JP2009215430A - Method for producing conjugated diene polymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a conjugated diene polymer having a high 1,4-cis structure content with an yttrium compound as a catalyst. <P>SOLUTION: The method for producing the conjugated diene polymer is characterized by polymerizing a conjugated diene compound with a catalyst obtained from (A) an yttrium compound, (B) an ionic compound comprising a non-coordinating anion and a cation, (C) an organometallic compound of an element selected from the groups 2, 12 and 13 of the periodic table, and (D) pyrrole. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

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

  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.

  Japanese Laid-Open Patent Publication No. 7-70143 (Patent Document 1) discloses an organometallic complex composed of yttrium (Y), neodymium (Nd) or praseodymium (Pr) and an organometallic compound of a group 13 element. However, no examples of polymerization are described for yttrium complexes.

  In JP-A-7-268013 (Patent Document 2), neodymium (Nd), praseodymium (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 praseodymium.

  Japanese Patent Laid-Open No. 2003-226721 (Patent Document 3) 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 praseodymium.

JP-A-7-70143 Japanese Patent Laid-Open No. 7-268013 JP 2003-226721 A

  The present invention provides a method for producing a conjugated diene polymer having a high 1,4-cis structure content using an yttrium compound as a catalyst.

  The present invention relates to (A) an yttrium compound, (B) an ionic compound comprising a non-coordinating anion and a cation, and (C) an organometallic element selected from Groups 2, 12 and 13 of the periodic table The present invention relates to a method for producing a conjugated diene polymer, characterized in that a conjugated diene compound is polymerized using a compound, (D) a catalyst obtained from pyrrole.

  In addition, the present invention relates to a method for producing the above conjugated diene polymer, wherein (A) the yttrium compound is an yttrium compound represented by the following general formula.

但し、Ｒ_１，Ｒ_２，Ｒ_３は水素、または炭素数１〜１２の置換基を表し、Ｏは酸素原子を表し、Ｙはイットリウム原子を表す。

_{However, R 1, R 2, R} 3 represents hydrogen, or a substituent having 1 to 12 carbon atoms, O represents an oxygen atom, Y represents yttrium atom.

  The present invention also relates to a method for producing a conjugated diene polymer, wherein (B) the non-coordinating anion is a boron-containing compound and the cation is a carbonium ion.

  Moreover, it is related with the manufacturing method of the conjugated diene polymer characterized by the (C) component being an organoaluminum compound.

  By using the catalyst of the present invention, a conjugated diene polymer having a high 1,4-cis structure content can be obtained.

  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 yttrium trichloride, yttrium tribromide, yttrium triiodide, yttrium nitrate, yttrium sulfate, yttrium trifluoromethanesulfonate, yttrium acetate, yttrium trifluoroacetate, yttrium malonate, octylic acid (ethylhexanoic acid) Yttrium salts such as yttrium, yttrium naphthenate, yttrium versatic acid, yttrium neodecanoate, alkoxides such as yttrium trimethoxide, yttrium triethoxide, yttrium triisopropoxide, yttrium tributoxide, yttrium triphenoxide, trisacetylacetonato Yttrium, Tris (hexane dionato) Yttrium, Tris (heptanedionato) Yttrium, Tris (di Organic yttrium compounds such as tilheptanedionato) yttrium, tris (tetramethylheptaneedionato) yttrium, trisacetoacetatoytrium, cyclopentadienyl yttrium dichloride, dicyclopentadienyl yttrium chloride, tricyclopentadienyl yttrium, Examples thereof include organic base complexes such as yttrium salt pyridine complex and yttrium salt picoline complex, yttrium salt hydrate, and yttrium salt alcohol complex.

  Moreover, the following yttrium compound can be used.

但し、Ｒ_１，Ｒ_２，Ｒ_３は水素、または炭素数１〜１２の置換基を表し、Ｏは酸素原子を表し、Ｙはイットリウム原子を表す。

_{However, R 1, R 2, R} 3 represents hydrogen, or a substituent having 1 to 12 carbon atoms, O represents an oxygen atom, Y represents yttrium atom.

Specific examples of R ₁ , R ₂ and R ₃ include hydrogen, methyl group, ethyl group, vinyl group, n-propyl group, isopropyl group, 1-propenyl group, allyl group, n-butyl group and s-butyl group. , 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-dimethyl Examples include propyl group, 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, a salt or complex of yttrium 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 (pentamethylheptanedionate) 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 and 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 (toluyl) 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.

  As a condensing agent, water is typically used, but in addition to this, any of the above-described trialkylaluminums that undergo a condensation reaction, for example, adsorbed water such as inorganic substances, diols, 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, And dialkylaluminum hydrides.

  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.

  The addition amount of pyrrole as the component (D) of the catalyst system in the present invention is preferably 0.05 to 1.0 mol, more preferably 0.1 to 0.9 mol, and still more preferably, with respect to 1 mol of yttrium. The amount is 0.2 to 0.85 mol, particularly preferably 0.3 to 0.8 mol.

  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.

  Molecular weight regulator (2) Metal hydride compounds include lithium hydride, sodium hydride, potassium hydride, magnesium hydride, calcium hydride, borane, aluminum hydride, gallium hydride, silane, germane, hydrogenated Examples thereof include lithium borohydride, sodium borohydride, lithium aluminum hydride, sodium aluminum hydride, and the like.

  Further, (3) hydrogenated organometallic compounds as molecular weight regulators include alkylboranes such as methylborane, ethylborane, propylborane, butylborane and phenylborane, dimethylborane, diethylborane, dipropylborane, dibutylborane and diphenylborane. Alkyl aluminum dihydrides such as dialkylborane, methylaluminum dihydride, ethylaluminum dihydride, propylaluminum dihydride, butylaluminum dihydride, phenylaluminum dihydride, dimethylaluminum hydride, diethylaluminum hydride, dipropylaluminum hydride, dibutylaluminum hydride Dialkylaluminum such as diphenylaluminum hydride Silanes such as muhydride, methylsilane, ethylsilane, propylsilane, butylsilane, phenylsilane, dimethylsilane, diethylsilane, dipropylsilane, dibutylsilane, diphenylsilane, trimethylsilane, triethylsilane, tripropylsilane, tributylsilane, triphenylsilane Class, 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, etc. 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, (D) component is added in the presence or absence of the conjugated diene compound monomer to be polymerized, and added in the order of (C) component, (A) component, and (B) component. To do.

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

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

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

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

  (6) 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), (B), and (D) are added in any order. Then, the above-described molecular weight regulator is added.

  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, 4-hexadiene and the like can be mentioned. Among these, a conjugated diene compound monomer mainly composed of 1,3-butadiene is preferable.

  These monomer components may be used alone 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) or solution polymerization using a conjugated diene compound monomer such as 1,3-butadiene as a polymerization solvent 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 0 to 100 ° C. The polymerization time is preferably in the range of 1 minute to 12 hours, particularly preferably 5 minutes to 5 hours.

  After performing the polymerization for a predetermined time, the inside of the polymerization tank is released as necessary, and post-treatment such as washing and drying steps is performed.

  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 higher the cis-1,4 structure content, the better the rubber properties such as rebound resilience, abrasion resistance and breaking strength.

  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 .

  Intrinsic viscosity ([η]) was measured at 30 ° C. using a toluene solution of the polymer.

Example 1
The inside of an autoclave with an internal volume of 1.5 L was purged with nitrogen, charged with a solution consisting of 390 ml of toluene and 210 ml of butadiene, and the temperature of the solution was 30 ° C., then 0.10 ml of a pyrrole toluene solution (0.2 mol / L) and 1.5 ml of a cyclohexane solution (2 mol / L) of triethylaluminum (TEA) was added and stirred for 3 minutes at 500 rpm. Next, 0.6 ml of a toluene solution (0.05 mol / L) of yttrium (III) tris (2,2,6,6-tetramethyl-3,5-heptanedioate) was added and heated to 40 ° C. did. After stirring for 2 minutes, 0.14 ml of a toluene solution (0.43 mol / L) of triphenylcarbenium tetrakis (pentafluorophenyl) borate was added to initiate polymerization. After polymerization at 40 ° C. for 25 minutes, 3 ml of an ethanol solution containing an antioxidant was added to stop 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 80 ° C. for 3 hours. The polymerization results are shown in Table 1.

(Example 2)
Polymerization was performed in the same manner as in Example 1 except that the amount of pyrrole in toluene (0.2 mol / L) added was 0.07 ml. The polymerization results are shown in Table 1.

(Comparative Example 1)
The inside of the autoclave with an internal volume of 1.5 L was purged with nitrogen, charged with a solution consisting of 390 ml of toluene and 210 ml of butadiene, the temperature of the solution was adjusted to 30 ° C., and a cyclohexane solution of triethylaluminum (TEA) (2 mol / L) 5 ml was added and stirred for 3 minutes at 500 rpm. Next, 0.6 ml of a toluene solution (0.05 mol / L) of yttrium (III) tris (2,2,6,6-tetramethyl-3,5-heptanedioate) was added and heated to 40 ° C. did. After stirring for 3 minutes, 0.14 ml of a toluene solution (0.43 mol / L) of triphenylcarbenium tetrakis (pentafluorophenyl) borate was added to initiate polymerization. After polymerization at 40 ° C. for 25 minutes, 3 ml of an ethanol solution containing an antioxidant was added to stop the polymerization. After the ethanol was added to the polymerization solution, the inside of the autoclave was released and polybutadiene was recovered. The recovered polybutadiene was then vacuum dried at 80 ° C. for 3 hours. The polymerization results are shown in Table 1.

Claims (4)

(A) an yttrium compound, (B) an ionic compound comprising a non-coordinating anion and a cation, (C) an organometallic compound of an element selected from Groups 2, 12 and 13 of the periodic table, and (D ) A method for producing a conjugated diene polymer, wherein a conjugated diene compound is polymerized using a catalyst obtained from pyrrole. (A) The method for producing a conjugated diene polymer according to claim 1, wherein the yttrium compound is an yttrium compound represented by the following general formula.

_{However, R 1, R 2, R} 3 represents hydrogen, or a substituent having 1 to 12 carbon atoms, O represents an oxygen atom, Y represents yttrium atom. (B) The method for producing a conjugated diene polymer according to claim 1 or 2, wherein the non-coordinating anion is a boron-containing compound and the cation is a carbonium ion. (C) A component is an organoaluminum compound, The manufacturing method of the conjugated diene polymer in any one of Claims 1-3 characterized by the above-mentioned.