JP4844111B2 - Process for producing modified conjugated diene polymer - Google Patents

Description

  The present invention relates to a method for modifying a conjugated diene polymer having a high cis 1,4-structure content, using a polymerization catalyst comprising an yttrium compound having a bulky ligand.

  Conventionally, as an automobile tire rubber, a rubber composition containing polybutadiene rubber (BR) or styrene-butadiene rubber (SBR) as a main component, and other natural rubber is used.

  In recent years, demands for lower fuel consumption of automobiles and driving safety requirements on snow and ice have increased, and automobile tire tread rubber has low rolling resistance (ie, high rebound resilience) and road surface grip on snow and ice (ie, Development of a rubber material having a large wet skid resistance) is desired. However, a rubber having high impact resilience such as polybutadiene rubber (BR) tends to have low wet skid resistance, whereas styrene-butadiene rubber (SBR) has high wet skid resistance but also high rolling resistance. was there.

  Conventionally, many methods for chemically modifying a low cisdiene rubber with a modifier in the presence of a lithium catalyst have been proposed as a method for solving the above problems. For example, a method of modifying low cis BR with a benzophenone compound has been proposed in Japanese Patent Application Laid-Open Nos. 58-162604 and 59-117514, and the rolling resistance of automobile tires is small and the wet skid resistance is large. It is also reported that the resilience is improved.

  Japanese Patent Publication No. 6-53766, Japanese Patent Publication No. 6-57769, and Japanese Patent Publication No. 6-78450 disclose diene rubbers having an active alkali metal terminal, such as nitroamino compounds, nitro compounds, nitroalkyl compounds, etc. It is described that a rubber having excellent impact resilience and low low-temperature hardness can be obtained by reacting with.

  However, low cis BR has insufficient wear resistance, and this problem cannot be solved even by modification. In addition, even the SBR has a low impact resilience, and even after modification, this defect cannot be sufficiently solved.

  Many proposals have been made on polymerization catalysts for conjugated dienes such as 1,3-butadiene and isoprene, some of which have been industrialized. For example, as a method for producing a conjugated diene polymer having a high cis-1,4 structure, a combination of a compound such as titanium, cobalt, nickel, neodymium and the like and organic aluminum is often used.

  Polymerization of conjugated dienes using a Group 3 element of the periodic table as a catalyst is known, and various polymerization methods have been proposed so far. For example, JP-A-6-228221 (Patent Document 1) discloses a support for (co) polymerization of a conjugated diene in which at least one compound of metals having an atomic number of 57 to 71 or 92 is supported on a support. A solid catalyst is disclosed. However, the yttrium catalyst having atomic number 39 is hardly described.

  JP-A-7-70143 (Patent Document 2) discloses an organometallic complex composed of an organometallic compound of a yttrium (Y), neodymium (Nd) or praseodymium (Pr) and a group 13 element. However, no examples of polymerization are described for yttrium complexes.

  In JP-A-7-268013 (Patent Document 3), neodymium (Nd), prazeodymium (Pr), dysprosium (Dy), lanthanum (La), gadolinium (Gd) and yttrium (Y) are substituted with aluminum alkyl and boron. Although a catalyst system combined with a trialkyl derivative is described, examples of a method for polymerizing 1,3-butadiene are limited to neodymium and prazeodymium.

  JP-A-8-325330 (patent document 4), JP-A-9-151219 (patent document 5), JP-A-10-60174 (patent document 6), JP-A-11-217465 (patent) Reference 7) and Japanese Patent Application Laid-Open No. 11-222536 (Patent Document 8) also mention yttrium as an example of a metal to be a catalyst for producing cis-1,4-polybutadiene. No specific examples are given.

  Japanese Patent Application Laid-Open No. 2003-226721 (Patent Document 9) discloses a method for producing cis-1,4-polybutadiene using a compound of an element selected from the group consisting of scandium, yttrium, lanthanoid, and actinoid as a catalyst. Although it is disclosed, a specific example using an yttrium catalyst is not given, and examples of a method for polymerizing 1,3-butadiene are limited to neodymium and prazeodymium.

JP-A-6-228221 JP-A-7-70143 Japanese Patent Laid-Open No. 7-268013 JP-A-8-325330 JP-A-9-151219 Japanese Patent Laid-Open No. 10-60174 JP-A-11-217465 JP-A-11-222536 JP 2003-226721 A

  (A) Yttrium compound having a bulky ligand represented by the following general formula, (B) an ionic compound comprising a non-coordinating anion and a cation, (C) Groups 2 and 12 of the periodic table Conjugated diene polymer modification characterized by polymerizing a conjugated diene compound using a catalyst obtained from an organometallic compound of an element selected from Group 13, and further modifying with a silicon compound having an amino group and an alkoxy group The present invention relates to a method for manufacturing a product.

但し、Ｒ１，Ｒ２，Ｒ３は水素、または炭素数１〜１２の炭化水素基を表し、Ｏは酸素原子を表し、Ｙはイットリウム原子を表す。

However, R1, R2, R3 represents hydrogen or a C1-C12 hydrocarbon group, O represents an oxygen atom, and Y represents an yttrium atom.

Conjugation characterized by adjusting molecular weight with a compound selected from (1) hydrogen, (2) metal hydride compound, and (3) hydrogenated organometallic compound when polymerizing a conjugated diene compound by the above method. The present invention relates to a method for producing a modified product comprising a diene polymer.

At least one of the organometallic compound of component (C) and the hydrogenated organometallic compound according to claim 2 is a dialkylaluminum hydride. .

The conjugated diene polymer is a cis-1,4-polybutadiene having 90% or more of a cis-1,4 structure.

  (A) an yttrium compound having a specific bulky ligand, (B) an ionic compound composed of a non-coordinating anion and a cation, (C) selected from Groups 2, 12, and 13 of the periodic table A conjugated diene compound is polymerized using a catalyst obtained from an organometallic compound of an element, and the molecular weight is adjusted with a compound selected from (1) hydrogen, (2) a hydrogenated metal compound, and (3) a hydrogenated organometallic compound. There is provided a method of modifying cis-1,4-polybutadiene having 90% or more of the cis-1,4 structure obtained by using a silicon compound having an amino group and an alkoxy group.

  The yttrium compound which is the component (A) of the catalyst system of the present invention is an yttrium compound having a bulky ligand represented by the following general formula.

但し、Ｒ１，Ｒ２，Ｒ３は水素、または炭素数１〜１２の炭化水素基を表し、Ｏは酸素原子を表し、Ｙはイットリウム原子を表す。

However, R1, R2, R3 represents hydrogen or a C1-C12 hydrocarbon group, O represents an oxygen atom, and Y represents an yttrium atom.

  Specific examples of R1, R2, and R3 include hydrogen, methyl group, ethyl group, vinyl group, n-propyl group, isopropyl group, 1-propenyl group, allyl group, n-butyl group, s-butyl group, and isobutyl group. T-butyl group, n-pentyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, 2,2-dimethylpropyl group, Examples include hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, cyclohexyl group, methylcyclohexyl group, ethylcyclohexyl group, phenyl group, benzyl group, toluyl group, and phenethyl group. Further, those in which a hydroxyl group, a carboxyl group, a carbomethoxy group, a carboethoxy group, an amide group, an amino group, an alkoxy group, a phenoxy group and the like are substituted at an arbitrary position are also included.

  As the yttrium compound which is the component (A) of the catalyst system of the present invention, an yttrium salt or complex is preferably used. Particularly preferred are tris (acetylacetonato) yttrium, tris (hexanedionato) yttrium, tris (heptanedionato) yttrium, tris (dimethylheptanedionato) yttrium, tris (trimethylheptanedionato) yttrium, tris (tetramethylheptane) Diato) yttrium, tris (pentamethylheptanedionat) yttrium, yttrium compounds such as tris (hexamethylheptanedionate) yttrium, trisacetoacetatoyttrium, and the like.

  In the ionic compound comprising a non-coordinating anion and a cation as the component (B) of the catalyst system of the present invention, examples of the non-coordinating anion include tetra (phenyl) borate, tetra (fluorophenyl) Borate, tetrakis (difluorophenyl) borate, tetrakis (trifluorophenyl) borate, tetrakis (tetrafluorophenyl) borate, tetrakis (pentafluorophenyl) borate, tetrakis (3,5-bistri Fluoromethylphenyl) borate, tetrakis (tetrafluoromethylphenyl) borate, tetra (triyl) borate, tetra (xylyl) borate, triphenyl (pentafluorophenyl) borate, tris (pentafluoro) Phenyl) (phenyl) borate, tridecahydride-7, - radical Bowne deca borate - DOO, tetrafluoroborate - DOO, hexafluorophosphate - such DOO and the like.

  On the other hand, examples of the cation include a carbonium cation, an oxonium cation, an ammonium cation, a phosphonium cation, a cycloheptatrienyl cation, and a ferrocenium cation.

  Specific examples of the carbonium cation include tri-substituted carbonium cations such as a triphenyl carbonium cation and a tri-substituted phenyl carbonium cation. Specific examples of the tri-substituted phenylcarbonium cation include tri (methylphenyl) carbonium cation and tri (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 (i-propyl) ammonium cation, dicyclohexylammonium cation and other dialkylammonium cations Mention may be made of cations.

  Specific examples of phosphonium cations include triphenylphosphonium cation, tetraphenylphosphonium cation, tri (methylphenyl) phosphonium cation, tetra (methylphenyl) phosphonium cation, tri (dimethylphenyl) phosphonium cation, tetra (dimethylphenyl) phosphonium cation, etc. Of arylphosphonium cations.

  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.

Moreover, you may use an alumoxane as (B) 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 is preferable. Examples of the organoaluminum compound used as an aluminoxane raw material include trialkylaluminums such as trimethylaluminum, triethylaluminum, and triisobutylaluminum, and mixtures thereof.

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

  Moreover, as a condensing agent, water can be mentioned as a typical example, but in addition to this, an arbitrary one that the trialkylaluminum undergoes a condensation reaction, for example, adsorbed water such as an inorganic substance, a diol, and the like.

  Examples of organometallic compounds of Group 2, 12 and 13 of the periodic table that are the component (C) of the catalyst system in the present invention include organic magnesium, organic zinc, and organic aluminum. Preferred among these compounds are dialkyl magnesium, alkyl magnesium chloride, alkyl magnesium bromide, dialkyl zinc, trialkyl aluminum, dialkyl aluminum chloride, dialkyl aluminum bromide, alkyl aluminum sesquichloride, alkyl aluminum sesquibromide, alkyl aluminum dichloride, Dialkylaluminum hydride and the like.

  Specific compounds include alkyl magnesium halides such as methyl magnesium chloride, ethyl magnesium chloride, butyl magnesium chloride, hexyl magnesium chloride, octyl magnesium chloride, ethyl magnesium bromide, butyl magnesium bromide, butyl magnesium iodide, and hexyl magnesium iodide. Can be mentioned.

  Furthermore, dialkyl magnesium such as dimethylmagnesium, diethylmagnesium, dibutylmagnesium, dihexylmagnesium, dioctylmagnesium, ethylbutylmagnesium, and ethylhexylmagnesium can be exemplified.

  Furthermore, trialkyl zinc such as dimethyl zinc, diethyl zinc, diisobutyl zinc, dihexyl zinc, dioctyl zinc, didecyl zinc and the like can be mentioned.

  Furthermore, trialkylaluminums such as trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, and the like can be given.

  In addition, dialkylaluminum chlorides such as dimethylaluminum chloride and diethylaluminum chloride, organoaluminum halogen compounds such as ethylaluminum sesquichloride and ethylaluminum dichloride, and hydrogenated organoaluminum compounds such as diethylaluminum hydride, diisobutylaluminum hydride and ethylaluminum sesquihydride. Can be mentioned.

  These organometallic compounds of Groups 2, 12, and 13 of the periodic table can be used alone or in combination of two or more.

  Although the conjugated diene can be polymerized using the above-mentioned catalyst, (1) hydrogen, (2) metal hydride compound, and (3) hydrogenated organometal as the molecular weight regulator of the resulting conjugated diene polymer. A compound selected from compounds can be used.

  Examples of the molecular weight regulator (2) metal hydride compound in the present invention include lithium hydride, sodium hydride, potassium hydride, magnesium hydride, calcium hydride, borane, aluminum hydride, gallium hydride, silane, and germane. , Lithium borohydride, sodium borohydride, lithium aluminum hydride, sodium aluminum hydride, and the like.

  In addition, (3) hydrogenated organometallic compounds as molecular weight regulators in the present invention include alkylboranes such as methylborane, ethylborane, propylborane, butylborane, and phenylborane, dimethylborane, diethylborane, dipropylborane, dibutylborane, and diphenyl. Dialkylborane such as borane, methylaluminum dihydride, ethylaluminum dihydride, propylaluminum dihydride, butylaluminum dihydride, phenylaluminum dihydride, etc., alkylaluminum dihydride, dimethylaluminum hydride, diethylaluminum hydride, dipropylaluminum hydride, Dia such as dibutylaluminum hydride and diphenylaluminum hydride Kill aluminum hydride, methylsilane, ethylsilane, propylsilane, butylsilane, phenylsilane, dimethylsilane, diethylsilane, dipropylsilane, dibutylsilane, diphenylsilane, trimethylsilane, triethylsilane, tripropylsilane, tributylsilane, triphenylsilane, etc. Silanes, methyl germane, ethyl germane, propyl germane, butyl germane, phenyl germane, dimethyl germane, diethyl germane, dipropyl germane, dibutyl germane, diphenyl germane, trimethyl germane, triethyl germane, tripropyl germane, tributyl germane, triphenyl germane And germanes.

  Among these, diisobutylaluminum hydride and diethylaluminum hydride are preferable, and diethylaluminum hydride is particularly preferable.

  The order of addition of the catalyst components is not particularly limited, but can be performed, for example, in the following order.

  (1) In an inert organic solvent, the component (C) is added in the presence or absence of the conjugated diene compound monomer to be polymerized, and the components (A) and (B) are added in any order.

  (2) In the inert organic solvent, the component (C) is added in the presence or absence of the conjugated diene compound monomer to be polymerized, the molecular weight regulator is added, and then the components (A) and (B ) Add ingredients in any order.

  (3) After adding the component (A) in the presence or absence of the conjugated diene compound monomer to be polymerized in an inert organic solvent, and adding the component (C) and the molecular weight regulator described above in any order. , (B) component is added.

  (4) After adding the component (B) in the presence or absence of the conjugated diene compound monomer to be polymerized in an inert organic solvent, and adding the component (C) and the molecular weight regulator described above in any order. , (A) component is added.

  (5) After adding component (C) in the presence or absence of a conjugated diene compound monomer to be polymerized in an inert organic solvent, and adding components (A) and (B) in any order Add the above-described molecular weight regulator.

  Moreover, you may age | cure and use each component previously. Especially, it is preferable to age | cure (A) component and (C) component.

  As aging conditions, the component (A) and the component (C) are mixed in an inert solvent in the presence or absence of the conjugated diene compound monomer to be polymerized. The aging temperature is -50 to 80 ° C, preferably -10 to 50 ° C, and the aging time is 0.01 to 24 hours, preferably 0.05 to 5 hours, particularly preferably 0.1 to 1 hour.

  In the present invention, each catalyst component may be supported on an inorganic compound or an organic polymer compound.

  Conjugated diene compound monomers include 1,3-butadiene, isoprene, 1,3-pentadiene, 2-ethyl-1,3-butadiene, 2,3-dimethylbutadiene, 2-methylpentadiene, 4-methylpentadiene, 2 1, 4-hexadiene and the like. Among them, a conjugated diene compound monomer mainly composed of 1,3-butadiene is preferable.

  These monomer components may be used singly or in combination of two or more.

  Here, the conjugated diene compound monomer to be polymerized may be the total amount or a part of the monomer. In the case of part of the monomer, the above contact mixture can be mixed with the remaining monomer or the remaining monomer solution. In addition to conjugated dienes, olefins such as ethylene, propylene, allene, 1-butene, 2-butene, 1,2-butadiene, pentene, cyclopentene, hexene, cyclohexene, octene, cyclooctadiene, cyclododecatriene, norbornene, norbornadiene, etc. A compound or the like may be contained.

  The polymerization method is not particularly limited, and bulk polymerization (bulk polymerization) using a conjugated diene compound monomer such as 1,3-butadiene itself as a polymerization solvent, or solution polymerization can be applied. Solvents for solution polymerization include aliphatic hydrocarbons such as butane, pentane, hexane, and heptane, alicyclic hydrocarbons such as cyclopentane and cyclohexane, aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene, Examples thereof include olefinic hydrocarbons such as olefin compounds and cis-2-butene and trans-2-butene.

  Among these, benzene, toluene, cyclohexane, or a mixture of cis-2-butene and trans-2-butene is preferably used.

  The polymerization temperature is preferably in the range of -30 to 150 ° C, particularly preferably in the range of 30 to 100 ° C. The polymerization time is preferably in the range of 1 minute to 12 hours, particularly preferably 5 minutes to 5 hours.

  The conjugated diene polymer obtained in the present invention is preferably cis-1,4-polybutadiene having a cis-1,4 structure of 90% or more, more preferably 92% or more, particularly preferably 96% or more. . [Η] of the conjugated diene polymer is preferably 0.1 to 10, more preferably 1 to 7, and particularly preferably 1.5 to 5.

  The modifier used in the present invention has an amino group (preferably an aminoalkyl group bonded to an alkyl group having 1 to 6 carbon atoms) and an alkoxy group (preferably an alkoxy group having 1 to 6 carbon atoms). A silicon compound (preferably a silane compound), and an aminoalkylalkoxysilane compound is preferable. Examples of specific compounds include 3-aminopropyldimethylmethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylethyldimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyldimethylethoxysilane, 3 -Aminopropylmethyldiethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldimethylbutoxysilane, 3-aminopropylmethyldibutoxysilane, 3- (2-aminoethylaminopropyl) dimethoxymethylsilane, 3- ( 2-aminoethylaminopropyl) dimethoxyethylsilane, 3- (2-aminoethylaminopropyl) dimethoxypropylsilane, 3- (2-aminoethylaminopropyl) dimethoxybutylsilane, 3- (2-amino Tilaminopropyl) diethoxymethylsilane, 3- (2-aminoethylaminopropyl) trimethoxysilane, 3- (2-aminoethylaminopropyl) triethoxysilane, 3- (2-aminoethylaminopropyl) tributoxysilane Etc. Among these compounds, 3-aminopropyltrimethoxysilane, 3- (2-aminoethylaminopropyl) dimethoxymethylsilane, and 3- (2-aminoethylaminopropyl) trimethoxysilane are particularly preferable. These modifiers may be used alone or in combination of two or more.

  When the modification reaction rate is slow, aluminum halide or alkyl halide can be used as a catalyst in order to increase the reaction rate. Examples of the aluminum halide include aluminum chloride, aluminum bromide, and aluminum iodide. Examples of the alkyl halide include alkyl halides having 1 to 6 carbon atoms such as ethyl bromide, ethyl iodide, butyl chloride, butyl bromide, butyl iodide and the like.

  The organic solvent used for the modification reaction can be freely used as long as it does not react with the diene rubber. Usually, the same solvent as used for the production of the diene rubber is used. Specific examples thereof include aromatic hydrocarbon solvents such as benzene, chlorobenzene, toluene and xylene, and aliphatic carbonization of 5 to 10 carbon atoms such as n-heptane, n-hexane, n-pentane and n-octane. Examples thereof include hydrogen solvents, cycloaliphatic hydrocarbon solvents such as cyclohexane, methylcyclohexane, tetralin, and decalin. Further, methylene chloride, tetrahydrofuran and the like can also be used.

  The temperature of the reaction solution for the modification reaction is preferably in the range of 0 to 100 ° C, and particularly preferably in the range of room temperature to 80 ° C. If the temperature is too low, the modification reaction proceeds slowly, and if the temperature is too high, the polymer is easily gelled. The time for the denaturation reaction is not particularly limited, but it is usually preferably in the range of 10 minutes to 6 hours. If the modification reaction time is too short, the reaction does not proceed sufficiently, and if the time is too long, the polymer tends to gel.

  The amount of the diene rubber in the modification reaction solution is usually in the range of 5 to 500 g, preferably 20 to 300 g, more preferably 30 to 200 g per liter of the solvent.

  The amount of the modifier used in the modification reaction is usually in the range of 0.01 to 150 mmol, preferably 0.1 to 100 mmol, more preferably 0.5 to 50 mmol with respect to 100 g of the diene rubber. If the amount used is too small, the amount of silicon element introduced into the modified diene rubber will be small, and the modification effect will be small. If the amount used is too large, unreacted modifier remains in the modified diene rubber, which is not preferable because it takes time to remove it.

  In carrying out the modification reaction, it is preferable to use a catalyst depending on the type of the modifying agent. The amount of the catalyst used in this reaction is usually 0.01 to 100 mmol, preferably 0.05 to 50 mmol, more preferably 0.08 to 20 mmol, with respect to 100 g of the diene rubber.

  The modified conjugated diene polymer of the present invention is blended alone or blended with other synthetic rubber or natural rubber, and if necessary, is oil-extended with a process oil, and then a filler such as carbon black, a vulcanizing agent, Vulcanization accelerators and other ordinary compounding agents are added to vulcanize and used for rubber applications that require mechanical properties and wear resistance such as tires, hoses, belts, and other various industrial products. It can also be used as a modifier for plastic materials.

  Examples according to the present invention will be specifically described below. The polymerization conditions and polymerization results are summarized in Table 1.

  The microstructure was performed by infrared absorption spectrum analysis. The microstructure was calculated from the absorption intensity ratio of cis 740 cm-1, trans 967 cm-1, and vinyl 910 cm-1.

Mooney viscosity (ML _{1 + 4} , 100 ° C.): After preheating at 100 ° C. for 1 minute using a Mooney viscometer manufactured by Shimadzu Corporation according to JIS-K6300, the Mooney viscosity of the rubber (ML _{1 + 4} , 100 ° C.).

  Silicon content: BR was sulfated and ashed, melted with alkali, dissolved by heating with nitric acid, diluted with ultrapure water, and quantitatively analyzed by ICP emission spectrometry.

Example 1
The inside of the autoclave with an internal volume of 2 L was purged with nitrogen, charged with a solution consisting of 260 ml of toluene and 140 ml of butadiene, the temperature of the solution was adjusted to 30 ° C., and then 3 ml of a toluene solution (1 mol / L) of triethylaluminum (TEA) was added. The mixture was stirred for 3 minutes at 550 rpm. Next, 1 ml of a toluene solution (20 mmol / L) of tris (2,2,6,6-tetramethylheptane-3,5-dionato) yttrium was added and heated to 40 ° C. After stirring for 4 minutes, 0.1 ml of a toluene solution (0.43 mol / L) of triphenylcarbenium tetrakispentafluorophenylborate was added to initiate polymerization. After polymerization at 40 ° C. for 30 minutes, 2.9 ml of a modifying agent, 3- (2-aminoethylaminopropyl) trimethoxysilane, in toluene (0.1 mol / L) was added and the modification reaction was performed at 40 ° C. for 10 minutes. It was. The reaction was stopped by adding 5 ml of an ethanol / heptane (1/1) solution containing an antioxidant. After releasing the pressure inside the autoclave, the polymerization solution was put into ethanol to recover polybutadiene. The recovered polybutadiene was then vacuum-dried at 70 ° C. for 6 hours to obtain modified polybutadiene.

  5 g of modified polybutadiene was dissolved in 100 ml of toluene, and then 200 ml of ethanol was added to reprecipitate polybutadiene. After repeating this operation twice, an anti-aging agent was added and dried at 70 ° C. for 2 hours to obtain polybutadiene for measuring silicon content. The results are shown in Table 1.

(Example 2)
The inside of the autoclave having an internal volume of 2 L was purged with nitrogen, charged with a solution consisting of 260 ml of toluene and 140 ml of butadiene, the temperature of the solution was adjusted to 30 ° C., and 1.6 ml of a toluene solution of diethylaluminum hydride (DEAH) (1 mol / L) And stirred for 3 minutes at 550 rpm. Next, 2 ml of a toluene solution (20 mmol / L) of tris (2,2,6,6-tetramethylheptane-3,5-dionato) yttrium was added and heated to 40 ° C. After stirring for 4 minutes, 0.2 ml of a toluene solution (0.43 mol / L) of triphenylcarbenium tetrakispentafluoroborate was added to initiate polymerization. After polymerization at 40 ° C. for 30 minutes, 0.6 ml of a modifying agent, 3- (2-aminoethylaminopropyl) trimethoxysilane, in toluene (1 mol / L) was added, and the modification reaction was carried out at 40 ° C. for 10 minutes. The reaction was stopped by adding 5 ml of an ethanol / heptane (1/1) solution containing an antioxidant. After releasing the pressure inside the autoclave, the polymerization solution was put into ethanol to recover polybutadiene. The recovered polybutadiene was then vacuum-dried at 70 ° C. for 6 hours to obtain modified polybutadiene.

  5 g of modified polybutadiene was dissolved in 100 ml of toluene, and then 200 ml of ethanol was added to reprecipitate polybutadiene. After repeating this operation twice, an anti-aging agent was added and dried at 70 ° C. for 2 hours to obtain polybutadiene for measuring silicon content. The results are shown in Table 1.

(Example 3)
Polymerization was conducted in the same manner as in Example 2 except that the amount of 3- (2-aminoethylaminopropyl) trimethoxysilane in toluene (1 mol / L) added was 1.2 ml. The results are shown in Table 1.

Example 4
The same procedure as in Example 2 was carried out except that the amount of 3- (2-aminoethylaminopropyl) trimethoxysilane in toluene (1 mol / L) added was 1.2 ml and the denaturation reaction was carried out at 40 ° C. for 30 minutes. . The results are shown in Table 1.

( Reference Example 1 )
The inside of the autoclave with an internal volume of 2 L was purged with nitrogen, charged with a solution consisting of 260 ml of toluene and 140 ml of butadiene, the temperature of the solution was adjusted to 30 ° C., and then 3 ml of a toluene solution (1 mol / L) of triethylaluminum (TEA) was added. The mixture was stirred for 3 minutes at 550 rpm. Next, 1 ml of a toluene solution (20 mmol / L) of tris (2,2,6,6-tetramethylheptane-3,5-dionato) yttrium was added and heated to 40 ° C. After stirring for 4 minutes, 0.1 ml of a toluene solution (0.43 mol / L) of triphenylcarbenium tetrakispentafluorophenylborate was added to initiate polymerization. After polymerization at 40 ° C. for 30 minutes, 5 ml of an ethanol / heptane (1/1) solution containing an antiaging agent was added to terminate the polymerization. After releasing the pressure inside the autoclave, the polymerization solution was put into ethanol to recover polybutadiene. The recovered polybutadiene was then vacuum-dried at 70 ° C. for 6 hours to obtain unmodified polybutadiene. The results are shown in Table 1.

( Reference Example 2 )
The inside of the autoclave having an internal volume of 2 L was purged with nitrogen, charged with a solution consisting of 260 ml of toluene and 140 ml of butadiene, the temperature of the solution was adjusted to 30 ° C., and then a toluene solution of diethylaluminum hydride (DEAH) (1 mol / L) 1.6 ml And stirred for 3 minutes at 550 rpm. Next, 2 ml of a toluene solution (20 mmol / L) of tris (2,2,6,6-tetramethylheptane-3,5-dionato) yttrium was added and heated to 40 ° C. After stirring for 4 minutes, 0.2 ml of a toluene solution (0.43 mol / L) of triphenylcarbenium tetrakispentafluoroborate was added to initiate polymerization. After polymerization at 40 ° C. for 30 minutes, 5 ml of an ethanol / heptane (1/1) solution containing an antiaging agent was added to terminate the polymerization. After releasing the pressure inside the autoclave, the polymerization solution was put into ethanol to recover polybutadiene. The recovered polybutadiene was then vacuum-dried at 70 ° C. for 6 hours to obtain unmodified polybutadiene. The results are shown in Table 1.

(Comparative Example 1)
The inside of the autoclave having an internal volume of 2 L was purged with nitrogen, and a solution consisting of 650 ml of cyclohexane and 350 ml of butadiene was charged. In a 50 ml flask purged with nitrogen, 8 ml of cyclohexane solution (1 mol / L) of diisobutylaluminum hydride (DIBAH), 0.32 ml of cyclohexane solution of butadiene (0.78 mol / L), neodymium versatate [Nd (ver) ₃ ] 0.5 ml of a cyclohexane solution (0.1 mol / L) was added and stirred for 2 minutes, then 0.33 ml of a cyclohexane solution (0.3 mol / L) of diethylaluminum chloride (DEAC) was added and stirred at 30 ° C. for 30 minutes.
After the autoclave was heated to 80 ° C., the entire amount of the catalyst solution was injected to initiate polymerization. After polymerization at 80 ° C. for 60 minutes, 1 ml of cyclohexane solution (1 mol / L) of 3- (2-aminoethylaminopropyl) trimethoxysilane as a modifying agent was added, and a modification reaction was performed at 80 ° C. for 30 minutes. The reaction was stopped by adding 5 ml of an ethanol / heptane (1/1) solution containing an antioxidant. After releasing the pressure inside the autoclave, the polymerization solution was put into ethanol to recover polybutadiene. The recovered polybutadiene was then vacuum-dried at 70 ° C. for 6 hours to obtain modified polybutadiene.

  5 g of modified polybutadiene was dissolved in 100 ml of toluene, and then 200 ml of methanol was added to reprecipitate polybutadiene. After repeating this operation twice, an anti-aging agent was added and dried at 70 ° C. for 2 hours to obtain polybutadiene for measuring silicon content. The results are shown in Table 1.

(Comparative Example 2)
The inside of the autoclave having an internal volume of 2 L was purged with nitrogen, and a solution consisting of 650 ml of cyclohexane and 350 ml of butadiene was charged. In a 50 ml flask purged with nitrogen, 8 ml of cyclohexane solution (1 mol / L) of diisobutylaluminum hydride (DIBAH), 0.32 ml of cyclohexane solution of butadiene (0.78 mol / L), neodymium versatate [Nd (ver) ₃ ] 0.5 ml of a cyclohexane solution (0.1 mol / L) was added and stirred for 2 minutes, then 0.33 ml of a cyclohexane solution (0.3 mol / L) of diethylaluminum chloride (DEAC) was added and stirred at 30 ° C. for 30 minutes.
After the autoclave was heated to 80 ° C., the entire amount of the catalyst solution was injected to initiate polymerization. After polymerization at 80 ° C. for 60 minutes, 5 ml of an ethanol / heptane (1/1) solution containing an antiaging agent was added to stop the reaction. After releasing the pressure inside the autoclave, the polymerization solution was put into ethanol to recover polybutadiene. The recovered polybutadiene was then vacuum dried at 70 ° C. for 6 hours to obtain unmodified polybutadiene. The results are shown in Table 1.

Claims (4)

(A) Yttrium compound having a bulky ligand represented by the following general formula, (B) an ionic compound comprising a non-coordinating anion and a cation, (C) Groups 2 and 12 of the periodic table Conjugated diene polymer modification characterized by polymerizing a conjugated diene compound using a catalyst obtained from an organometallic compound of an element selected from Group 13, and further modifying with a silicon compound having an amino group and an alkoxy group Manufacturing method.

However, R1, R2, R3 represents hydrogen or a C1-C12 hydrocarbon group, O represents an oxygen atom, and Y represents an yttrium atom. When polymerizing a conjugated diene compound by the method according to claim 1, the molecular weight is adjusted with a compound selected from (1) hydrogen, (2) a metal hydride compound, and (3) a hydrogenated organometallic compound. A method for producing a modified product comprising a conjugated diene polymer. The conjugate according to any one of claims 1 to 2 , wherein at least one of the organometallic compound of component (C) in claim 1 and the hydrogenated organometallic compound in claim 2 is a dialkylaluminum hydride. A method for producing a modified product comprising a diene polymer. The conjugated diene polymer modified product according to any one of claims 1 to 3 , wherein the conjugated diene polymer is cis-1,4-polybutadiene having a cis-1,4 structure of 90% or more. Production method.