JP2007161918A - Method for producing conjugated diene polymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a conjugated diene polymer, by which the conjugated diene polymer having a high cis-1,4-structure content is produced in the presence of a polymerization catalyst comprising a yttrium compound having a bulky ligand have not been mentioned in previous examples among conjugated diene polymerization catalysts containing the group 3 elements in the periodic table. <P>SOLUTION: This method for producing the conjugated diene polymer is characterized by polymerizing a conjugated diene compound in the presence of a catalyst obtained from (A) an yttrium compound having a bulky ligand, (B) an ionic compound comprising a non-coordinating anion and a cation, and (C) an organic metal compound of an element selected from the group 2, 12, and 13 elements in the periodic table. <P>COPYRIGHT: (C)2007,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 having a bulky ligand.

  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 yttrium (Y), neodymium (N
An organometallic complex composed of d) or praseodymium (Pr) and an organometallic compound of a group 13 element is disclosed. 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 (1), (B) an ionic compound comprising a non-coordinating anion and a cation, (C) Group 2 of the periodic table The present invention relates to a method for producing a conjugated diene polymer, wherein a conjugated diene compound is polymerized using a catalyst obtained from an organometallic compound of an element selected from Group 12 and Group 13.

但し、Ｅは窒素またはリン原子を表し、Ｚ¹，Ｚ²は炭素またはケイ素原子を表し、Ｒ¹，Ｒ²，Ｒ³，Ｒ⁴，Ｒ⁵，Ｒ⁶は水素、または炭素数１〜１２の置換基を表し、Ｙはイットリウム原子を表す。

However, E is represents a nitrogen or phosphorus atom, Z ^1, Z ² represents a carbon or silicon ^{atom, R 1, R 2, R} 3, R 4, R 5, R 6 is hydrogen or 1 to 12 carbon atoms, And Y represents an yttrium atom.

The present invention relates to a method for producing the above conjugated diene polymer, wherein the molecular weight is adjusted with a compound selected from (1) hydrogen, (2) a metal hydride compound, and (3) a hydrogenated organometallic compound.

(1) It relates to a method for producing the above conjugated diene polymer, wherein E in the formula is a nitrogen atom.

The conjugated diene polymer is polybutadiene or polyisoprene, and relates to a method for producing the conjugated diene polymer.

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) a group 2 or 12 or 13 in the periodic table Provided is a method for producing a conjugated diene polymer, wherein a conjugated diene compound is polymerized using a catalyst obtained from an organometallic compound of an element.

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、Ｅは窒素またはリン原子を表し、Ｚ¹，Ｚ²は炭素またはケイ素原子を表し、Ｒ¹，Ｒ²，Ｒ³，Ｒ⁴，Ｒ⁵，Ｒ⁶は水素、または炭素数１〜１２の置換基を表し、Ｙはイットリウム原子を表す。

However, E is represents a nitrogen or phosphorus atom, Z ^1, Z ² represents a carbon or silicon ^{atom, R 1, R 2, R} 3, R 4, R 5, R 6 is hydrogen or 1 to 12 carbon atoms, And Y represents an yttrium atom.

Specific examples of R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ include hydrogen, methyl group, ethyl group, vinyl group, n-propyl group, isopropyl group, 1-propenyl group, allyl group, n-butyl group, 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-dimethylpropyl 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, A toluyl group, a phenethyl group, etc. are mentioned. 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 [N, N-bis (trimethylsilyl) amido] yttrium, tris [N, N-bis (triethylsilyl) amido] yttrium, tris [N, N-bis (dimethylphenylsilyl) amido] yttrium, And yttrium compounds such as tris [N, N-bis (t-butyl) amido] yttrium and tris [N, N-bis (dimethylphenylmethyl) amido] yttrium.

  In the ionic compound comprising a non-coordinating anion and a cation that is 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-bistrifluoromethylphenyl) borate, tetrakis (tetrafluoromethylphenyl) ) Borate, tetra (triyl) borate, tetra (xylyl) borate, triphenyl (pentafluorophenyl) borate, tris (pentafluorophenyl) (phenyl) borate, tridecahydride-7, - dicarbaundecaborate Bowne deca borate, tetrafluoroborate, hexafluorophosphate 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 them, as the ionic compound, triphenylcarbonium tetrakis (pentafluorophenyl) borate, triphenylcarbonium tetrakis (fluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, 1, 1′-dimethylferrocenium tetrakis (pentafluorophenyl) borate and the like are preferable. 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 is typically used, but in addition to this, any agent that undergoes a condensation reaction of the trialkylaluminum, for example, adsorbed water such as an inorganic substance, diol, and the like can be used.

  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.

  Furthermore, 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 an inert organic solvent, the component (C) 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, the component (A) and the component (B) Add ingredients in any order.

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

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

  (5) 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. Add molecular weight regulator as described above.

  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 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 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.

  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.

  Examples according to the present invention will be specifically described below. The polymerization conditions and polymerization results are summarized in Tables 1-2.

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 .

  The molecular weight and molecular weight distribution were evaluated by the weight average molecular weight Mw determined from GPC using polystyrene as a standard substance, and the ratio Mw / Mn of Mw and number average molecular weight Mn.

Example 1
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 2 ml of a toluene solution (1 mol / L) of triethylaluminum (TEA) was added. The mixture was stirred at 500 rpm for 3 minutes. Next, 1 ml of a toluene solution (20 mmol / L) of tris [N, N-bis (trimethylsilyl) amido] yttrium was added and heated to 40 ° C. After stirring for 4 minutes, 0.1 ml of a toluene solution (0.4 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. The polymerization conditions are shown in Table 1, and the polymerization results are shown in Table 2.

(Example 2)
Polymerization was carried out in the same manner as in Example 1 except that the toluene solution (1 mol / L) of triethylaluminum (TEA) was changed to a toluene solution (1 mol / L) of diethylaluminum hydride (DEAH). The polymerization conditions are shown in Table 1, and the polymerization results are shown in Table 2.

Claims (5)

(A) Yttrium compound having a bulky ligand represented by the following general formula (1), (B) an ionic compound comprising a non-coordinating anion and a cation, (C) Group 2 of the periodic table And a conjugated diene compound is polymerized using a catalyst obtained from an organometallic compound of an element selected from Group 12, Group 13, and the like.

However, E is represents a nitrogen or phosphorus atom, Z ^1, Z ² represents a carbon or silicon ^{atom, R 1, R 2, R} 3, R 4, R 5, R 6 is hydrogen or 1 to 12 carbon atoms, And Y represents an yttrium atom. The method for producing a conjugated diene polymer according to claim 1, wherein the molecular weight is adjusted with a compound selected from (1) hydrogen, (2) a hydrogenated metal compound, and (3) a hydrogenated organometallic compound. (1) E of a formula is a nitrogen atom, The manufacturing method of the conjugated diene polymer of Claims 1-2 characterized by the above-mentioned. The method for producing a conjugated diene polymer according to claim 1, wherein the conjugated diene polymer is polybutadiene or polyisoprene. The method for producing a conjugated diene polymer according to claim 1, wherein the conjugated diene polymer is cis-1,4-polybutadiene having 90% or more of a cis-1,4 structure.