium dichloride, (1,3-bis (trimethylsilyl) ) Cyclopentadienyl) vanadium dichloride, indenyl vanadium dichloride, (2-methylindenyl) vanadium dichloride, (2-trimethylsilylindenyl) vanadium dichloride, fluorenyl vanadi Dichloride body such Mujikuroraido, or dimethyl body and the like obtained by substituting chlorine atoms of these compounds with a methyl group.

Also included are those in which R and X are bonded by a hydrocarbon group or a silyl group. For example, amide chlorides such as (t-butylamido) dimethyl (η ⁵ -cyclopentadienyl) silane vanadium chloride, (t-butylamido) dimethyl (tetramethyl-η ⁵ -cyclopentadienyl) silane vanadium chloride, or these The methyl body which substituted the chlorine atom of the compound of this by the methyl group etc. are mentioned.

  Cyclopentadienyl vanadium dimethoxide, cyclopentadienyl vanadium di-iso-propoxide, cyclopentadienyl vanadium di-t-butoxide, cyclopentadienyl vanadium diphenoxide, cyclopentadienyl vanadium methoxychloride, cyclopenta Examples include alkoxides such as dienylvanadium-iso-propoxychloride, cyclopentadienylvanadium-t-butoxychloride, cyclopentadienylvanadium phenoxychloride, or methyl compounds in which the chlorine atom of these compounds is substituted with a methyl group. It is done.

  Bisamides such as (cyclopentadienyl) bis (diethylamido) vanadium, (cyclopentadienyl) bis (di-iso-propylamido) vanadium, (cyclopentadienyl) bis (di-n-octylamido) vanadium Can be mentioned.

  Cyclopentadienyl vanadium dichloride / bistriethylphosphine complex, cyclopentadienyl vanadium dichloride / bistrimethylphosphine complex, (cyclopentadienyl) bis (diiso-propylamido) vanadium trimethylphosphine complex, monomethylcyclopentadienyl vanadium dichloride / Examples include phosphine complexes such as bistriethylphosphine complex.

Among the specific compounds represented by Rn MX _3-n · La, n = 2 compounds include dicyclopentadienyl vanadium chloride, bis (methylcyclopentadienyl) vanadium chloride, bis (1,3 -Dimethylcyclopentadienyl) vanadium chloride, bis (1-butyl-3-methylcyclopentadienyl) vanadium chloride, bis (pentamethylcyclopentadienyl) vanadium chloride, bis (trimethylsilylcyclopentadienyl) vanadium chloride, Bis (1,3-bis (trimethylsilyl) cyclopentadienyl) vanadium chloride, diindenyl vanadium chloride, bis (2-methylindenyl) vanadium chloride, bis (2-trimethylsilylindenyl) vanadium chloride Chlorides body such difluorenylamino fluorenyl vanadium chloride, or the like methyl bodies chlorine atom substituted with a methyl group of these compounds.

  Dicyclopentadienyl vanadium methoxide, dicyclopentadienyl vanadium-iso-propoxide, dicyclopentadienyl vanadium-t-butoxide, dicyclopentadienyl vanadium phenoxide, dicyclopentadienyl (diethylamide) vanadium, Examples include dicyclopentadienyl (di-iso-propylamide) vanadium and dicyclopentadienyl (di-n-octylamide) vanadium.

Those in which R is bonded by a hydrocarbon group or a silyl group are also included. For example, chloride bodies such as dimethylbis (η ⁵ -cyclopentadienyl) silane vanadium chloride, dimethylbis (tetramethyl-η ⁵ -cyclopentadienyl) silane vanadium chloride, or the chlorine atom of these compounds as a methyl group Examples include substituted methyl.

Specific compounds represented by RMX ₃ include the following (i) to (xvi).

  (I) cyclopentadienyl vanadium trichloride. Monosubstituted cyclopentadienyl vanadium trichloride, for example, methylcyclopentadienyl vanadium trichloride, ethylcyclopentadienyl vanadium trichloride, propylcyclopentadienyl vanadium trichloride, isopropylcyclopentadienyl vanadium trichloride, t- Butylcyclopentadienyl vanadium trichloride, (1,1-dimethylpropyl) cyclopentadienyl vanadium trichloride, (benzyl) cyclopentadienyl vanadium trichloride, (2-phenyl-2-propyl) cyclopentadienyl vanadium Trichloride, (3-pentyl) cyclopentadienyl vanadium trichloride, (3-methyl-3-pentyl) cyclopentadienyl vanadium tri Roraido, (3-phenyl-3-pentyl) cyclopentadienyl vanadium trichloride, and the like (trimethylsilyl cyclopentadienyl) vanadium trichloride.

  (Ii) 1,2-disubstituted cyclopentadienyl vanadium trichloride, such as (1,2-dimethylcyclopentadienyl) vanadium trichloride, (1-ethyl-2-methylcyclopentadienyl) vanadium trichloride , (1-methyl-2-propylcyclopentadienyl) vanadium trichloride, (1-butyl-2-methylcyclopentadienyl) vanadium trichloride, (1-methyl-2-bis (trimethylsilyl) methylcyclopentadi Enyl) vanadium trichloride, 1,2-bis (trimethylsilyl) cyclopentadienyl) vanadium trichloride, (1-methyl-2-phenylcyclopentadienyl) vanadium trichloride, (1-methyl-2-tolylcyclopenta) Dienyl) vanadium Rikuroraido, (1-methyl-2- (2,6-dimethylphenyl) cyclopentadienyl) vanadium trichloride, and the like.

(Iii) 1,3-disubstituted cyclopentadienyl vanadium trichloride, for example, (1,3-dimethylcyclopentadienyl) vanadium trichloride, (1-ethyl-3-methylcyclopentadienyl) vanadium trichloride , (1-methyl-3-propylcyclopentadienyl) vanadium trichloride, (1-butyl-3-methylcyclopentadienyl) vanadium trichloride, (1-methyl-3-bis (trimethylsilyl) methylcyclopentadi Enyl) vanadium trichloride, 1,3-bis (trimethylsilyl) cyclopentadienyl) vanadium trichloride, (1-methyl-3-phenylcyclopentadienyl) vanadium trichloride, (1-methyl-3-tolylcyclopenta) Dienyl) Vanadiu Trichloride, (1-methyl-3- (2,6-dimethylphenyl) cyclopentadienyl) vanadium trichloride, and the like.

  (Iii) 1,2,3-trisubstituted cyclopentadienyl vanadium trichloride such as (1,2,3-trimethylcyclopentadienyl) vanadium trichloride.

  (Iv) 1,2,4-trisubstituted cyclopentadienyl vanadium trichloride, for example, (1,2,4-trimethylcyclopentadienyl) vanadium trichloride and the like.

  (V) tetra-substituted cyclopentadienyl vanadium trichloride, for example, (1,2,3,4-tetramethylcyclopentadienyl) vanadium trichloride, (1,2,3,4-tetraphenylcyclopentadienyl) ) Vanadium trichloride and the like.

  (Vi) penta-substituted cyclopentadienyl vanadium trichloride such as (pentamethylcyclopentadienyl) vanadium trichloride, (1,2,3,4-tetramethyl-5-phenylcyclopentadienyl) vanadium trichloride , (1-methyl-2,3,4,5-tetraphenylcyclopentadienyl) vanadium trichloride and the like.

  (Vii) Indenyl vanadium trichloride is mentioned.

  (Viii) Substituted indenyl vanadium trichloride, such as (2-methylindenyl) vanadium trichloride, (2-trimethylsilylindenyl) vanadium trichloride, and the like.

  (Ix) Monoalkoxides, dialkoxides, trialkoxides in which the chlorine atoms of the compounds of (i) to (viii) are substituted with alkoxy groups, and the like. For example, cyclopentadienyl vanadium tri-t-butoxide, cyclopentadienyl vanadium-iso-propoxide, cyclopentadienyl vanadium dimethoxy chloride, trimethylsilylcyclopentadienyl vanadium di-iso-propoxy chloride, cyclopentadienyl vanadium di -T-butoxy chloride, cyclopentadienyl vanadium diphenoxy chloride, cyclopentadienyl vanadium-iso-propoxy dichloride, cyclopentadienyl vanadium-t-butoxy dichloride, cyclopentadienyl vanadium phenoxy dichloride, trimethylsilylcyclopentadienyl Vanadium tri-t-butoxide, trimethylcyclopentadienyl vanadium tri-iso-pro Oxide, trimethylsilylcyclopentadienyl vanadium dimethoxy chloride, trimethylsilylcyclopentadienyl vanadium di-iso-propoxychloride, trimethylsilylcyclopentadienyl vanadium di-t-butoxychloride, trimethylsilylcyclopentadienyl vanadium diphenoxychloride, trimethylsilylcyclopenta Examples include dienyl vanadium-iso-propoxy dichloride, trimethylsilylcyclopentadienyl vanadium-t-butoxy dichloride, trimethylsilylcyclopentadienyl vanadium phenoxy dichloride, and the like.

  (X) The methyl body which substituted the chlorine atom of (i)-(ix) with the methyl group is mentioned.

(Xi) R is bonded by a hydrocarbon group or a silyl group. For example, (t-butylamido) dimethyl (η ⁵ -cyclopentadienyl) silane vanadium dichloride, (t-butylamido) dimethyl (trimethyl-η ⁵ -cyclopentadienyl) silane vanadium dichloride, (t-butylamido) dimethyl (tetra Methyl- (eta) ⁵ -cyclopentadienyl) silane vanadium dichloride etc. are mentioned.

  (Xii) The methyl body which substituted the chlorine atom of (xi) with the methyl group is mentioned.

  (Xiii) The monoalkoxy body and dialkoxy body which substituted the chlorine atom of (xi) with the alkoxy group are mentioned.

  (Xiv) A compound obtained by substituting the monochloro body of (xiii) with a methyl group.

  (Xv) Amides obtained by substituting the chlorine atoms of (i) to (viii) with amide groups. For example, cyclopentadienyltris (diethylamide) vanadium, silylcyclopentadienyltris (iso-propylamide) vanadium, cyclopentadienyltris (n-octylamido) vanadium, cyclopentadienylbis (diethylamide) vanadium chloride, (Trimethylsilylcyclopentadienyl) bis (iso-propylamido) vanadium chloride, (trimethylsilylcyclopentadienyl) bis (n-octylamido) vanadium chloride, cyclopentadienyl (diethylamido) vanadium dichloride, cyclopentadienyl (iso) -Propylamide) vanadium dichloride, cyclopentadienyl (n-octylamide) vanadium dichloride, (trimethylsilylcyclopenta Enyl) tris (diethylamido) vanadium, (trimethylsilylcyclopentadienyl) tris (iso-propylamido) vanadium, (trimethylsilylcyclopentadienyl) tris (n-octylamido) vanadium, (trimethylsilylcyclopentadienyl) bis (diethylamide) ) Vanadium chloride, (trimethylsilylcyclopentadienyl) bis (iso-propylamide) vanadium chloride, (trimethylsilylcyclopentadienyl) bis (n-octylamide) vanadium chloride, (trimethylsilylcyclopentadienyl) (diethylamide) vanadium dichloride , (Trimethylsilylcyclopentadienyl) (iso-propylamido) vanadium dichloride, (trimethylsilylsilane) Ropentajieniru) (such as n- octyl amide) vanadium dichloride and the like.

  (Xvi) The methyl body which substituted the chlorine atom of (xv) with the methyl group is mentioned.

Specific compounds represented by RM (O) X ₂ include cyclopentadienyloxovanadium dichloride, methylcyclopentadienyloxovanadium dichloride, benzylcyclopentadienyloxovanadium dichloride, (1,3-dimethylcyclohexane). Pentadienyl) oxovanadium dichloride, (1-butyl-3-methylcyclopentadienyl) oxovanadium dichloride, (pentamethylcyclopentadienyl) oxovanadium dichloride, (trimethylsilylcyclopentadienyl) oxovanadium dichloride, (1 , 3-Bis (trimethylsilyl) cyclopentadienyl) oxovanadium dichloride, indenyloxovanadium dichloride, (2-methylindenyl) oxovanadium dichloride Ride, (2-trimethylsilylindenyl) oxovanadium dichloride, fluorenyloxovanadium dichloride and the like. The methyl body which substituted the chlorine atom of each said compound with the methyl group is also mentioned.

Also included are those in which R and X are bonded by a hydrocarbon group or a silyl group. For example, amide chlorides such as (t-butylamido) dimethyl (η ⁵ -cyclopentadienyl) silane oxovanadium chloride, (t-butylamido) dimethyl (tetramethyl-η ⁵ -cyclopentadienyl) silane oxovanadium chloride, Or the methyl body etc. which substituted the chlorine atom of these compounds with the methyl group are mentioned.

  Cyclopentadienyloxovanadium dimethoxide, cyclopentadienyloxovanadium di-iso-propoxide, cyclopentadienyloxovanadium di-t-butoxide, cyclopentadienyloxovanadium diphenoxide, cyclopentadienyloxovanadium Examples thereof include methoxy chloride, cyclopentadienyloxovanadium-iso-propoxychloride, cyclopentadienyloxovanadium-t-butoxychloride, cyclopentadienyloxovanadium phenoxychloride, and the like. The methyl body which substituted the chlorine atom of each said compound with the methyl group is also mentioned.

  (Cyclopentadienyl) bis (diethylamido) oxovanadium, (cyclopentadienyl) bis (di-iso-propylamido) oxovanadium, (cyclopentadienyl) bis (di-n-octylamido) oxovanadium, etc. Can be mentioned.

Specific compounds represented by Rn MX _3-n (NR ′) include cyclopentadienyl (methylimide) vanadium dichloride, cyclopentadienyl (phenylimide) vanadium dichloride, cyclopentadienyl (2,6- Dimethylphenylimide) vanadium dichloride, cyclopentadienyl (2,6-diiso-propylphenylimide) vanadium dichloride, (methylcyclopentadienyl) (phenylimide) vanadium dichloride, (1,3-dimethylcyclopentadiene) Enyl) (phenylimide) vanadium dichloride, (1-butyl-3-methylcyclopentadienyl) (phenylimide) vanadium dichloride, (pentamethylcyclopentadienyl) (phenylimide) vanadium dichloride Indenyl (phenylimide) vanadium dichloride, 2-methylindenyl (phenylimide) vanadium dichloride, fluorenyl (phenylimide) vanadium dichloride, and the like.

Also included are those in which R and X are bonded by a hydrocarbon group or a silyl group. For example, (t-butylamido) dimethyl (η ⁵ -cyclopentadienyl) silane (phenylimide) vanadium chloride, (t-butylamido) dimethyl (tetramethyl-η ⁵ -cyclopentadienyl) silane (phenylimide) vanadium chloride And amide chlorides such as those obtained by substituting the chlorine atom of these compounds with a methyl group.

Those in which R is bonded by a hydrocarbon group or a silyl group are also included. For example, dimethylbis (η ⁵ -cyclopentadienyl) silane (phenylimide) vanadium chloride, dimethylbis (η ⁵ -cyclopentadienyl) silane (tolylimide) vanadium chloride, dimethyl (tetramethyl-η ⁵ -cyclopentadi) Imenyl chlorides such as enyl) silane (phenylimide) vanadium chloride, dimethyl (tetramethyl-η ⁵ -cyclopentadienyl) silane (tolylimide) vanadium chloride, or methyl compounds in which the chlorine atom of these compounds is substituted with a methyl group Etc.

  Cyclopentadienyl vanadium (phenylimide) dimethoxide, cyclopentadienyl vanadium (phenylimide) diiso-propoxide, cyclopentadienyl vanadium (phenylimide) (iso-propoxy) chloride, (cyclopentadienyl) bis (diethylamide) ) Vanadium (phenylimide), (cyclopentadienyl) bis (diiso-propylamide) vanadium (phenylimide), and the like.

  Examples of the non-coordinating anion constituting the ionic compound as the catalyst component include, for example, tetra (phenyl) borate, tetra (fluorophenyl) borate, tetrakis (difluorophenyl) borate, tetrakis (tri Fluorophenyl) borate, tetrakis (tetrafluorophenyl) borate, tetrakis (pentafluorophenyl) borate, tetrakis (3,5-bistrifluoromethylphenyl) borate, tetrakis (tetrafluoromethylphenyl) borate -To, tetra (triyl) borate, tetra (xylyl) borate, triphenyl (pentafluorophenyl) borate, tris (pentafluorophenyl) (phenyl) borate, tridecahydride-7,8 -Dicarbaound decaborate, tetrafluoroborate , Hexafluorophosphate - such DOO and the like.

  On the other hand, examples of the cation constituting the ionic compound as the catalyst component include a carbonium cation, an oxonium cation, an ammonium cation, a phosphonium cation, a cycloheptyltrienyl cation, and a ferrocenium cation having a transition metal. it can.

  Specific examples of the carbonium cation include trisubstituted carbonium cations such as a triphenylcarbonium cation and a tris (substituted phenyl) carbonium cation. Specific examples of the tris (substituted phenyl) carbonium cation include tri (methylphenyl) carbonium cation and tris (dimethylphenyl) carbonium cation.

  Specific examples of the ammonium cation include trialkylammonium cation, triethylammonium cation, tripropylammonium cation, tributylammonium cation, tri (n-butyl) ammonium cation, and the like, N, N-dimethylanilinium cation, N N, N-diethylanilinium cation, N, N-2,4,6-pentamethylanilinium cation and other N, N-dialkylanilinium cation, di (iso-propyl) ammonium cation, dicyclohexylammonium cation and other dialkylammonium cations Mention may be made of cations.

  Specific examples of the phosphonium cation include triarylphosphonium cations such as a triphenylphosphonium cation, a tri (methylphenyl) phosphonium cation, and a tri (dimethylphenyl) phosphonium cation.

  As the ionic compound, those arbitrarily selected and combined from the non-coordinating anions and cations exemplified above can be preferably used.

  Among these, as ionic compounds, triphenylcarbonium tetrakis (pentafluorophenyl) borate, triphenylcarbonium tetrakis (fluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate. And 1,1′-dimethylferrocenium tetrakis (pentafluorophenyl) borate are preferred.

  An ionic compound may be used independently and may be used in combination of 2 or more type.

  The organometallic compound as a constituent component of the catalyst is preferably an organometallic compound of Group 1 to 3 elements of the periodic table, and as an organometallic compound of Group 1 to 3 elements of the periodic table, organoaluminum compounds Organic lithium compounds, organic magnesium compounds, organic zinc compounds, organic boron compounds, and the like.

  Specific compounds include methyl lithium, butyl lithium, phenyl lithium, benzyl lithium, neopentyl lithium, trimethylsilylmethyl lithium, bistrimethylsilylmethyl lithium, dibutyl magnesium, dihexyl magnesium, diethyl zinc, dimethyl zinc, trimethyl aluminum, triethyl aluminum, Examples include triisobutylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, boron trifluoride, triphenylboron and the like.

  In addition, organometallic halogen compounds such as ethylmagnesium chloride, butylmagnesium chloride, dimethylaluminum chloride, diethylaluminum chloride, sesquiethylaluminum chloride, ethylaluminum dichloride, hydrogenated organometallic compounds such as diethylaluminum hydride, sesquiethylaluminum hydride Is also included.

  As the organometallic compound as the catalyst component, an organoaluminum compound is preferable. Specific examples of organoaluminum compounds include trialkylaluminums such as trimethylaluminum, triethylaluminum, and triisobutylaluminum, organoaluminum halogen compounds such as dimethylaluminum chloride, diethylaluminum chloride, sesquiethylaluminum chloride, and ethylaluminum dichloride, diethyl And hydrogenated organoaluminum compounds such as aluminum hydride and sesquiethylaluminum hydride.

  Moreover, alumoxane can be used as the organometallic compound which is a catalyst component. The alumoxane is obtained by bringing an organoaluminum compound and a condensing agent into contact with each other, and includes a chain aluminoxane represented by the general formula (-Al (R ') O-) n or a cyclic aluminoxane. (R ′ is a hydrocarbon group having 1 to 10 carbon atoms, including those partially substituted with a halogen atom and / or an alkoxy group. N is the degree of polymerization and is 5 or more, preferably 10 or more) . Examples of R ′ include a methyl group, an ethyl group, a propyl group, and an isobutyl group, and a methyl group and an ethyl group are preferable. Examples of the organoaluminum compound used as an aluminoxane raw material include trialkylaluminums such as trimethylaluminum, triethylaluminum, and triisobutylaluminum, and mixtures thereof.

  An alumoxane using a mixture of trimethylaluminum and tributylaluminum as a raw material can be suitably used.

  Moreover, as a condensing agent, water is typically used, but in addition to this, an arbitrary one in which the trialkylaluminum undergoes a condensation reaction, for example, adsorbed water such as an inorganic substance, a diol, and the like. Two or more of the above organometallic compounds can be used in combination.

  The order of addition of the catalyst components is not particularly limited, but can be performed, for example, in the following order. After adding the organometallic compound as the catalyst component to the conjugated diene compound monomer to be polymerized or a mixture of the monomer and the solvent, the metallocene complex of the transition metal compound as the catalyst component and the ionic compound as the catalyst component in any order Added.

  Here, the conjugated diene compound monomer to be polymerized may be the whole amount or a part thereof. In the case of part of the monomer, the contact mixture can be mixed with the remaining monomer or the remaining monomer solution. Examples of the conjugated diene compound monomer include 1,3-butadiene, isoprene, 1,3-pentadiene, 2-ethyl-1,3-butadiene, and 2,3-dimethylbutadiene.

Hydrosilylation Modification The conjugated diene polymer modification product according to the present invention is preferably one having the chemical formula shown in (Formula 1), and particularly preferably hydrosilylated with diethylaminodimethylsilane. In addition, bis (dimethylamino) methylsilane, which is a bifunctional aminosilane, can also be used.

Bis (dimethylamino) methylsilane, which is a bifunctional aminosilane, is known to exhibit a much stronger interaction than diethylaminodimethylsilane, which is a monofunctional aminosilane. Therefore, as shown in Comparative Example 1 in Table 1, the Mooney viscosity of polybutadiene modified with the silane compound is increased.

  In Formula 1, R ′ is (a) an alkoxy group, preferably having 1 to 6 carbon atoms, and particularly preferably an ethoxy group. Further, (b) an alkyl group, preferably having 1 to 6 carbon atoms, particularly preferably a methyl group, and (c) a dialkylamino group, particularly a dimethyl group or a di-n-propylamino group. Di-iso-propylamino group, particularly preferably a diethylamino group. Further, (d) an aminoalkyl group, preferably having 1 to 6 carbon atoms, more preferably having 1 to 3 carbon atoms, and most preferably an aminopropyl group. Further, (e) an aminoalkoxy group, preferably having 1 to 6 carbon atoms, more preferably having 1 to 3 carbon atoms, and most preferably an aminoethoxy group. (F) Halogens, most preferably chlorine. Further, (g) a chloroalkoxy group, preferably having 1 to 6 carbon atoms, more preferably having 1 to 3 carbon atoms, and most preferably a chloroethoxy group. Further, (h) a chloroalkyl group, preferably having 1 to 6 carbon atoms, more preferably having 1 to 3 carbon atoms, and most preferably a chloroethyl group. Further, (i) an aromatic ring, most preferably a phenyl group or a chlorophenyl group. Further, (j) a cyanoalkyl group, preferably having 1 to 6 carbon atoms, more preferably having 1 to 3 carbon atoms, and most preferably a cyanopropyl group. Further, (k) a mercaptoalkyl group, preferably having 1 to 6 carbon atoms, more preferably having 1 to 3 carbon atoms, and most preferably a mercaptopropyl group. Further, (l) a hydroxyalkyl group, preferably having 1 to 6 carbon atoms, more preferably having 1 to 3 carbon atoms, and most preferably a hydroxypropyl group. Further, (m) a glycidoxyalkyl group, preferably having 1 to 6 carbon atoms, more preferably having 1 to 3 carbon atoms, and most preferably a glycidoxypropyl group. Further, (n) a nitrogen-containing cycloaliphatic group having 3 to 5 carbon atoms is preferable, and a piperidyl group is particularly preferable. (O) a piperidinoalkyl group, preferably having 1 to 6 carbon atoms, more preferably having 1 to 3 carbon atoms, and most preferably a piperidinoethyl group. Further, (p) a piperidinoalkoxy group, preferably having 1 to 6 carbon atoms, more preferably having 1 to 3 carbon atoms, and most preferably a piperidinoethoxy group. (Q) A piperazinoalkyl group, preferably having 1 to 6 carbon atoms, more preferably having 1 to 3 carbon atoms, and most preferably a piperazinopropyl group.

R ″ is (a) an alkoxy group, preferably having 1 to 6 carbon atoms, particularly preferably an ethoxy group, and (b) an alkyl group having 1 to 6 carbon atoms. And (c) alkylsiloxane (R ₃ SiO), wherein R is an alkyl group, particularly a methyl group, and (d) a dialkylamino group. In particular, a dimethyl group, a di-n-propylamino group, a di-iso-propylamino group, particularly preferably a diethylamino group, and (e) an aminoalkyl group having 1 to 6 carbon atoms. In particular, those having 1 to 3 carbon atoms are more preferred, and aminopropyl is particularly preferred, and (f) an aminoalkoxy group having 1 to 6 carbon atoms is preferred. 1 to A number of 3 is more preferred, particularly aminoethoxy, (g) halogen, most preferably chlorine, and (h) an aromatic ring, most preferably a phenyl group and a phenyl chloride group. Further, (i) a nitrogen-containing cycloaliphatic group having 3 to 5 carbon atoms is more preferred, and a piperidyl group is most preferred.

  A carbon number greater than 6 is not preferred because the alkyl group is too large and the reaction activity becomes low, and the hydrophobic function for reducing the affinity for silica becomes too high.

  Specific compounds include triethoxysilane, 1,1,1,3,5,5,5-heptamethyltrisiloxane (1,1,1,3,5,5,5-heptamethyltrisiloxane), 1,1. , 1,3,3,5,5-heptamethyltrisiloxane (1,1,1,3,3,5,5-heptamethyltrisiloxane), diethylaminodimethylsilane and the like are particularly good hydrosilylating agents. Usually, these hydrosilylating agents are used alone, but two or more kinds may be used in combination.

  As the catalyst used for hydrosilylation in the modified conjugated diene polymer according to the present invention, those described in US Pat. No. 3,419,593 and US Pat. No. 3,715,334 can be referred to.

  The hydrosilylation reaction solvent is preferably a hydrocarbon compound, and for example, pentane, hexane, heptane, octane, cyclohexane or aromatic hydrocarbon is more preferable. More preferred are benzene, toluene and xylene, and most preferred is toluene.

Platinum catalysts used for modification include (a) H ₂ PtCl _{6 in} toluene known as Speier catalyst, (b) Pt-divinyltetramethoxysilane in toluene / xylene known as Karstedt catalyst or (C) Lamoreaux catalyst (H ₂ PtCl _{6 in} n-octanol).

  The amount of platinum catalyst used in the reaction varies with the molar ratio of platinum to vinyl groups in the polymer backbone. The molar ratio (platinum / vinyl group) is more preferably 0.1-1 mmol / mol, 0.13-0.5 mmol / mol, particularly preferably 0.15-0.30 mmol / mol, and most preferably, It is 0.15-0.25 mmol / mol.

  The molar ratio of platinum catalyst and silane with respect to these vinyl contents is the optimum condition that can provide a sufficiently high vinyl conversion rate or hydrosilylation while avoiding excessive crosslinking due to condensation or interaction between silyl side chains. It is a range.

  When the molar ratio (platinum / vinyl group) is too lower than the above range, the addition rate is deteriorated and a sufficient effect cannot be obtained. If it is too high, the addition rate increases and the interaction between the polymers becomes stronger. Therefore, processability is inferior and there is a risk of non-uniformity during polymer blending.

  The hydrosilylation reaction is performed in a nitrogen atmosphere, but other inert gases such as helium and argon may be used.

The Mooney viscosity (ML _{1 + 4} , 100 ° C.) of the hydrosilylated modified polybutadiene is 80 to 130, preferably 82 to 129, particularly preferably 85 to 128. If the Mooney viscosity is too lower than the above range, there will be a problem of deterioration of mechanical properties. Conversely, if it is too high, the filler dispersibility at the time of kneading will deteriorate, and sufficient performance will not be exhibited, and there will be a problem in workability. It is not preferable because it occurs.

  Since hydrosilylation reactions at high temperatures always cause a significant proportion of silane crosslinking, 40-80 ° C, more preferred temperatures are 45-70 ° C, and particularly preferred temperatures are in the range 50-60 ° C. The reaction time is also preferably 2 to 5 hours to control the degree of crosslinking.

  The reactivity of the hydrosilylation is confirmed by FT-IR spectrum by monitoring the conversion of 1,2-vinyl content in the cis polybutadiene main chain. It is represented by the following (Formula 2).

  After the hydrosilylation reaction, about 1,000 ppm of antioxidant per 100 g of rubber is added to the ethanol solution to stop the reaction, and then the hydrosilylated cis-polybutadiene solution in cyclohexane is dried at 100 ° C. for 1 hour under vacuum.

  Further, the modified conjugated diene polymer in the present invention is a golf ball, an industrial belt, a footwear member (outsole), a rubber crawler, a medical device, an OA device, a vibration isolating rubber, a seismic isolation rubber, and a rubber composition for construction materials. Can be used as a raw material.

  Examples of the modified conjugated diene polymer according to the present invention will be described below. The physical property values of the examples were measured as follows.

(Measurement of hydrosilylation conversion)
The conversion of the microstructure and vinyl group was measured by measuring the FT-IR spectrum of Shimadzu-8700 manufactured by Shimadzu Corporation using a standard KBr film or CS ₂ solution method.

(Molecular weight measurement)
The molecular weight and molecular weight distribution were calculated using a standard polystyrene calibration curve using two columns in series using HLC-8220 GPC manufactured by Tosoh Corporation. The column used was Shodex GPC KF-805L column, which was measured by measuring a column temperature of 40 ° C. in THF.

(Silicon content measurement)
The silicone content was measured by ICP of Vista-MPX manufactured by Variance. Sample solutions were prepared by standard methods using sulfuric acid, nitric acid and alkaline solutions.

(Mooney viscosity measurement)
The Mooney viscosity (ML _{1 + 4} , 100 ° C.) measurement was performed in accordance with JIS K-6300 standard.

(Payne effect)
The dynamic strain sweep analysis was performed using a rubber processability analyzer RPA-2000 manufactured by Alpha Technologies under conditions of a frequency of 150 ° C. and 1 Hz.

(Reference Example 1)
(1) 900 ml of 1,3-butadiene cyclohexane dehydrated with molecular sieve after degassing a 1.5 liter stainless steel autoclave equipped with a magnetic induction rotating impeller and a thermocouple and substituting with nitrogen at normal pressure The solution (1,3-butadiene = 197.4 g) was added. 1.2 μL of deionized water was added with a microsyringe and stirred vigorously for 30 minutes at room temperature. Thereafter, the stirring speed was reduced to 500 rpm, and 105 ml of hydrogen was directly introduced from the gas cylinder at a flow rate of 50 ml per minute. 1.48 mmol of a heptane solution of triethylaluminum having a concentration of 0.59 M was added using a gas tight syringe and then aged for 3 minutes. Thereafter, a toluene solution 0.011mmol of _{C 5 H 5 V (O)} C l2 catalyst concentration 2.25 mM, was added using a gas tight syringe. After the reactor was heated to the desired temperature of 50 ° C., 0.016 mmol of 3.25 mM concentration of Ph ₃ CB (C ₆ F ₅ ) ₄ promoter was added from a gas tight syringe. The polymerization was carried out at 50 ° C. for 30 minutes.
(2) Thereafter, an ethanol solution of about 1000 ppm of 4,6-bis (octylthioethyl) -ortho-cresol was added as an antioxidant into the reactor to stop the reaction.
(3) Further immediately after that, the reactor was cooled to 30 ° C.
(4) Unreacted 1,3-butadiene was removed by reducing the pressure to 0.3 kgf / cm ² .
(5) The polybutadiene solution in cyclohexane was dried in vacuum at 100 ° C. for 1 hour.
(6) Thereafter, a polybutadiene sample was measured by FT-IR or GPC.
The number average molecular weight (Mn) of the cis-polybutadiene before hydrosilylation was 196,893 g / mol, and the molecular weight distribution (Mw / Mn) was 2.31.

(Reference Example 2)
(1) 900 ml of 1,3-butadiene cyclohexane dehydrated with molecular sieve after degassing a 1.5 liter stainless steel autoclave equipped with a magnetic induction rotating impeller and a thermocouple and substituting with nitrogen at normal pressure The solution (1,3-butadiene = 197.4 g) was added. 1.2 μL of deionized water was added with a microsyringe and stirred vigorously for 30 minutes at room temperature. Thereafter, the stirring speed was reduced to 500 rpm, and 105 ml of hydrogen was directly introduced from the gas cylinder at a flow rate of 50 ml per minute. 1.48 mmol of a heptane solution of triethylaluminum having a concentration of 0.59 M was added using a gas tight syringe and then aged for 3 minutes. Thereafter, a toluene solution 0.011mmol of _{C 5 H 5 V (O)} C l2 catalyst concentration 2.25 mM, was added using a gas tight syringe. After the reactor was heated to the desired temperature of 50 ° C., 0.016 mmol of 3.25 mM concentration of Ph ₃ CB (C ₆ F ₅ ) ₄ promoter was added from a gas tight syringe. The polymerization was carried out at 50 ° C. for 30 minutes.
(2) Immediately after polymerization, 1 ml of isopropyl alcohol is added as a reaction terminator.
(3) Further immediately after that, the reactor was cooled to 30 ° C.
(4) Unreacted 1,3-butadiene was removed by reducing the pressure to 0.3 kgf / cm ² .
(5) The polybutadiene solution in cyclohexane was dried in vacuum at 100 ° C. for 1 hour.
(6) Thereafter, a polybutadiene sample was measured by FT-IR or GPC.
The number average molecular weight (Mn) of the cis polybutadiene before hydrosilylation was 196,893 g / mol, and the molecular weight distribution (Mw / Mn) was 2.09.

(Comparative Example 1)
After performing the polymerization reaction by the same operation as (1) of Reference Example 1, the operation of (3) and (4) was performed without performing the operation of adding the antioxidant of (2).
(5) Next, the hydrosilylation reaction of the obtained polybutadiene was reacted at 40 to 80 ° C., more preferably at 50 to 60 ° C. in the presence of a Speier catalyst (H ₂ PtCl ₆ ) in isopropanol together with diethylaminodimethylsilane. .
(6) Thereafter, an ethanol solution of about 1000 ppm of 4,6-bis (octylthioethyl) -ortho-cresol per 100 g of rubber was added to the reactor as an antioxidant to stop the reaction.
(7) The hydrosilylated cis-polybutadiene solution in cyclohexane was dried in vacuum at 100 ° C. for 1 hour.
The molecular weight distribution is 3.29, and the difference from the molecular weight distribution of Reference Example 1 is 0.98.

(Comparative Example 2)
After performing the polymerization reaction by the same operation as (1) of Reference Example 1, the operation of (3) and (4) was performed without performing the operation of adding the antioxidant of (2).
(5) Next, the hydrosilylation reaction of the obtained polybutadiene was reacted at 40 to 80 ° C., more preferably at 50 to 60 ° C. in the presence of a Speier catalyst (H ₂ PtCl ₆ ) in isopropanol together with diethylaminodimethylsilane. .
(6) Thereafter, an ethanol solution of about 1000 ppm of 4,6-bis (octylthioethyl) -ortho-cresol per 100 g of rubber was added to the reactor as an antioxidant to stop the reaction.
(7) The hydrosilylated cis-polybutadiene solution in cyclohexane was dried in vacuum at 100 ° C. for 1 hour.
The molecular weight distribution is 2.88, and the difference from the molecular weight distribution of Reference Example 1 is 0.57.

(Comparative Example 3)
After performing the polymerization reaction by the same operation as (1) of Reference Example 1, the operation of (3) and (4) was performed without performing the operation of adding the antioxidant of (2).
(5) Next, the hydrosilylation reaction of the obtained polybutadiene was reacted at 40 to 80 ° C., more preferably at 50 to 60 ° C. in the presence of a Speier catalyst (H ₂ PtCl ₆ ) in isopropanol together with diethylaminodimethylsilane. .
(6) Thereafter, an ethanol solution of about 1000 ppm of 4,6-bis (octylthioethyl) -ortho-cresol per 100 g of rubber was added to the reactor as an antioxidant to stop the reaction.
(7) The hydrosilylated cis-polybutadiene solution in cyclohexane was dried in vacuum at 100 ° C. for 1 hour.
The molecular weight distribution is 2.90, and the difference from the molecular weight distribution of Reference Example 1 is 0.59.
(Comparative Example 4)
After performing the polymerization reaction by the same operation as (1) of Reference Example 1, the operations of (3) and (4) were performed without performing the operation of adding the antioxidant of 2).
(5) Next, the hydrosilylation reaction of the obtained polybutadiene was reacted at 40 to 80 ° C., more preferably at 50 to 60 ° C. in the presence of a Speier catalyst (H ₂ PtCl ₆ ) in isopropanol together with diethylaminodimethylsilane. .
(6) Thereafter, an ethanol solution of about 1000 ppm of 4,6-bis (octylthioethyl) -ortho-cresol per 100 g of rubber was added to the reactor as an antioxidant to stop the reaction.
(7) Dry the hydrosilylated cis-polybutadiene solution in cyclohexane at 100 ° C. for 1 hour under vacuum.
The molecular weight distribution is 2.93, and the difference from the molecular weight distribution of Reference Example 1 is 0.62.
Example 1
After performing the polymerization reaction in the same manner from (1) to (4) in Reference Example 2,
(5) Next, the hydrosilylation reaction of the obtained polybutadiene was reacted at 40 to 80 ° C., more preferably at 50 to 60 ° C. in the presence of a Speier catalyst (H ₂ PtCl ₆ ) in isopropanol together with diethylaminodimethylsilane. .
(6) Thereafter, an ethanol solution of about 1000 ppm of 4,6-bis (octylthioethyl) -ortho-cresol per 100 g of rubber was added to the reactor as an antioxidant to stop the reaction.
(7) The hydrosilylated cis-polybutadiene solution in cyclohexane was dried in vacuum at 100 ° C. for 1 hour.
The molecular weight distribution is 2.34, and the difference from the molecular weight distribution of Reference Example 2 is 0.28.

Table 1 shows the physical property results of the vulcanizate containing silica.
From Table 1, the molecular weight distribution increases (Δ (Mw / Mn)) of the modified butadiene rubbers (Comparative Examples 1 to 4) prepared by the conventional method are all 0.59 or more, and the molecular weight greatly increases. It can be seen. On the other hand, the increase (Δ (Mw / Mn)) of the molecular weight distribution of the modified butadiene rubber produced by the method of the present invention is 0.28, indicating that the expansion of the molecular weight distribution is suppressed.

FIG. 1 shows a GPC chart of unmodified and modified butadiene rubber.
As can be seen from FIG. 1, the sample produced by the method of the present invention has no high molecular weight tailing and the polymerization is completely stopped. In particular, in comparison with unmodified butadiene rubber, it can be seen that there is a difference in molecular weight distribution at the stage of polymerization. Furthermore, when the modified butadiene rubber using these unmodified butadiene rubbers is produced by the method of the present invention, high molecular weight tailing is hardly observed.

GPC chart of unmodified and modified butadiene rubber

Claims (6)

In the method for producing a modified conjugated diene polymer,
(1) Immediately after polymerizing the conjugated diene polymer, water or an alcohol having 5 or less carbon atoms is added as a reaction terminator,
(2) Next, the reaction system is cooled,
(3) A method for producing a modified conjugated diene polymer, wherein the conjugated diene polymer is then hydrosilylated with an organosilane compound.   The modified conjugated diene polymer according to claim 1, wherein the conjugated diene polymer has a 1,4-cis structure of 80 to 95% and a 1,2-vinyl structure of 4 to 19 mol%. Method. The conjugated diene polymer is produced by polymerization using a metallocene vanadium complex compound, an ionic compound of a non-coordinating anion and a cation, and a catalyst composed of an organometallic compound. 3. A process for producing a modified conjugated diene polymer according to any one of 2 above.   The method for producing a modified conjugated diene polymer according to claim 1, wherein the reaction terminator used in (1) in the production method of claim 1 is isopropyl alcohol.   The method for producing a modified conjugated diene polymer according to claim 1, wherein the organosilane compound is diethylaminodimethylsilane. A modified conjugated diene polymer produced by the method according to claim 1.

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