JP5370076B2 - Modified conjugated diene polymer and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a modified rubber having high Mooney viscosity with a polybutadiene hydrosilylated with a diethylamino dimethylsilane, and its manufacturing method. <P>SOLUTION: The conjugated diene polymer modified product includes a polybutadiene including 80 mol% or more of a 1,4-cis structure and 20 mol% or less of a 1,2-vinyl structure hydrosilylated with a diethylamino dimethylsilane with its Mooney viscosity (ML<SB>1+4'</SB>100&deg;C) being 80-130. Also provided is its manufacturing method. <P>COPYRIGHT: (C)2011,JPO&amp;INPIT

Description

The present invention relates to a modified conjugated diene polymer obtained by hydrosilylating polybutadiene with diethylaminodimethylsilane and a method for producing the same.

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.

The present invention provides a modified rubber having a high Mooney viscosity in which polybutadiene is hydrosilylated with diethylaminodimethylsilane and a method for producing the same.

In the present invention, polybutadiene having a 1,4-cis structure of 80% or more and a 1,2-vinyl structure of 20 mol% or less is hydrosilylated with diethylaminodimethylsilane and has a Mooney viscosity (ML _{1 + 4} , 100 ° C.). The present invention relates to a modified conjugated diene polymer that is 80 to 130.

The modified conjugated diene polymer is characterized in that the 1,4-cis structure is 80 to 95% and the 1,2-vinyl structure is 4 to 19 mol%.

The polybutadiene is produced by polymerization using a catalyst comprising a metallocene complex of a vanadium compound, an ionic compound of a non-coordinating anion and a cation, and an organometallic compound. Related to things.

  A step of polymerizing 1,3-butadiene in a non-aromatic hydrocarbon solvent using the catalyst, and a step of hydrosilylating the polymerized polybutadiene using diethylaminodimethylsilane without purifying the polymerized polybutadiene. And a process for producing the modified conjugated diene polymer.

Polybutadiene In the polybutadiene used in the modified conjugated diene polymer according to the present invention, the hydrosilylation is preferably such that the vinyl group of polybutadiene is hydrosilylated.
The idea of the present invention is that high cis polybutadiene having a vinyl group content of only about 10% (1,4-cis structure 80-95 mol%, due to the limitation that hydrosilylation tends to react with vinyl side chains of polybutadiene. In order to modify the vinyl side chain of 1,2-vinyl structure (4 to 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 number average molecular weight (Mn) of the polybutadiene is 180,000 to 380,000 g / mol, particularly 220,000 to 350,000 g / mol. Further, the molecular weight distribution (Mw / Mn) is preferably 2.0 to 3.7, and particularly preferably 2.4 to 3.2.

  This polybutadiene is preferably produced by polymerization using a catalyst comprising a metallocene complex of a transition metal compound, an ionic compound of a non-coordinating anion and a cation, and 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.

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, and 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 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.

  The modified conjugated diene polymer according to the present invention preferably has a chemical formula represented by (Formula 1), and is 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.

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 as catalysts used for hydrosilylation of polybutadiene. The denaturation method performed in the steps (I) to (IV) is shown below.
(I) Polymerization of 1,3-polybutadiene in cyclohexane at a monomer concentration of 25-35 wt% and a temperature of 40-70 ° C., preferably 45-55 ° C. The catalyst system used in the polymerization is (a) a half vanadocene (V) catalyst represented by the chemical formula (C ₅ R ₅ ) VOX ₂ . Here, R = H and X = Cl.
(b) An aluminium compound represented by the chemical formula AlR ₃ . Where R = alkyl group
(c) Organoboric acid compound Ph ₃ CB (C ₆ F ₅ ) ₄
(II) The hydrosilylation reaction of cis-polybutadiene is carried out at 40 to 80 ° C. in the presence of a Speier catalyst (H ₂ PtCl ₆ ) in isopropanol together with a silane compound represented by the chemical formula SiH (R ′) (R ″) _2. Preferably obtained from (I) which is soluble in cyclohexane after releasing unreacted 1,3-polybutadiene monomer at 50-60 ° C., where R ′ is preferably ethoxy, methyl, diethylamino, R "Is preferably ethoxy, methyl, hexamethyltrisiloxane.
(III) About 1,000 ppm of antioxidant per 100 g of rubber is added to the ethanol solution to stop the reaction.
(IV) Dry the hydrosilylated cis-polybutadiene solution in cyclohexane at 100 ° C. for 1 hour under vacuum.

  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 include (a) H ₂ PtCl _{6 in} toluene known as the Speier catalyst, (b) Pt-divinyltetramethoxysilane in toluene / xylene known as the 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. Since it occurs, it is not preferable.

  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).

A method for producing a modified conjugated diene polymer and a method for producing a modified conjugated diene polymer include a step of polymerizing 1,3-butadiene in a non-aromatic hydrocarbon solvent using the catalyst, and then polymerization. And hydrosilylating the resulting polybutadiene with a silicon-containing compound without purification.

The monomer concentration is preferably 10 to 50 wt%, more preferably 20 to 40 wt%, and particularly preferably 25 to 35 wt%. If the concentration is lower than the above range, the polymerization activity is too low, which is disadvantageous because the molecular weight does not increase. On the other hand, if the concentration is higher than the above range, the polymerization activity is too high, so that it is difficult to control the temperature, and the resulting rubber tends to show high crosslinkability by modification, which is not preferable.

The metallocene complex of the transition metal compound, which is the catalyst component of the polymerization catalyst used, is not particularly limited as long as it is a metallocene complex of a group 3-6 transition metal in the periodic table. Of these, the metallocene-type complex is preferable, and among them, a half-vanadene (V) catalyst using metal vanadium is particularly preferable. As the half vanadocene (V) catalyst, a chemical formula (C ₅ R ₅ ) MtOX ₂ is preferable. Further, R is hydrogen or a methyl group, and X is a halogen element, and chlorine is particularly preferable. Mt represents a metal.

Organic boron can be used as the non-coordinating anion which is a catalyst component. As the counter cation, carbonium, ammonium, or phosphonium cation is used. In particular, as the counter cation, a triallyl carbonium cation or an N, N-dialkylanilinium cation can also be used.

Examples of the compound containing a non-coordinating anion and a counter cation include triphenylcarbonium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, triphenylcarbonium tetrakis [3, 5-bis (trifluoromethyl) phenyl] borate and N, N-dimethylanilinium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, and triphenylcarbonium tetrakis (pentafluorophenyl) borate preferable.

Moreover, as an organometallic compound which is a catalyst component, an alkylaluminum compound represented by the formula AlR ₃ is preferable. Here, R is an alkyl group, more preferably an ethyl group.

  The polymerization temperature of polybutadiene is preferably 40 to 70 ° C, and more preferably 50 to 65 ° C. Moreover, it is preferable to use cyclohexane as the polymerization solvent.

In the hydrosilylation reaction, n-hexane, n-pentane, and cyclic non-aromatic hydrocarbons such as cyclopentane and cyclohexane are preferable as the solvent, and cyclohexane is most preferable, and the solvent is represented by the formula (1). The presence of a Speier catalyst (H ₂ PtCl ₆ ) in isopropanol together with the silicon-containing compound to be released, releasing the unreacted 1,3-polybutadiene monomer and then reacting at 40-80 ° C., more preferably 50-60 ° C. Is preferred. Here, in the compound represented by the formula (1), R ′ is preferably ethoxy, methyl or diethylamino, and R ″ is preferably ethoxy, methyl or hexamethyltrisiloxane.

  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.

Rubber Reinforcer-Containing Rubber Composition (A) Vulcanizable diene rubber used in the rubber reinforcing agent-containing rubber composition according to the present invention includes (a1) natural rubber or polyisoprene rubber and (a2) 1, 4 -A combination of diene rubbers other than (a1) having a cis structure of 80 to 99.5 mol% and a 1,2-vinyl structure of 0.5 to 20 mol% is desirable.

  The blending amount of the vulcanizable diene rubber (A) is 50 to 99 phr, more preferably 60 to 95 phr, and particularly preferably 70 to 90 phr.

  (A1) Natural rubber or polyisoprene rubber is usually used alone, but may be used in combination. Among these, it is desirable to use natural rubber alone.

  (A1) The blending amount of natural rubber or polyisoprene rubber is 10 to 90 phr, more preferably 15 to 70 phr, and particularly preferably 20 to 60 phr.

  If the blending amount of (a1) is smaller than the above range, problems such as inferior mechanical properties such as tensile strength and elongation at break occur. This is not preferable because it causes the following problem.

Moreover, as a physical property, Mooney viscosity (ML1 _{+ 4} , 100 degreeC) has more preferable 40-120, 45-100, Most preferably, it is 50-90.

  If the Mooney viscosity of (a1) is smaller than the above range, the entanglement between molecules is weak and rubber properties such as mechanical properties when vulcanized tend to be lowered. When knead | mixed, since a molding process performance is inferior and a problem is produced in workability, it is not preferable.

  (A2) 1,4-polybutadiene rubber as the diene rubber other than (a1) having a 1,4-cis structure of 80 to 99.5 mol% and a 1,2-vinyl structure of 0.5 to 20 mol% Styrene-butadiene rubber, acrylonitrile-butadiene rubber, chloroprene rubber, MBR, VCR (rubber in which fibrous 1,2-polybutadiene is dispersed in a 1,4-polybutadiene matrix), and a combination of two or more of these May be.

  The diene rubber other than (a2) having a 1,4-cis structure of 80 to 99.5 mol% and a 1,2-vinyl structure of 0.5 to 20 mol% is diethyl aluminum chloride. Commercially available cis-1,4-polybutadiene prepared by solution polymerization of 1,3-butadiene in the presence of a cobalt (II) octaate cobalt catalyst combined with a novel organoaluminum compound can be used. However, it is not limited to the above-mentioned commercial products.

  (A2) includes commercially available cis-1,4-polybutadiene produced by solution polymerization of 1,3-butadiene in the presence of a cobalt (II) octaate cobalt catalyst combined with an organoaluminum compound such as diethylaluminum chloride. It is desirable to use alone or use MBR alone.

As a physical property of (a2), Mooney viscosity (ML1 _{+ 4} , 100 degreeC) is 10-70, More preferably, it is 20-65, Most preferably, it is 30-60.

If the Mooney viscosity (ML _{1 + 4} , 100 ° C.) of (a2) is smaller than the above range, the entanglement between the molecules is weak and the rubber properties such as mechanical properties at the time of vulcanization tend to be lowered. When the kneading is carried out together with the compounding agent, the entanglement between them is so strong that the molding process performance is inferior and the workability is problematic.

  As a compounding quantity of (a2), 10-90 phr and 20-70 are preferable, Most preferably, it is 30-50 phr.

  When the blending amount of (a2) is smaller than the above range, problems such as deterioration of wear resistance, slip resistance, and viscoelasticity occur, which is not preferable.

  The amount of (B) hydrosilylated modified conjugated diene polymer used in the rubber reinforcing agent-containing rubber composition according to the present invention is 1 to 50 phr, more preferably 5 to 40 phr, and particularly preferably 10 to 30 phr. . If the blending amount of (B) is smaller than the above range, the effect on the interaction between the rubber reinforcing material and the rubber will be low, and conversely if larger than the above range, problems such as a decrease in physical properties of the rubber matrix will occur. It is not preferable.

  The rubber components used in the rubber reinforcing agent-containing rubber composition include (a1) natural rubber or polyisoprene rubber and (a2) 1,4-cis structure of 80 to 99.5 mol%, and 1,2-vinyl structure. Diene-based rubber other than (a1) having a B content of 0.5 to 20 mol% and (B) vinyl of polybutadiene having a 1,4-cis structure of 80 to 95 mol% and a 1,2-vinyl structure of 4 to 19 mol% A three-component rubber of a modified conjugated diene polymer in which a group is hydrosilylated is more desirable.

  As the (C) rubber reinforcing agent used in the rubber reinforcing agent-containing rubber composition according to the present invention, any reinforcing material such as an inorganic rubber reinforcing agent and an organic rubber reinforcing agent can be applied. Inorganic rubber reinforcing agents include precipitated silica, metal oxides, alkali metal salts, and carbon black. However, it is not limited to these. An example of the organic rubber reinforcing agent is fibrous 1,2-polybutadiene. However, it is not limited to this.

  As the rubber reinforcing agent, two or more kinds may be combined in addition to using each reinforcing agent described above alone. For example, silica and carbon black may be used in combination.

  When the rubber reinforcing agent is silica, those obtained by acidification of precipitated silica, particularly soluble silicic acid such as sodium silicate are preferred. Furthermore, as described above, these silicas may be combined with carbon black.

  In addition, commercially available precipitated silica can be used, for example, Rhodia silica (Trademark Hi-Sil) such as Z1165MP and Z165GR, Tosoh VN2 (Trademark Nippon), Evonik Silica VN2 and VN3, etc. Can be given. In addition, wet silica (hydrous silicic acid), dry silica (anhydrous silicic acid), calcium silicate, aluminum silicate, etc. are listed. Among them, the improvement effect of fracture resistance, wet grip and low rolling resistance are compatible. Wet silica is most preferred because it is most effective.

The most preferable rubber reinforcing agent is an inorganic rubber reinforcing agent, and in particular, precipitated silica having a BET surface area of 100 to 300 m ² / g and a particle size of 0.01 to 0.1 μm.

  The amount of the rubber reinforcing agent is 20 to 80 phr, more preferably 25 to 75 phr, and particularly preferably 30 to 70 phr.

In the rubber composition containing a rubber reinforcing agent of the present invention, various chemicals usually used in the rubber industry, for example, a vulcanizing agent, a vulcanization accelerator, a process oil, are used as long as the object of the present invention is not impaired. Anti-aging agent, scorch preventing agent, zinc white, stearic acid and the like can be contained.
Further, the rubber composition of the present invention is obtained by kneading using a kneader such as an open kneader such as a roll, a closed kneader such as a Banbury mixer, and vulcanized after molding. Applicable to various rubber products.

  The (D) vulcanizing agent used in the rubber composition for blending a rubber reinforcing agent according to the present invention is not particularly limited, but is mainly sulfur, preferably 0.1 to 10 phr, and 1 to 5 More preferred. It is known that when the amount of the vulcanizing agent is too large, the elasticity of the rubber vulcanizate is lost because the crosslinking proceeds too much. On the other hand, if the amount of the vulcanized product is too small, rubber elasticity and frictional resistance are insufficient.

  Further, the vulcanization accelerator used in the rubber composition for compounding a rubber reinforcing agent according to the present invention is 2-mercaptobenzothiazole (M), dibenzylzothiazyl disulfide (DM), N-cyclohexyl-2-benzothia. These are, but are not limited to, disulfenamide (CZ) and diphenylguanidine (DD). These vulcanization accelerators may be used in combination. A preferred use amount is 0.1 to 5 phr, more preferably 1 to 3 phr.

In the present invention, in addition to the main components described above, (E) a silane coupling agent, an active polysulfide, and the like can be blended and used. The silane coupling agent has an active silane when forming a bond with a silanol group on the silica surface. The active polysulfide contains 2-6 sulfur atoms that interact with the elastomer.
The amount of the silane coupling agent or active polysulfide is 1 to 10 phr, more preferably 1 to 5 phr. For example, if the blending amount of the silane coupling agent is too large, such as 10 phr or more, the crosslinking process proceeds only a few percent in the coupling process. Conversely, if the blending amount is too small, such as 10 phr or less, the silica is not sufficiently dispersed in the rubber matrix. It becomes. The active polysulfide shows the same tendency.

  Examples of commercially available silane coupling agents include, but are not limited to, the following. Bis (3-triethoxysilylpropyl) tetrasulfide, bis (3-triethoxysilylpropyl) trisulfide, bis (3-triethoxysilylpropyl) disulfide, bis (2-triethoxysilylpropyl) tetrasulfide, bis (3 -Trimethoxysilylpropyl) tetrasulfide, bis (2-trimethoxysilylpropyl) tetrasulfide, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethoxysilane 3-triethoxysilylpropyl-N, N-dimethylthiocarbamoyl tetrasulfide, 3-triethoxysilylpropyl-N, N-dimethylthiocarbamoyl tetrasulfide, 2-triethoxy Silylethyl-N, N-dimethylthiocarbamoyl tetrasulfide, 3-trimethoxysilylpropylbenzothiazole tetrasulfide, 3-triethoxysilylpropylbenzothiazole tetrasulfide, 3-triethoxysilylpropyl methacrylate monosulfide, 3-trimethoxysilylpropyl Methacrylate monosulfide. In the present invention, bis (3-triethoxysilylpropyl) tetrasulfide is most preferred.

  Process oil, zinc oxide, stearic acid, antioxidant, vulcanization accelerator, and sulfur may be used in the rubber mixing step and the vulcanization step as other compounding components of the rubber composition for compounding a rubber reinforcing agent according to the present invention. I can do it.

  Examples of the process oil include paraffin oil, naphthenic oil, and aroma oil, but are not limited to these, and aroma oil is preferable. Aroma oils are used to maintain the maximum tensile strength and friction resistance performance of rubber compositions. A preferred amount of process oil is 1-50 phr, more preferably 5-30 phr.

  The rubber reinforcing agent rubber composition according to the present invention comprises (A) a vulcanizable rubber, (B) a hydrosilylated conjugated diene polymer modified product, and (C) a rubber reinforcing agent. As a result, it is possible to provide a rubber composition containing a rubber reinforcing agent excellent in low hysteresis loss (tan δ) and low fuel consumption and a method for producing the same. Furthermore, an environmentally friendly rubber composition material can be provided by applying the rubber reinforcing agent-containing rubber composition described above.

  The rubber reinforcing agent-containing rubber composition in the present invention can be used for, for example, a low fuel consumption rubber material. Further, by combining with other natural rubbers and synthetic diene rubbers, other industries have high applicability for use including rubber components.

  Moreover, the rubber reinforcing agent-containing rubber composition in the present invention is used for golf balls, industrial belts, footwear members (outsole), rubber crawlers, medical devices, OA equipment, vibration-proof rubbers, seismic isolation rubbers, construction materials, and the like. be able to.

  The rubber reinforcing agent-containing rubber composition obtained in the present invention comprises the step of mixing the (A) vulcanizable diene rubber, the (B) modified conjugated diene polymer and the (C) rubber reinforcing agent, Thereafter, (D) at least one of a vulcanizing agent and a vulcanization accelerator is added and vulcanized.

Mixing step (method for producing the first rubber composition)
In the mixing step, all the rubber compositions except for the vulcanizing agent and the vulcanization accelerator are mixed within 90 minutes at 90 ° C. in a closed kneader such as a Banbury mixer. Immediately thereafter, the mixture is cooled in a temperature range of 30 to 60 ° C. using a mixing roll and then formed into a sheet. Therefore, the said mixing process means the premixing or the mixing process except the vulcanization raw material.

The Mooney viscosity is measured using a sample of the sheet-like rubber composition.
The Mooney viscosity (ML _{1 + 4} , 100 ° C.) of the silica compounded rubber composition is 55 to 175, more preferably 65 to 175, and particularly preferably 110 to 175.

When the Mooney viscosity (ML _{1 + 4} , 100 ° C.) of the silica compounded rubber composition is larger than the above range, the molding process performance is inferior, causing a problem in workability. There is a problem in dispersibility of silica.

The Payne effect is confirmed using a sample of the sheet-like rubber composition.
The Payne effect can confirm silica-rubber interaction and silica dispersion using Alpha Technology RPA-2000.

Vulcanization preliminary process (method for producing the second rubber composition)
The silica-rubber compound sheet obtained from the mixing step described above is mixed with a vulcanizing agent and a vulcanization accelerator using a mixing roll in a temperature range of 30 to 60 ° C.
As described above, sulfur is preferable as the vulcanizing agent.

The rubber composition in the preliminary vulcanization process is drawn into a sheet, and the sample is Mooney viscosity (ML _{1 + 4} , 100 ° C.), the optimal vulcanization point with a curastometer at 150 ° C., and vulcanized at 150 ° C. with RPA-2000. A measurement of tan δ in the sulfur is made.

The Mooney viscosity (ML _{1 + 4} , 100 ° C.) of the second rubber composition in the preliminary vulcanization process is smaller than the Mooney viscosity of the first compound obtained from the mixing process, and its value is 60 to 150, more preferably 70. ˜130, particularly preferably 85˜115.

If the Mooney viscosity (ML _{1 + 4} , 100 ° C.) of the second rubber composition in the vulcanization preparatory process is larger than the above range, the molding process performance is inferior, causing problems in workability. The tensile stress of the vulcanizate cannot be obtained, resulting in workability problems.

Vulcanization characteristics of silica compounded rubber composition and physical properties of vulcanizate The silica compounded rubber composition of the second rubber composition in the preliminary vulcanization process is the optimum vulcanization measured by the above-mentioned Curalastometer (registered trademark) According to the point, it is made by press molding at 150 ° C. The rubber vulcanizate of the present invention follows the measurement of viscoelastic properties through temperature sweep, tensile strength and exothermic properties. Furthermore, the dispersibility of the precipitated silica in the rubber vulcanizate was observed using an electron transmission microscope (TEM).

  By measuring the viscoelastic characteristics of the vulcanizate by temperature sweep, the basic characteristics of the rubber composition in each application can be estimated.

  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.

Polymerization method of polybutadiene (reference example)
A 1.5 liter stainless steel autoclave equipped with a magnetically induced rotating stirring blade and a thermocouple was degassed, purged with nitrogen at normal pressure, and then dehydrated with molecular sieves in 900 ml of 1,3-butadiene in cyclohexane solution (1 , 3-butadiene = 197.4 g). 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 2.25mM 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. The reactor was then immediately cooled to 30 ° C. and unreacted 1,3-butadiene was removed by reducing the pressure to 0.3 kgf / cm ² . Thereafter, a polybutadiene sample was measured by FTIR or GPC.
The number average molecular weight (Mn) of the cis polybutadiene before hydrosilylation was 167,000 g / mol, and the molecular weight distribution (Mw / Mn) was 3.2.

Example 1
The polymerization method of unmodified cis 1,4-polybutadiene is generally according to the above preparation method, but the polybutadiene used in the present invention has a polymerization temperature of 60 ° C. and a hydrogen amount of 95 ml as a molecular weight regulator for adjusting the molecular weight. Changed to
The microstructure of the unmodified cis 1,4-polybutadiene is 88.4% for the 1,4-cis structure, 10.6% for the 1,2-vinyl structure, and 1.0% for the 1,4-trans structure. This was confirmed by FT-IR. The number average molecular weight of unmodified cis 1,4-polybutadiene is 239,000, and the molecular weight distribution (Mw / Mn) is 2.8.
Since the molecular weight of cis 1,4-polybutadiene hydrosilylated with diethylaminodimethylsilane was high, the conversion of 1,2-vinyl could not be clearly confirmed by FTIR.
Therefore, as a result of measuring the silicon content by IPC, it was 300 ppm. The hydrosilylated cis 1,4-polybutadiene is partially crosslinked, bluish brown, and has a Mooney viscosity of 86.1. Table 1 shows the measured values.

Example 2
The polymerization method of unmodified cis 1,4-polybutadiene is generally based on the above-described preparation method, but the polybutadiene used in the present invention has a polymerization temperature of 60 ° C. and a hydrogen amount of 65 ml as a molecular weight regulator to adjust the molecular weight. Changed to
The microstructure of the unmodified cis 1,4-polybutadiene is 88.0% for the 1,4-cis structure, 10.9% for the 1,2-vinyl structure, and 1.1% for the 1,4-trans structure. This was confirmed by FT-IR. The number average molecular weight of unmodified cis 1,4-polybutadiene is 324,000, and the molecular weight distribution (Mw / Mn) is 3.1.
Since the molecular weight of cis 1,4-polybutadiene hydrosilylated with diethylaminodimethylsilane was high, the conversion of 1,2-vinyl could not be clearly confirmed by FTIR.
Therefore, as a result of measuring the silicon content by IPC, it was 460 ppm. The hydrosilylated cis 1,4-polybutadiene is partially crosslinked, bluish brown, and has a Mooney viscosity of 116.2. Table 1 shows the measured values.

Example 3
The polymerization method of unmodified cis 1,4-polybutadiene is generally based on the above-described preparation method, but the polybutadiene used in the present invention has a polymerization temperature of 65 ° C. and a hydrogen amount of 65 ml as a molecular weight regulator to adjust the molecular weight. Changed to
The microstructure of unmodified cis 1,4-polybutadiene is 88.7% for 1,4-cis structure, 10.2% for 1,2-vinyl structure, and 1.1% for 1,4-trans structure. This was confirmed by FT-IR. The number average molecular weight of unmodified cis 1,4-polybutadiene is 340,000, and the molecular weight distribution (Mw / Mn) is 2.9.
Since the molecular weight of cis 1,4-polybutadiene hydrosilylated with diethylaminodimethylsilane was high, the conversion of 1,2-vinyl could not be clearly confirmed by FTIR.
Therefore, as a result of measuring the silicon content by IPC, it was 370 ppm. The hydrosilylated cis 1,4-polybutadiene is partially crosslinked, bluish brown, and has a Mooney viscosity of 128. Table 1 shows the measured values.

Comparative Example 1
The polymerization method of unmodified cis 1,4-polybutadiene is generally based on the preparation method described above, but the polybutadiene used in the present invention has a polymerization temperature of 65 ° C. and a hydrogen amount of 95 ml as a molecular weight regulator to adjust the molecular weight. Changed to
The microstructure of the unmodified cis 1,4-polybutadiene is 88.5% for 1,4-cis structure, 10.6% for 1,2-vinyl structure, and 0.9% for 1,4-trans structure. This was confirmed by FT-IR. The number average molecular weight of unmodified cis 1,4-polybutadiene is 250,000, and the molecular weight distribution (Mw / Mn) is 3.1.
Bifunctional aminosilane bis (dimethylamino) methylsilane (SiH: Vinyl molar ratio 1:12) was used as a modifier instead of diethylaminodimethylsilane (SiH: Vinyl molar ratio 1: 4). Due to the high molecular weight of hydrosilylated cis 1,4-polybutadiene, the conversion of 1,2-vinyl could not be clearly confirmed by FTIR.
Therefore, as a result of measuring the silicon content by IPC, it was 1900 ppm. The hydrosilylated cis 1,4-polybutadiene is partially crosslinked, bluish brown, and has a Mooney viscosity of 148.5. Table 1 shows the measured values.

  Next, examples of the rubber reinforcing agent-containing rubber composition according to the present invention will be described. The physical property values of the examples were measured as follows.

(Rubber microstructure)
The microstructure and 1,2-vinyl conversion were measured by measuring the FT-IR spectrum of Shimadzu-87000 manufactured by Shimadzu Corporation using a standard KBr film and the CS ₂ solution method. 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 above (Formula 2).

(Confirmation of existence of organic silyl group in hydrosilylated cis-1,4-polybutadiene)
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.

(Optimum vulcanization point)
The optimum vulcanization point was measured using a JSR curast meter in accordance with the JIS K-6300-2 standard at a measurement temperature of 150 ° C.

(Viscoelasticity measurement)
The dynamic temperature sweep analysis was performed using EPLEXOR 100N (manufactured by GABO, Germany) at a temperature of −125 to 105 ° C., a constant frequency of 10 Hz, 1.0% static strain and 0.3% dynamic strain. Made in

(Exothermic)
Measurement of heat generation and compression set is based on JIS K-6,265 standard and US standard ASTM D-623 (ISO 4,666 / 3: 1,982), using Goodrich Flexometer (manufactured by Ueshima Seisakusho). The test was carried out at a temperature of 100 ° C., a weight of 55 pounds, a 0.175 stroke, and a frequency of 1,800 times per minute.

(Fracture properties (tensile strength))
The tensile strength and tensile elongation in the fracture measurement were measured using a TENSILON RTG-1,310 tensiometer (manufactured by A & D) in accordance with JIS K-6,251.

(Image of silica dispersion)
Transmission electron microscope (TEM) analysis was performed under the conditions of a magnification of 20,000 to 100,000 with a voltage of 10 KV using H-7100FA manufactured by Hitachi, Ltd. Vulcanized samples were sliced using an Ultracut-S ultramicrotome manufactured by EM-Reichert.

(Abrasion resistance)
The abrasion resistance of the vulcanizate was measured according to JIS K6265 at a sliding speed of 20% and 60% using a lamborn abrasion measuring device.

  The molecular weight and molecular weight distribution measurement, Mooney viscosity measurement and Payne effect were measured in the same manner as the modified conjugated diene polymer.

Examples A to D and Comparative Examples A and B
By kneading in a laboratory plastic lab mill manufactured by Toyo Seiki with a start temperature of 90 ° C., an end temperature of 150 ° C., and a mixing time of within 5 minutes, natural rubber and commercial grade cis-1,4-polybutadiene ( A diene rubber component, UBEPOL BR150L), was blended with cis-1,4-polybutadiene (HSBR) that was first hydrosilylated. Precipitated silica (Nipsil VN3) was then added and blended with silane coupling agent (Si69) and pre-mix components silica, aroma oil, zinc oxide, stearic acid and antioxidant (6C). The first rubber composition obtained from the mixing process was stretched at a temperature of 30 to 60 ° C. using a 6-inch mixing roll. The sample was subjected to Payne effect analysis using Mooney viscosity measurement and RPA-2000 manufactured by Alpha Technologies. In the vulcanization preliminary process, the first rubber composition sheet obtained immediately is added with sulfur and a vulcanization accelerator (CZ and D) at a temperature of 30 to 60 ° C. using a 6-inch mixing roll. Further, the film was drawn into a sheet. The sample of the obtained second rubber composition was measured for the optimum vulcanization point using Payne effect analysis and a JSR curast meter using Mooney viscosity measurement and RPA-2,000 manufactured by Alpha Technologies. It was. The silica compounded rubber composition obtained from the vulcanization preliminary process was produced by a molding press at a temperature of 150 ° C. within the optimum vulcanization point observed by a curast meter, particularly in the range of 5 to 15 minutes. A rubber vulcanizate which is a sample of various forms in the present invention is a transmission electron microscope for measuring viscoelasticity, tensile strength, exothermic characteristics by temperature sweep, and dispersibility of precipitated silica in the rubber vulcanizate ( TEM) analysis was followed. The amount of each compound is shown in Table 2.

  Table 3 shows the physical property results of the vulcanized silica compound.

FIG. 1 shows an FTIR spectrum of cis 1,4-polybutadiene hydrosilylated with diethylaminodimethylsilane used in Example 2. C—N—C asymmetric stretching vibration based on a diethylamino group is observed as a wide and small peak at a wave number of 1180 to 1230 cm ⁻¹ .

As shown in FIG. 2, the hysteresis loss (tan δ) at 50 ° C. of the vulcanizates of Examples A to D is lower than that of Comparative Example 2, and the hysteresis loss tends to be proportional to the molecular weight (Mooney viscosity). That is, the higher the molecular weight (the higher the Mooney viscosity), the lower the hysteresis loss (tan δ).
Among the cis 1,4-polybutadiene hydrosilylated with diethylaminodimethylsilane, Example D, which has the highest molecular weight, has the lowest tan δ value of 8.1% compared to Comparative Example B.
On the other hand, the hysteresis loss (tan δ) of all vulcanizates in the glass transition state at −30 ° C. is 1.4 to 14% higher than that of Comparative Example B. It can also be seen that the wet skid resistance at ice and snow temperatures is improved.

From the value of compression set, it can be seen that the high molecular weight hydrosilylated cis 1,4-polybutadiene contributes to the improvement of the dimensional stability of the vulcanizate during the exothermic test by rotational compression vibration.
The higher the molecular weight of the hydrosilylated cis 1,4-polybutadiene, the more effective is to improve the dimensional stability of the vulcanizate.

It can be seen that the tensile modulus of 300% elongation of the entire vulcanizate is higher than that of Comparative Example B. Further, with respect to cis 1,4-polybutadiene hydrosilylated with diethylaminodimethylsilane (Examples A, C, and D), the higher the molecular weight (Moone viscosity), the higher the tensile elastic modulus at 300% elongation.
Also, as the amount of hydrosilylated cis 1,4-polybutadiene is increased from 20 to 30 parts (phr), the 300% tensile modulus (Examples A and B) increases.
The highest tensile modulus value of 300% was that of Comparative Example A. This is because bis (dimethylamino) methylsilane, which is a bifunctional aminosilane, exerts a strong interaction between aminosilyl groups.

The elongation at break of the vulcanizates modified with diethylaminodimethylsilane (Examples A to D) is slightly lower than the value of Comparative Example B. On the other hand, the elongation at break of the vulcanizate modified with bis (dimethylamino) methylsilane (Comparative Example A) is significantly reduced. This is because the elasticity of aminosilane introduced into the cis 1,4-polybutadiene molecular main chain is so strong that the elasticity is remarkably lost.

From Table 3, it can be seen that all the vulcanizates (Examples A to D and Comparative Example A) have improved wear resistance results on the basis of Comparative Example B.
As shown in FIG. 3, the higher the molecular weight (Moone viscosity) of the cis 1,4-polybutadiene hydrosilylated with diethylaminodimethylsilane (Examples A, C and D), the higher the wear resistance.
Example D, which has a high molecular weight (Mooney viscosity), has improved wear resistance by 25%, which is the most improved.

  FIGS. 4 and 5 show natural rubber (NR) / UBEPOL BR150L silica compounded rubber composition (Comparative Example B) and natural rubber (NR) / UBEPOL BR150L / cis 1,4-polybutadiene hydrosilylated with diethylaminodimethylsilane ( The transmission electron microscope (TEM) photograph of Example C) is shown.

Compared with FIG. 4, FIG. 5 shows that the continuous phase (dark part) of cis 1,4-polybutadiene is clearly larger and blended more uniformly with natural rubber (bright part). That is, it can be seen that the high molecular weight hydrosilylated cis 1,4-polybutadiene has an effect of making other rubber components more uniform in the rubber vulcanizate.
Silica agglomerates are still observed in the continuous phase of cis 1,4-polybutadiene, but the ratio is lower than that of Comparative Example B, and it can be said that the dispersibility of silica is improved.

FT-IR spectrum of diethylaminodimethylsilane modified cis-polybutadiene according to Example 2 Effect of Mooney Viscosity of Diethylaminodimethylsilane Modified Cis Polybutadiene on Tanδ (50 ° C) of Rubber Vulcanizates Effect of Mooney Viscosity of Diethylaminodimethylsilane Modified Cis Polybutadiene on Abrasion Resistance (60% Slip Rate) of Rubber Vulcanizates TEM image of Comparative Example B (NR / UBEPOL150L = 40: 60) TEM image of Example C (NR / UBEPOL150L / Example 2 = 40: 40: 20)

Claims (4)

Polybutadiene having a 1,4-cis structure of 80% or more and a 1,2-vinyl structure of 20 mol% or less is hydrosilylated with diethylaminodimethylsilane and has a Mooney viscosity (ML _{1 + 4} , 100 ° C.) of 80 to 130. A modified conjugated diene polymer.   The modified conjugated diene polymer according to claim 1, wherein the 1,4-cis structure is 80 to 95% and the 1,2-vinyl structure is 4 to 19 mol%.   The polybutadiene is produced by polymerization using a catalyst comprising a metallocene complex of a vanadium compound, an ionic compound of a non-coordinating anion and a cation, and an organometallic compound. Modified product of conjugated diene polymer. A step of polymerizing 1,3-butadiene in a non-aromatic hydrocarbon solvent using the catalyst, and a step of hydrosilylating the polymerized polybutadiene using diethylaminodimethylsilane without purifying the polymerized polybutadiene. The method for producing a modified conjugated diene polymer according to claim 3 .

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