JP2007161919A - Manufacturing method of polyisoprene - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing method of polyisoprene using a polymerization catalyst system comprised of an yttrium compound that has never been actually employed among polymerization catalysts for a conjugated diene comprised of a group 3 element in the periodic table. <P>SOLUTION: The manufacturing method of the polyisoprene comprises polymerizing isoprene using a catalyst obtained from (A) the yttrium compound, (B) an ionic compound comprised of a non-coordinating anion and a cation and (C) an organometallic compound of an element selected from among 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 polyisoprene using a polymerization catalyst system 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.

  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 in combination with a trialkyl derivative is described, no example of polymerization of isoprene is described.

  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 a butadiene-isoprene copolymer using a compound of an element selected from the group consisting of scandium, yttrium, lanthanoid, and actinoid as a catalyst. However, specific examples using an yttrium catalyst are not given, and examples of a method for polymerizing a butadiene-isoprene copolymer 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

It is obtained from (A) an yttrium compound, (B) an ionic compound comprising a non-coordinating anion and a cation, and (C) an organometallic compound of an element selected from Groups 2, 12, and 13 of the periodic table. The present invention relates to a method for producing polyisoprene, wherein isoprene is polymerized using a catalyst.

  It is obtained from (A) an yttrium compound, (B) an ionic compound comprising a non-coordinating anion and a cation, and (C) an organometallic compound of an element selected from Groups 2, 12, and 13 of the periodic table. A method for producing polyisoprene, characterized by polymerizing isoprene using a catalyst.

  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, yttrium octylate (ethylhexanoate). , Yttrium naphthenate, yttrium neodecanoate, tris [N, N-bis (trimethylsilyl) amido] yttrium, tris [N, N-bis (triethylsilyl) amido] yttrium, tris [N, N-bis (dimethylphenylsilyl) Amido] yttrium, tris [N, N-bis (t-butyl) amido] yttrium, yttrium salts such as tris [N, N-bis (dimethylphenylmethyl) amido] yttrium, yttrium trimethoxide, yttrium triethoxide The Alkoxides such as thorium tributoxide, yttrium triphenoxide, tris (acetylacetonato) yttrium, tris (hexanedionato) yttrium, tris (heptanedionato) yttrium, tris (dimethylheptaneedionato) yttrium, tris (trimethylheptandionato) yttrium , Tris (tetramethylheptanedionate) yttrium, tris (pentamethylheptanedionate) yttrium, tris (hexamethylheptanedionate) yttrium, trisacetoacetatoyttrium, cyclopentadienyl yttrium dichloride, dicyclopentadienyl yttrium Organic yttrium compounds such as chloride, tricyclopentadienyl yttrium, yttrium salt pyridine complex, Organic base complexes such as thorium salt picoline complex of yttrium salt hydrates include yttrium salt alcohol complexes.

  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, 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.

  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.

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

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

  (2) Add component (A) in the presence or absence of the isoprene monomer or conjugated diene compound to be polymerized in an inert organic solvent, and add component (B) and component (C) in any order. .

  (3) Add component (B) in the presence or absence of the isoprene monomer or conjugated diene compound to be polymerized in an inert organic solvent, and add components (A) and (C) in any order. .

  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 a conjugated diene compound. 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.

  1,3-butadiene, 1,3-pentadiene, 2-ethyl-1,3-butadiene, 2,3-dimethylbutadiene, 2-methylpentadiene, 4-methylpentadiene, 2,4-hexadiene, etc. are conjugated to isoprene monomer. Dienes may be included.

  Here, the isoprene 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.

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

Microstructure was performed by H ⁺ -NMR 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.

  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 260 ml of toluene and 140 ml of isoprene, the temperature of the solution was adjusted to 30 ° C., and then 1 ml of a toluene solution (1 mol / L) of triethylaluminum (TEA) was added every minute. The mixture was stirred at 500 rpm for 3 minutes. Next, 1 ml of a toluene solution (20 mmol / L) of tris (2,2,6,6-tetramethylheptane-3,5-dionato) yttrium was added and stirred for 2 minutes. After heating the autoclave to a temperature of 40 ° C., 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 polyisoprene. The recovered polyisoprene 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)
The inside of the autoclave having an internal volume of 2 L was purged with nitrogen, charged with 390 ml of toluene and 180 ml of isoprene, 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 every minute. The mixture was stirred at 500 rpm for 3 minutes. Next, 1.5 ml of a toluene solution (20 mmol / L) of tris (2,2,6,6-tetramethylheptane-3,5-dionato) yttrium was added and stirred for 2 minutes. After heating the autoclave to a temperature of 40 ° C., 0.15 ml of a toluene solution (0.4 mol / L) of triphenylcarbenium tetrakispentafluorophenylborate was added to initiate polymerization. After polymerization at 40 ° C. for 45 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 polyisoprene. The recovered polyisoprene 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 3)
Polymerization was carried out in the same manner as in Example 1 except that the amount of triethylaluminum (TEA) toluene solution (1 mol / L) added was 4 ml. The polymerization conditions are shown in Table 1, and the polymerization results are shown in Table 2.

Example 4
The inside of the autoclave having an internal volume of 2 L was purged with nitrogen, charged with 520 ml of toluene and 280 ml of isoprene, the temperature of the solution was adjusted to 30 ° C., and then 16 ml of a toluene solution (1 mol / L) of triethylaluminum (TEA) was added every minute. The mixture was stirred at 500 rpm for 3 minutes. Next, 2 ml of a toluene solution (20 mmol / L) of tris (2,2,6,6-tetramethylheptane-3,5-dionato) yttrium was added and stirred for 2 minutes. After heating the autoclave to a temperature of 40 ° C., 0.2 ml of a toluene solution (0.4 mol / L) of triphenylcarbenium tetrakispentafluorophenylborate was added to initiate polymerization. After polymerization at 40 ° C. for 45 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 polyisoprene. The recovered polyisoprene 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.

Claims (1)

It is obtained from (A) an yttrium compound, (B) an ionic compound comprising a non-coordinating anion and a cation, and (C) an organometallic compound of an element selected from Groups 2, 12, and 13 of the periodic table. A method for producing polyisoprene, characterized in that isoprene is polymerized using a catalyst.