JP2018104548A - Catalyst solution for conjugate diene polymerization and polymerization method therewith - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of preparing a solution of a pentafluorophenyl borate salt characterized by using an aromatic hydrocarbon and a halogenated hydrocarbon in combination as a solvent, thus, to result in that a solution polymerization due to a homogeneous solution becomes possible, a concentration irregularity or a local irregular reaction in a reaction system is suppressed, olefine and conjugate diene copolymer having less foreign matter and excellent mechanical characteristics are provided.SOLUTION: The present invention relates to a catalyst for polymerizing olefine, conjugated diene characterized by using a solution of a pentafluorophenyl borate salt in which an aromatic hydrocarbon and a halogenated hydrocarbon are used in combination as a solvent as a catalyst component.SELECTED DRAWING: None

Description

  The present invention relates to an olefin / conjugated diene polymerization catalyst using a high concentration solution of pentafluorophenylborate salt and a polymerization method using the same.

  Conventionally, transition metal compounds (for example, salts or metallocene complexes) have been used as catalysts for coordination polymerization of olefins and dienes and catalysts for organic synthesis reactions, and many reports have been made. These catalysts are usually used together with an organic metal compound, for example, an activator such as alkyllithium, alkylaluminum, alkylaluminoxane, or tris (pentafluorophenyl) borane, or a cocatalyst, but pentafluorophenyl which is an ionic compound. Borate salts are also known to be useful.

  Alkyl aluminum, alkylaluminoxane, and tris (pentafluorophenyl) borane are useful as co-catalysts for olefin polymerization, and these are easily dissolved in common hydrocarbon solvents such as hexane and toluene. Therefore, it can be easily applied to a homogeneous solution reaction, and the solution can be easily prepared when the supported catalyst is produced.

On the other hand, pentafluorophenylborate salt, which is an ionic compound, is soluble to some extent in aromatic hydrocarbon solvents such as benzene and toluene, but even when preparing a uniform solution, it is about several millimoles / liter at room temperature. A concentration of about 1% by weight or less is the limit. Moreover, it is substantially insoluble in aliphatic saturated hydrocarbons such as petroleum ether, gasoline, n-hexane, cyclohexane and heptane.

  In addition, some pentafluorophenylborate salts are separated into a dilute solution phase and a concentrated solution phase at a certain concentration above a certain concentration, and a homogeneous solution with a concentration of the dilute solution phase and higher than the concentrated solution phase is prepared. There are things you can't do. In this case, even if an attempt is made to prepare a solution having a desired concentration not less than the diluted solution phase and not more than the concentrated solution phase, the uniform state cannot be maintained. When such a non-uniform mixed solution is used, there is a problem that concentration unevenness occurs in the reaction system, causing a local abnormal reaction and further causing foreign matters in the product.

For example, Japanese Patent Publication No. 9-503542 uses a slurry in which 1,2-ethylene-bridged zirconocene dichloride is suspended in gasoline as a catalyst, and dimethylanilinium tetrakis (pentafluorophenyl) borate as a catalyst. A method for producing an olefin polymer using a slurry suspended therein is disclosed.

JP-A-9-316122, JP-A-11-322850, Japanese Patent No. 3562182, etc. use a toluene solution of cyclopentadienyl vanadium trichloride (CpVCl3) as a catalyst, and triphenylcarbonium tetrakis. A method for producing a conjugated diene polymer using a dilute toluene solution (concentration of 2.5 to 5 mmol / liter) of (pentafluorophenyl) borate (Ph3CB (C6F5) 4) is disclosed.

JP 2007-161798 A and JP 522311 A use a yttrium compound having a bulky ligand as a catalyst, and a concentrated toluene solution (concentration) of triphenylcarbenium tetrakis (pentafluorophenyl) borate. 430 mmol / liter) is disclosed.

Thus, conventionally, when adding pentafluorophenyl borate salt to a reaction vessel, it is added in a large amount as a suspension or as a low-concentration solution, or a specific high-concentration solution obtained as a phase-separated concentrated phase It was necessary to add. If a suspension or a specific high-concentration solution is used, unreacted pentafluorophenyl borate salt may remain in the product as a foreign substance, which is not preferable. In addition, when a large amount of a low-concentration solution is added, a process for recovering a large amount of a storage facility and a large amount of solvent is required, which is not economically preferable.

JP-T 9-503542 JP-A-9-316122 JP-A-11-322850 Japanese Patent No. 3562182 JP 2007-161798 A Japanese Patent No. 522311

  An object of the present invention is to prepare a high concentration solution of pentafluorophenyl borate salt at an arbitrary concentration, and to provide a catalyst for polymerization of olefins and conjugated dienes using the high concentration solution, and a polymerization method using the same. is there.

The present invention relates to a catalyst for polymerization of olefins and conjugated dienes using a high-concentration solution of pentafluorophenylborate salt characterized by using an aromatic hydrocarbon and a halogenated hydrocarbon in combination as a solvent, and polymerization using the same Regarding the method.

In particular, the present invention relates to the above-mentioned catalyst for polymerization of olefins and conjugated dienes, and a polymerization method using the same, wherein the pentafluorophenylborate salt is triphenylcarbenium tetrakispentafluorophenylborate.

  According to the present invention, a uniform organic solvent solution of pentafluorophenyl borate characterized in that the concentration is 5 mmol / liter or more and 430 mmol / liter or less at room temperature, and a catalyst for polymerization of olefin and conjugated diene, and It can be used for polymerization using the same.

The present invention provides a method for preparing a solution of a pentafluorophenyl borate salt, which comprises using an aromatic hydrocarbon and a halogenated hydrocarbon in combination as a solvent. As a result, solution polymerization using a homogeneous solution is possible, and it is possible to provide an olefin or conjugated diene polymer that suppresses uneven concentration in the reaction system and local abnormal reactions, has few foreign matters, and has excellent mechanical properties.

  The present invention relates to an olefin and conjugated diene polymerization catalyst characterized by using, as a catalyst component, a solution of an aromatic hydrocarbon and a pentafluorophenyl borate salt in which a halogenated hydrocarbon is used as a solvent.

  Examples of the pentafluoroborate salt of the present invention include triphenylcarbenium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) borate, tris (pentafluorophenyl) (phenyl) borate, diphenylbis ( And salts such as pentafluorophenyl) borate and triphenyl (pentafluorophenyl) borate.

  On the other hand, as the cation constituting the pentafluoroborate salt of the present invention, typical metal ions such as alkali metal ions and alkaline earth metal ions, transition metal ions, carbonium cations, oxonium cations, ammonium cations, phosphonium cations, Examples thereof include cycloheptatrienyl cation and ferrocenium cation.

  Specific examples of metal ions include lithium ions, sodium ions, potassium ions, calcium ions, strontium ions, barium ions, aluminum ions, gallium ions, indium ions, titanium ions, zirconium ions, vanadium ions, manganese ions, iron ions, Examples include nickel ions, cobalt ions, zinc ions, copper ions, silver ions, gold ions, lanthanum ions, neodymium ions, samarium ions, gadolinium ions, praseodymium ions, terbium ions, and complex ions thereof.

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 pentafluoroborate salt, those selected and combined arbitrarily from the cations exemplified above can be preferably used.

  Among them, triphenyl carbonium tetrakis (pentafluorophenyl) borate, triphenyl carbonium tetrakis (fluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, 1,1 ′ -Dimethylferrocenium tetrakis (pentafluorophenyl) borate and the like are preferable, and triphenylcarbonium tetrakis (pentafluorophenyl) borate is more preferable. An ionic compound may be used independently and may be used in combination of 2 or more type.

There are no particular restrictions on the combination of the aromatic hydrocarbon used as the solvent and the halogenated hydrocarbon used together, but examples of the aromatic hydrocarbon include benzene, toluene, o-xylene, m-xylene, p-xylene, ethylbenzene, and propyl. Alkylbenzenes such as benzene, butylbenzene, hexylbenzene, dodecylbenzene, cumene, and p-cymene are preferable, and alkylbenzene substituted with an alkyl group having 1 to 12 carbon atoms is more preferable. Of these, toluene, ethylbenzene, and xylene (o-xylene, p-xylene) are particularly preferable from the viewpoint of versatility.

Examples of halogenated hydrocarbons include aliphatic halogenated hydrocarbons such as dichloromethane, chloroform, butyl chloride, hexyl chloride and dichlorohexane, chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, o-chlorotoluene, Aromatic halogenated hydrocarbons such as m-chlorotoluene, p-chlorotoluene, dichlorotoluene, trichlorobenzene and ethylchlorobenzene are preferred. Of these, chlorobenzene and o-dichlorobenzene (1,2-dichlorobenzene) are particularly preferable.

The amount ratio of the aromatic hydrocarbon used as the solvent and the halogenated hydrocarbon used in combination is not particularly limited, and can be mixed and used at an arbitrary amount ratio. A mixture of halogenated hydrocarbons in a range of 0.01 to 100 volumes, preferably 0.1 to 50 volumes, particularly preferably 1 to 30 volumes can be used.

Although there is no particular limitation on the method for dissolving the pentafluoroborate salt of the present invention, since it is generally highly soluble in halogenated hydrocarbons, after dissolving the pentafluoroborate salt in the halogenated hydrocarbon in advance, the aromatic hydrocarbon It is preferable to dilute with.

  The concentration of the homogeneous organic solvent solution of pentafluorophenylborate salt (triphenylcarbenium tetrakis (pentafluorophenyl) borate) is higher than 5 mmol / liter and lower than 430 mmol / liter. Within this range, it is effective in that a uniform (not suspended) solution of the pentafluorophenyl borate salt can be obtained.

  The solution adjustment temperature of the pentafluoroborate salt of the present invention is 0 ° C to 100 ° C, preferably 10 ° C to 80 ° C, and particularly preferably 15 ° C to 60 ° C. At low temperatures, the pentafluoroborate salt may be precipitated due to a decrease in solubility. At high temperatures, concentration due to volatilization of the solvent or thermal decomposition of the pentafluoroborate salt is not preferable.

  Examples of the olefin and conjugated diene polymerization catalyst that can be used in this embodiment include a combination of the above pentafluoroborate salt and a metal complex. Examples of the metal used for the metal complex include transition metals such as vanadium, cobalt, and nickel, and rare earth metals such as yttrium, lanthanum, samarium, neodymium, gadolinium, terbium, dysprosium, praseodymium, holmium, erbium, and thulium. Of these, vanadium complexes and rare earth metal complexes are particularly preferred.

Examples of vanadium complexes include cyclopentadienyl vanadium trichloride, methylcyclopentadienyl vanadium trichloride, ethylcyclopentadienyl vanadium trichloride, propylcyclopentadienyl vanadium trichloride, isopropylcyclopentadienyl vanadium trichloride, ( 1,2-dimethylcyclopentadienyl) vanadium trichloride, (1,3-dimethylcyclopentadienyl) vanadium trichloride, (1,2,3-trimethylcyclopentadienyl) vanadium trichloride, (1,2 , 4-Trimethylcyclopentadienyl) vanadium trichloride, (1,2,3,4-tetramethylcyclopentadienyl) vanadium trichloride, (pentamethylcyclopenta Enyl) vanadium trichloride, (2-methylindenyl) vanadium trichloride, cyclopentadienyl vanadium tri-t-butoxide, cyclopentadienyl vanadium tri-propoxide, cyclopentadienyl vanadium dimethoxy chloride, (t-butylamide) Dimethyl (η5-cyclopentadienyl) silane vanadium dichloride, cyclopentadienyl tris (diethylamide) vanadium, cyclopentadienyl tris (i-propylamido) vanadium, cyclopentadienyloxovanadium dichloride, methylcyclopentadienyloxo Vanadium dichloride, benzylcyclopentadienyloxovanadium dichloride, (1,3-dimethylcyclopentadienyl) oxovanadium Dichloride, (t-butylamido) dimethyl (η5-cyclopentadienyl) silane oxovanadium chloride, cyclopentadienyl oxovanadium dimethoxide, cyclopentadienyl oxovanadium di-propoxide, (cyclopentadienyl) bis ( Diethylamide)
Examples include oxovanadium. Among these, cyclopentadienyl vanadium trichloride and cyclopentadienyl oxo vanadium dichloride are preferable. The addition amount of the vanadium complex is usually preferably 1 × 10 ⁻⁷ to 1 × 10 ⁻⁴ mol, particularly preferably 1 × 10 ⁻⁶ to 1 × 10 ⁻⁵ mol, with respect to 1 mol of the diene monomer. .

  In this embodiment, it is preferable to use an organoaluminum compound as a promoter. Examples of the organoaluminum compound include trialkylaluminum such as trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, and tridecylaluminum. In addition, dialkylaluminum chloride such as dimethylaluminum chloride and diethylaluminum chloride; dialkylaluminum bromide; alkylaluminum sesquichloride such as sesquiethylaluminum chloride; alkylaluminum sesquibromide; organoaluminum halogen compounds such as alkylaluminum dichloride such as ethylaluminum dichloride Can be mentioned. Further, organic aluminum hydride compounds such as diethylaluminum hydride, diisobutylaluminum hydride, sesquiethylaluminum hydride, and the like can be given.

  These organoaluminum compounds can be used alone or in combination of two or more.

  The amount of the organoaluminum compound added is preferably in the range of 50 to 2000 mol with respect to 1 mol of the metal catalyst.

When a transition metal complex is used as a catalyst, it is preferable from the viewpoint of polymerization activity to add an appropriate amount of water. In this case, the amount of water added is preferably such that the molar ratio (Al / H ₂ O) between the organoaluminum compound and water is 1.00 to 2.00, more preferably 1.05 to 1.95. Preferably, it is 1.10 to 1.90, more preferably 1.10 to 1.80. When Al / H ₂ O is smaller than 1.00 or larger than 2.00, the productivity of the conjugated diene polymer tends to decrease or the gel content in the product tends to increase, such being undesirable.

  The organoaluminum compound and water are preferably aged, and the aging time is preferably 3 to 30 minutes, more preferably 4 to 25 minutes, and particularly preferably 4.5 to 15 minutes. When the aging time is shorter than 3 minutes, the conjugated diene polymer tends to be colored and discolored with time. When the aging time is longer than 30 minutes, the yield of the rubber itself decreases and the productivity tends to deteriorate. It is not preferable.

  Examples of rare earth metal complexes include yttrium (Y), lanthanum (La), neodymium (Nd), gadolinium (Gd), terbium (Tb), dysprosium (Dy), praseodymium (Pr), holmium (Ho), and erbium (Er). , And metal compounds containing thulium (Tm). These metal compounds may be used alone or in combination of two or more.

The rare earth metal complex only needs to be soluble in a nonpolar organic solvent, and may be a metallocene-type metal compound or a nonmetallocene-type metal compound. Among them, nonmetallocene metal compounds that are relatively simple to synthesize than metallocene metal compounds are preferred.

  Examples of rare earth metal complexes include non-metallocene metal compounds such as inorganic salts, halides, alkoxides, carboxylates, amide complexes, diketone complexes, and ketoester complexes.

  Examples of inorganic salts include nitrates, sulfates, and hydroxides. Examples of the halide include fluoride, chloride, bromide, and iodide. Examples of the alkoxide include methoxide, ethoxide, propoxide, isopropoxide, butoxide, and the like. Carboxylates include acetate, oxalate, propionate, malonate, succinate, valerate, pivalate, ethylhexanoate, versatic acid, neodecanoate, naphthenate, etc. Is mentioned. Examples of the amide complex include dimethylamide, diethylamide, diisopropylamide, bistrimethylsilylamide, and the like.

  The rare earth metal complex used in the conjugated diene polymerization catalyst according to the present invention is particularly preferably a nonmetallocene metal compound represented by the following general formula (1). By using the nonmetallocene type metal compound represented by the general formula (1), a conjugated diene polymer having a high cis-1,4 structure content and various excellent properties can be obtained.

(However, R1, R2, and R3 each represent hydrogen or a C1-C12 substituent. O represents an oxygen atom, Ln represents yttrium (Y), lanthanum (La), neodymium (Nd), gadolinium ( Gd), terbium (Tb), dysprosium (Dy), praseodymium (Pr), holmium (Ho), erbium (Er), thulium (Tm).

  Specific examples of the substituent having 1 to 12 carbon atoms in R1 to R3 of the general formula (1) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an s-butyl group, and an 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, Saturated hydrocarbon groups such as hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, and dodecyl group, unsaturated hydrocarbon groups such as vinyl group, 1-propenyl group, and allyl group, cyclohexyl group, Alicyclic hydrocarbon groups such as methylcyclohexyl and ethylcyclohexyl groups, and phenyl, benzyl, toluyl, and phenethyl groups Such as aromatic hydrocarbon groups. Furthermore, 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. Among them, a saturated hydrocarbon group having 1 to 12 carbon atoms is preferable, and a saturated hydrocarbon group having 1 to 6 carbon atoms is particularly preferable.

  In R1 to R3 of the general formula (1), R2 is preferably hydrogen or a substituent having 1 to 12 carbon atoms, and R1 and R3 are preferably substituents having 1 to 12 carbon atoms. In particular, R2 is preferably hydrogen or a substituent having 1 to 6 carbon atoms, and R1 and R3 are preferably substituents having 1 to 6 carbon atoms.

  In R1 to R3 of the general formula (1), R2 is preferably hydrogen or a saturated hydrocarbon group having 1 to 12 carbon atoms, and R1 and R3 are preferably saturated hydrocarbon groups having 1 to 12 carbon atoms. In particular, R2 is preferably hydrogen or a saturated hydrocarbon group having 1 to 6 carbon atoms, and R1 and R3 are preferably saturated hydrocarbon groups having 1 to 6 carbon atoms.

  Specific examples of the nonmetallocene metal compound (A) of the general formula (1) in which Ln is yttrium (Y) include tris (2,2,6,6-tetramethyl-3,5-heptanedionato) yttrium, Tris (2,6,6-trimethyl-3,5-heptanedionato) yttrium, Tris (2,6-dimethyl-3,5-heptanedionato) yttrium, Tris (3,5-heptanedionato) yttrium, Tris (2,4- Pentandionato) yttrium, tris (2,4-hexanedionate) yttrium, tris (1,5-dicyclopentyl-2,4-pentanedionate) yttrium, tris (1,5-dicyclohexyl-2,4-pentane (Dionato) yttrium.

  Among them, preferably, tris (2,2,6,6-tetramethyl-3,5-heptanedionato) yttrium, tris (2,6-dimethyl-3,5-heptaneedionato) yttrium, tris (2,4-pentanedioated) Nato) yttrium. Particularly preferred are tris (2,2,6,6-tetramethyl-3,5-heptanedionato) yttrium and tris (2,6-dimethyl-3,5-heptaneedionato) yttrium.

  Specific examples of the nonmetallocene metal compound (A) of the general formula (1) in which Ln is lanthanum (La) include tris (2,2,6,6-tetramethyl-3,5-heptanedionate) lanthanum, Tris (2,6,6-trimethyl-3,5-heptanedionato) lanthanum, Tris (2,6-dimethyl-3,5-heptaneedionato) lanthanum, Tris (3,5-heptaneedionato) lanthanum, Tris (2,4- Pentanedionato) lanthanum, tris (2,4-hexanedionato) lanthanum, tris (1,5-dicyclopentyl-2,4-pentanedionato) lanthanum, tris (1,5-dicyclohexyl-2,4-pentane) Diato) lanthanum and the like.

  Among them, preferably, tris (2,2,6,6-tetramethyl-3,5-heptanedionate) lanthanum, tris (2,6-dimethyl-3,5-heptanedionate) lanthanum, tris (2,4-pentanedio) Nato) lanterns. Particularly preferred are tris (2,2,6,6-tetramethyl-3,5-heptanedionate) lanthanum and tris (2,6-dimethyl-3,5-heptanedionate) lanthanum.

  Specific examples of the non-metallocene type metal compound (A) of the general formula (1) in which Ln is neodymium (La) include tris (2,2,6,6-tetramethyl-3,5-heptanedionato) neodymium, Tris (2,6,6-trimethyl-3,5-heptanedionato) neodymium, Tris (2,6-dimethyl-3,5-heptaneedionato) neodymium, Tris (3,5-heptaneedionato) neodymium, Tris (2,4- Pentandionato) neodymium, tris (2,4-hexanedionate) neodymium, tris (1,5-dicyclopentyl-2,4-pentanedionate) neodymium, tris (1,5-dicyclohexyl-2,4-pentane) Dionato) and neodymium.

  Among them, preferably, tris (2,2,6,6-tetramethyl-3,5-heptanedionate) neodymium, tris (2,6-dimethyl-3,5-heptanedionate) neodymium, tris (2,4-pentanedio) NATO) Neodymium. Particularly preferred are tris (2,2,6,6-tetramethyl-3,5-heptanedionate) neodymium and tris (2,6-dimethyl-3,5-heptanedionate) neodymium.

  Specific examples of the nonmetallocene metal compound (A) of the general formula (1) in which Ln is gadolinium (Gd) include tris (2,2,6,6-tetramethyl-3,5-heptanedionato) gadolinium, Tris (2,6,6-trimethyl-3,5-heptanedionato) gadolinium, tris (2,6-dimethyl-3,5-heptanedionato) gadolinium, tris (3,5-heptanedionato) gadolinium, tris (2,4- Pentanedionato) gadolinium, tris (2,4-hexanedionato) gadolinium, tris (1,5-dicyclopentyl-2,4-pentanedionato) gadolinium, tris (1,5-dicyclohexyl-2,4-pentane) (Dionato) gadolinium and the like.

  Among them, preferably, tris (2,2,6,6-tetramethyl-3,5-heptanedionato) gadolinium, tris (2,6-dimethyl-3,5-heptaneedionato) gadolinium, tris (2,4-pentanedioe) is preferable. Nato) gadolinium and the like. Particularly preferred are tris (2,2,6,6-tetramethyl-3,5-heptanedionato) gadolinium and tris (2,6-dimethyl-3,5-heptanedionato) gadolinium.

  Specific examples of the nonmetallocene metal compound (A) of the general formula (1) in which Ln is terbium (Tb) include tris (2,2,6,6-tetramethyl-3,5-heptanedionato) terbium, Tris (2,6,6-trimethyl-3,5-heptanedionato) terbium, Tris (2,6-dimethyl-3,5-heptanedionato) terbium, Tris (3,5-heptanedionato) terbium, Tris (2,4- Pentandionato) terbium, tris (2,4-hexanedionate) terbium, tris (1,5-dicyclopentyl-2,4-pentandionato) terbium, tris (1,5-dicyclohexyl-2,4-pentane) (Dionato) terbium and the like.

  Among them, preferably tris (2,2,6,6-tetramethyl-3,5-heptanedionato) terbium, tris (2,6-dimethyl-3,5-heptaneedionato) terbium, tris (2,4-pentanedioe) Nato) terbium. Particularly preferred are tris (2,2,6,6-tetramethyl-3,5-heptanedionato) terbium and tris (2,6-dimethyl-3,5-heptanedionato) terbium.

  Specific examples of the nonmetallocene metal compound (A) of the general formula (1) in which Ln is dysprosium (Dy) include tris (2,2,6,6-tetramethyl-3,5-heptanedionato) dysprosium, Tris (2,6,6-trimethyl-3,5-heptanedionato) dysprosium, Tris (2,6-dimethyl-3,5-heptanedionato) dysprosium, Tris (3,5-heptanedionato) dysprosium, Tris (2,4- Pentanedionate) dysprosium, tris (2,4-hexanedionato) dysprosium, tris (1,5-dicyclopentyl-2,4-pentanedionato) dysprosium, tris (1,5-dicyclohexyl-2,4-pentane) And diatoprosium).

  Among them, preferably, tris (2,2,6,6-tetramethyl-3,5-heptanedionato) dysprosium, tris (2,6-dimethyl-3,5-heptaneedionato) dysprosium, tris (2,4-pentanedioe) Nato) dysprosium. Particularly preferred are tris (2,2,6,6-tetramethyl-3,5-heptanedionato) dysprosium and tris (2,6-dimethyl-3,5-heptaneedionato) dysprosium.

  Specific examples of the nonmetallocene type metal compound (A) of the general formula (1) in which Ln is praseodymium (Pr) include tris (2,2,6,6-tetramethyl-3,5-heptanedionato) praseodymium, Tris (2,6,6-trimethyl-3,5-heptanedionato) praseodymium, Tris (2,6-dimethyl-3,5-heptanedionato) praseodymium, Tris (3,5-heptanedionato) praseodymium, Tris (2,4- Pentanedionate) praseodymium, tris (2,4-hexanedionate) praseodymium, tris (1,5-dicyclopentyl-2,4-pentanedionate) praseodymium, tris (1,5-dicyclohexyl-2,4-pentane) Zionato) praseodymium and the like.

  Among these, preferably, tris (2,2,6,6-tetramethyl-3,5-heptanedionato) praseodymium, tris (2,6-dimethyl-3,5-heptaneedionato) praseodymium, tris (2,4-pentanedioe) Nato) Praseodymium. Particularly preferred are tris (2,2,6,6-tetramethyl-3,5-heptanedionato) praseodymium and tris (2,6-dimethyl-3,5-heptanedionato) praseodymium.

  Specific examples of the nonmetallocene metal compound (A) of the general formula (1) in which Ln is holmium (Ho) include tris (2,2,6,6-tetramethyl-3,5-heptanedionato) holmium, Tris (2,6,6-trimethyl-3,5-heptanedionato) holmium, Tris (2,6-dimethyl-3,5-heptanedionato) holmium, Tris (3,5-heptanedionato) holmium, Tris (2,4- Pentandionato) holmium, tris (2,4-hexanedionate) holmium, tris (1,5-dicyclopentyl-2,4-pentandionato) holmium, tris (1,5-dicyclohexyl-2,4-pentane) And diato) holmium.

  Among them, preferably, tris (2,2,6,6-tetramethyl-3,5-heptanedionato) holmium, tris (2,6-dimethyl-3,5-heptanedionato) holmium, tris (2,4-pentanedioe) Nato) holmium and the like. Particularly preferred are tris (2,2,6,6-tetramethyl-3,5-heptanedionato) holmium and tris (2,6-dimethyl-3,5-heptanedionato) holmium.

  Specific examples of the nonmetallocene metal compound (A) of the general formula (1) in which Ln is erbium (Er) include tris (2,2,6,6-tetramethyl-3,5-heptanedionato) erbium, Tris (2,6,6-trimethyl-3,5-heptanedionato) erbium, Tris (2,6-dimethyl-3,5-heptanedionato) erbium, Tris (3,5-heptanedionato) erbium, Tris (2,4- Pentandionato) erbium, tris (2,4-hexanedionate) erbium, tris (1,5-dicyclopentyl-2,4-pentandionato) erbium, tris (1,5-dicyclohexyl-2,4-pentane) (Dionato) Erbium.

  Among them, preferably tris (2,2,6,6-tetramethyl-3,5-heptanedionato) erbium, tris (2,6-dimethyl-3,5-heptaneedionato) erbium, tris (2,4-pentanedioe) Nato) Erbium. Particularly preferred are tris (2,2,6,6-tetramethyl-3,5-heptanedionato) erbium and tris (2,6-dimethyl-3,5-heptanedionato) erbium.

  Specific examples of the non-metallocene metal compound (A) of the general formula (1) in which Ln is thulium (Tm) include tris (2,2,6,6-tetramethyl-3,5-heptanedionato) thulium, Tris (2,6,6-trimethyl-3,5-heptanedionato) thulium, tris (2,6-dimethyl-3,5-heptaneedionato) thulium, tris (3,5-heptaneedionato) thulium, tris (2,4- Pentandionato) thulium, tris (2,4-hexanedionate) thulium, tris (1,5-dicyclopentyl-2,4-pentanedionato) thulium, tris (1,5-dicyclohexyl-2,4-pentane) (Dionato) thulium and the like.

  Among them, preferably, tris (2,2,6,6-tetramethyl-3,5-heptanedionato) thulium, tris (2,6-dimethyl-3,5-heptaneedionato) thulium, tris (2,4-pentanedioated) Nato) thulium. Particularly preferred are tris (2,2,6,6-tetramethyl-3,5-heptanedionato) thulium and tris (2,6-dimethyl-3,5-heptaneedionato) thulium.

  These nonmetallocene-type metal compounds may be used alone or in combination of two or more.

  In this embodiment, it is preferable to use an organometallic compound of an element selected from Groups 2, 12, and 13 of the periodic table as a promoter. For example, organic magnesium, organic zinc, organic aluminum, etc. are used. Among these compounds, preferred are dialkylmagnesium; alkylmagnesium halides such as alkylmagnesium chloride and alkylmagnesium bromide; dialkylzinc; trialkylaluminum; dialkylaluminum chloride, dialkylaluminum bromide; alkylaluminum sesquichloride, alkylaluminum sesquibromide Organic aluminum halogen compounds such as alkylaluminum dichloride; organoaluminum hydride compounds such as dialkylaluminum hydride.

  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, dialkyl zinc, such as dimethyl zinc, diethyl zinc, diisobutyl zinc, dihexyl zinc, dioctyl zinc, and didecyl zinc, 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 elements selected from Groups 2, 12, and 13 of the periodic table can be used alone or in combination of two or more. Among them, an organometallic compound of a group 13 element is preferable, among which organic aluminum is preferable, and examples thereof include trimethylaluminum, triethylaluminum, and triisobutylaluminum. Particularly preferred is triethylaluminum.

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

  The ratio of the metal compound (A), pentafluorophenyl borate salt (B) of the catalyst for conjugated diene polymerization of the present invention, the organometallic compound (C) of an element selected from Groups 2, 12, and 13 of the periodic table is Although not particularly limited, the amount of the component (B) is preferably 0.5 to 10 mol, particularly preferably 1 to 5 mol, per mol of the component (A). The amount of the component (C) is preferably 10 to 10000 mol, particularly preferably 50 to 7000 mol, per 1 mol of the component (A).

  The raw material conjugated diene compound monomer includes 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. Among them, a conjugated diene compound monomer containing 1,3-butadiene as a main component (for example, 50 mol% or more, preferably 80 mol% or more, more preferably 90 mol% or more) is preferable. These monomer components may be used individually by 1 type, and may be used in combination of 2 or more type.

In addition to the above conjugated diene, the raw material monomer of the conjugated diene polymer of the present invention is ethylene, propylene, allene, 1-butene, 2-butene, 1,2-butadiene, pentene, cyclopentene, hexene, cyclohexene, octene, Olefin compounds such as cyclooctadiene, cyclododecatriene, norbornene and norbornadiene may be included.
In the present invention, the conjugated diene is polymerized using the catalyst having the components (A), (B), and (C) described above, but the conjugation obtained is within the range not impeding the effects of the present invention. Diene polymer molecular weight regulators and the like can be added.

  As the molecular weight regulator, a compound selected from hydrogen, a metal hydride compound, and a hydrogenated organometallic compound can be used.

  Metal hydride compounds include lithium hydride, sodium hydride, potassium hydride, magnesium hydride, calcium hydride, borane, aluminum hydride, gallium hydride, silane, germane, lithium borohydride, sodium borohydride , Lithium aluminum hydride, sodium aluminum hydride and the like.

  Examples of the hydrogenated organometallic compound include alkylboranes such as methylborane, ethylborane, propylborane, butylborane and phenylborane, dialkylboranes such as dimethylborane, diethylborane, dipropylborane, dibutylborane and diphenylborane, and methylaluminum dihydride. Alkyl aluminum dihydride such as ethyl aluminum dihydride, propyl aluminum dihydride, butyl aluminum dihydride, phenyl aluminum dihydride, dimethyl aluminum hydride, diethyl aluminum hydride, dipropyl aluminum hydride, dinormal butyl aluminum hydride, diisobutyl aluminum hydride, Diphenylaluminum high dry Dialkylaluminum hydride such as, methylsilane, ethylsilane, propylsilane, butylsilane, phenylsilane, dimethylsilane, diethylsilane, dipropylsilane, dibutylsilane, diphenylsilane, trimethylsilane, triethylsilane, tripropylsilane, tributylsilane, triphenylsilane Silanes such as, 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, tributyl germane Examples thereof include germanes such as phenyl germane.

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

  In the method for producing a conjugated diene polymer according to the present invention, the order of addition of the organometallic compound (C) of the element selected from the pentafluorophenyl borate salt (B), Group 2, Group 12 and Group 13 of the periodic table is: Although there is no restriction | limiting in particular, For example, it can carry out in the following order.

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

  (2) Add component (C) in the presence or absence of a conjugated diene compound monomer in an inert organic solvent, add the molecular weight regulator as described above, and then optionally add component (A) and component (B) Add in order.

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

  (4) In the inert organic solvent, the component (B) is added in the presence or absence of the conjugated diene compound monomer, and the component (C) and the molecular weight regulator described above are added in an arbitrary order, and then (A ) Add ingredients.

  (5) In the inert organic solvent, the (C) component is added in the presence or absence of the conjugated diene compound monomer, the (A) component and the (B) component are added in any order, and then the molecular weight described above. Add modifier.

  Here, the monomer added first may be the total amount of the monomer or a part thereof.

  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, ethylbenzene, and cumene, Examples thereof include olefinic hydrocarbons such as olefin compounds and cis-2-butene and trans-2-butene. Among them, benzene, toluene, xylene, cyclohexane, or cis-2-butene and trans-2-butene. And the like are preferably used. These solvent may be used individually by 1 type, and may be used in combination of 2 or more type.

The polymerization of the conjugated diene polymer can be stopped by adding water, alcohol, organic acid or inorganic acid and / or phenol in a usual manner. Among these, dispersibility is good, and preferable polymerization terminators include water and lower alcohols.
The lower alcohol preferably has 5 or less carbon atoms, and specifically includes methanol, ethanol, propanol, isopropanol, butanol, ter-butyl alcohol, pentanol and isomers thereof. These may be used alone or in combination of two or more.
The amount of water is preferably ratio raw material mixed solution total is 1.38 × ¹⁰ -8 ~9.9vol%, more preferably 2.76 × ¹⁰ -8 ~5vol%, It is still more preferable that it is 4.14 * 10 < ^-8 > -3vol%. The total raw material mixed solution is the total amount of a diene monomer as a raw material charged into the reactor, a mixed solution of organic solvents such as cyclohexane and butene, and a raw material mixed solution added before modification.

  In this embodiment, the polymerization terminator and the antioxidant may be added simultaneously, or after the polymerization terminator, the antioxidant may be added, or the order in which the antioxidant and the polymerization terminator are added. May be reversed. Further, when the polymerization terminator is other than water, the addition of the antioxidant can be omitted.

  Examples of the antioxidant include, for example, 4,6-bis (octylmethyl) -o-cresol (CAS-No. 110553-27-0), octadecyl-3- (3,5-ditert. Butyl-4-hydroxyphenyl) propionate (CAS No. 2082-79-3), pentaerythritol tetrakis [3 (3,5-ditertbutyl-4-hydroxyphenyl) propionate] (CAS-No. 6683-19-8) Etc. Other examples include phosphorus antioxidants.

As an addition amount of the antioxidant, a necessary amount may be appropriately added depending on the period of stable storage, but 5 × 10 ^{−6 to} 3 × 10 ⁻⁴ mol is preferable with respect to 1 mol of the diene monomer. 1 * 10 < ^-5 > -2 * 10 <^-4> mol is more preferable. Even if the amount of the antioxidant is too small, the anti-deterioration function cannot be obtained.

  In this embodiment, a known molecular weight regulator, for example, non-conjugated dienes such as cyclooctadiene and allene, α-olefins such as ethylene, propylene, and butene-1, hydrogen, and the like are used during polymerization. Can do.

  The polymerization temperature is preferably in the range of -30 to 100 ° C, particularly preferably in the range of 30 to 80 ° C. The polymerization time is preferably in the range of 5 minutes to 12 hours, particularly preferably 10 minutes to 6 hours. The polymerization pressure can be carried out under normal pressure or a pressure up to about 10 atmospheres (gauge pressure).

The conjugated diene polymer produced according to the present embodiment has a microstructure having a 1,4-cis structure of 80 to 99.9% and a 1,2-vinyl structure of 0.1 to 20%. Is preferred. [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 number average molecular weight (Mn) of the conjugated diene polymer obtained in the present invention is preferably 10,000 to 1,000,000, more preferably 100,000 to 700,000, particularly preferably 150,000 to 550000. Further, the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the conjugated diene polymer is preferably 1.5 to 10, more preferably 1.5 to 7, particularly preferably. 1.5-5 is mentioned. If Mw / Mn is small, workability may be deteriorated.

  The polymer produced by this embodiment can be used for all kinds of molding processes, and can be used for films, electrical insulating materials, packaging materials, battery materials, and the like. Also, because vulcanizates can be produced, for example, for producing tires, hoses, footwear members, industrial belts, medical rubber, sporting goods, crawlers or packing, as well as vinyl aromatic compounds, for example It can also be used for the impact modification of polymers based on polystyrene and bulk-processed ABS-polymers.

  Examples according to the present invention will be specifically described below.

Example 1
Under a nitrogen atmosphere at room temperature, 2.3 g of triphenylcarbenium tetrakispentafluorophenylborate was diluted to 500 ml with a pre-dehydrated mixed solvent (2.5 volumes of orthodichlorobenzene per 100 volumes of toluene) to obtain an orange color. A homogeneous solution was obtained. The concentration is 4.6 g / L (5 mmol / L).

(Example 2)
Under a nitrogen atmosphere at room temperature, 23 ml of previously dehydrated orthodichlorobenzene was added to 4.61 g of triphenylcarbenium tetrakispentafluorophenylborate to obtain a dark reddish brown solution. This solution was diluted to 500 ml with previously dehydrated toluene to obtain an orange uniform solution. The concentration is 9.2 g / L (10 mmol / L).

(Example 3)
Under a nitrogen atmosphere at room temperature, 46 ml of previously dehydrated orthodichlorobenzene was added to 9.22 g of triphenylcarbenium tetrakispentafluorophenylborate to obtain a dark reddish brown solution. This solution was diluted to 500 ml with previously dehydrated toluene to obtain an orange uniform solution. The concentration is 18.4 g / L (20 mmol / L).

Example 4
Under a nitrogen atmosphere at room temperature, 70 ml of previously dehydrated orthodichlorobenzene was added to 23.1 g of triphenylcarbenium tetrakispentafluorophenylborate to obtain a dark reddish brown solution. This solution was diluted to 500 ml with previously dehydrated toluene to obtain a dark orange uniform solution. The concentration is 46.2 g / L (50 mmol / L).

(Example 5)
Under a nitrogen atmosphere at room temperature, 70 ml of previously dehydrated orthodichlorobenzene was added to 46.1 g of triphenylcarbenium tetrakispentafluorophenylborate to obtain a dark reddish brown solution. This solution was diluted to 500 ml with previously dehydrated toluene to obtain a dark orange uniform solution. The concentration is 92.2 g / L (100 mmol / L).

(Example 6)
Under a nitrogen atmosphere at room temperature, 30 ml of previously dehydrated orthodichlorobenzene was added to 45.0 g of triphenylcarbenium tetrakispentafluorophenylborate to obtain a dark reddish brown solution. This solution was diluted with pre-dehydrated toluene to 250 ml to obtain a dark reddish brown uniform solution. The concentration is 180 g / L (195 mmol / L).

(Comparative Example 1)
Under a nitrogen atmosphere at room temperature, to 20 g of triphenylcarbenium tetrakispentafluorophenylborate, 20 ml of liquid paraffin previously dehydrated and zirconia beads were added and pulverized with a rotating ball mill to obtain a yellow slurry. It diluted with the liquid paraffin and prepared so that a density | concentration might be 180 g / L (195 mmol / L).

(Comparative Example 2)
The slurry obtained in Comparative Example 1 was diluted with liquid paraffin to prepare a concentration of 46.2 g / L (50 mmol / L).

(Comparative Example 3)
Under a nitrogen atmosphere at room temperature, 9.9 g of triphenylcarbenium tetrakispentafluorophenylborate was added with previously dehydrated toluene and diluted to 25 ml to obtain a dark reddish brown uniform solution. The concentration is 397 g / L (430 mmol / L).

  The microstructure of the polymer 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.

Weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (Mw / Mn) were measured by GPC (column: Shodex KF-805L × 2) using tetrahydrofuran as a solvent at 40 ° C. It calculated | required as a value of standard polystyrene conversion from the curve.

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

(Synthesis Example 1)
The inside of an autoclave having an internal volume of 1.7 L is purged with nitrogen, charged with 380 ml of cyclohexane and 220 ml of butadiene and stirred. Next, 6 μl of water was added and stirring was continued at 30 ° C. for 30 minutes. 100 ml of hydrogen at 20 ° C. and 1 atmospheric pressure was metered in with an integrating mass flow meter, and then 0.6 ml of a 1 mol / L cyclohexane solution of triethylaluminum (TEA) was added and stirred for 3 minutes. 0.9 ml of a toluene solution of 5 mmol / L of enilvanadium trichloride (CpVCl3), a solution 1 of 5 mmol / L of triphenylcarbenium tetrakis (pentafluorophenyl) borate (Ph3CB (C6F5) 4) obtained in Example 1 Polymerization was carried out for 30 minutes at a polymerization temperature of 40 ° C. in the order of 35 ml. After the reaction, ethanol containing 2,6-di-t-butyl-p-cresol was injected to stop the reaction, and the solvent was evaporated and dried to obtain 70.7 g of polybutadiene. Table 1 (Synthesis Example 1) shows the physical properties of the obtained polybutadiene.

(Synthesis Example 2)
Polymerization was carried out in the same manner as in Synthesis Example 1 except that 0.68 ml of a 10 mmol / L solution of triphenylcarbenium tetrakis (pentafluorophenyl) borate (Ph3CB (C6F5) 4) obtained in Example 2 was used. 71.4 g of polybutadiene was obtained. Table 1 (Synthesis Example 2) shows the physical properties of the obtained polybutadiene.

(Synthesis Example 3)
Polymerization was carried out in the same manner as in Synthesis Example 1 except that 0.34 ml of a 20 mmol / L solution of triphenylcarbenium tetrakis (pentafluorophenyl) borate (Ph3CB (C6F5) 4) obtained in Example 3 was used. 71.1 g of polybutadiene was obtained. Table 1 (Synthesis Example 3) shows the physical properties of the obtained polybutadiene.

(Synthesis Example 4)
Polymerization was carried out in the same manner as in Synthesis Example 1 except that 0.14 ml of a 50 mmol / L solution of triphenylcarbenium tetrakis (pentafluorophenyl) borate (Ph3CB (C6F5) 4) obtained in Example 4 was used. 72.0 g of polybutadiene was obtained. Table 1 (Synthesis Example 4) shows the physical properties of the obtained polybutadiene.

(Synthesis Example 5)
Polymerization was carried out in the same manner as in Synthesis Example 1 except that 68 μl of 100 mmol / L of triphenylcarbenium tetrakis (pentafluorophenyl) borate (Ph 3 CB (C 6 F 5) 4) obtained in Example 5 was used. 0.6 g was obtained. Table 1 (Synthesis Example 5) shows the physical properties of the obtained polybutadiene.

(Synthesis Example 6)
Polymerization was carried out in the same manner as in Synthesis Example 1 except that 35 μl of a 195 mmol / L solution of triphenylcarbenium tetrakis (pentafluorophenyl) borate (Ph 3 CB (C 6 F 5) 4) obtained in Example 6 was used. .8 g was obtained. Table 1 (Synthesis Example 6) shows the physical properties of the obtained polybutadiene.

(Synthesis Example 7)
Polymerization was carried out in the same manner as in Synthesis Example 1 except that 35 μl of a 195 mmol / L slurry of triphenylcarbenium tetrakis (pentafluorophenyl) borate (Ph 3 CB (C 6 F 5) 4) obtained in Comparative Example 1 was used. 0.2 g was obtained. Table 1 (Synthesis Example 7) shows the physical properties of the obtained polybutadiene. A brownish foreign material was observed in the polybutadiene.

(Synthesis Example 8)
Polymerization was carried out in the same manner as in Synthesis Example 1, except that 0.14 ml of 50 mmol / L of triphenylcarbenium tetrakis (pentafluorophenyl) borate (Ph3 CB (C6 F5) 4) obtained in Comparative Example 2 was used. 49.2 g of polybutadiene was obtained. Table 1 (Synthesis Example 8) shows the physical properties of the obtained polybutadiene. A slight brownish foreign material was observed in the polybutadiene.

(Synthesis Example 9)
Polymerization was carried out in the same manner as in Synthesis Example 1 except that 16 μl of a solution of 430 mmol / L of triphenylcarbenium tetrakis (pentafluorophenyl) borate (Ph 3 CB (C 6 F 5) 4) obtained in Comparative Example 3 was used. .4 g was obtained. Table 1 (Synthesis Example 9) shows the physical properties of the obtained polybutadiene. A brownish foreign material was observed in the polybutadiene.

(Synthesis Example 10) Y-based catalyst The inside of an autoclave having an internal volume of 2 L was purged with nitrogen, charged with a solution consisting of 390 ml of toluene and 210 ml of butadiene, and hydrogen was introduced under pressure up to a gauge pressure of 1.0 kgf / cm 2 at 25 ° C. Then, 0.2 ml of a toluene solution (2 mol / L) of diethylaluminum hydride (DEAH) was added and stirred at 550 rpm for 3 minutes. Next, 0.6 ml of a toluene solution (20 mmol / L) of tris [N, N-bis (trimethylsilyl) amido] yttrium was added and stirred for 4 minutes, and then the temperature was raised to 40 ° C. to obtain Example 3. Polymerization was initiated by adding 1.2 ml of a 20 mmol / L solution of triphenylcarbenium tetrakis (pentafluorophenyl) borate (Ph3 CB (C6 F5) 4). 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 3 hours to obtain 54.9 g of polybutadiene. The polymerization results are shown in Table 2.

(Synthesis Example 11) Y-based catalyst The inside of an autoclave having an internal volume of 2 L was purged with nitrogen, and a solution consisting of 390 ml of toluene and 210 ml of butadiene was charged. After the temperature of the solution was adjusted to 30 ° C., 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) (Y (dpm) 3) was added. After aging at 30 ° C. for 2 minutes, 0.6 ml of a solution of 100 mmol / L of triphenylcarbenium tetrakis (pentafluorophenyl) borate (Ph 3 CB (C 6 F 5) 4) obtained in Example 5 was added. . After polymerization at 10 ° 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, ethanol was added to the polymerization solution to recover polybutadiene. The recovered polybutadiene was then vacuum-dried at 70 ° C. for 3 hours to obtain 7.7 g of polybutadiene. The polymerization results are shown in Table 2.

(Synthesis Example 12) Y-based catalyst The inside of an autoclave having an internal volume of 2 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) 6.25 ml was added and stirred at 500 rpm for 3 minutes. Next, 0.15 ml of a toluene solution (50 mmol / L) of yttrium (III) tris (2,2,6,6-tetramethyl-3,5-heptanedioate) (Y (dpm) 3) was added. Warmed to 40 ° C. After stirring for 2 minutes, 0.3 ml of a solution of 50 mmol / L of triphenylcarbenium tetrakis (pentafluorophenyl) borate (Ph3CB (C6F5) 4) obtained in Example 4 was added, and the temperature was raised to 80 ° C. did. After polymerization at 80 ° C. for 15 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. Next, the recovered polybutadiene was vacuum dried at 70 ° C. for 3 hours to obtain 39.7 g of polybutadiene. The polymerization results are shown in Table 2.

(Synthesis Example 13) Gd-based catalyst The inside of an autoclave having an internal volume of 1.5 L was purged with nitrogen, and a solution consisting of 245 ml of cyclohexane solvent and 250 ml of butadiene was charged. Next, 1.5 ml of a cyclohexane solution (2 mol / L) of triethylaluminum (TEAL) was added. Next, 1.35 ml of a toluene solution (0.003 mol / L) of tris (2,2,6,6-tetramethyl-3,5-heptanedionato) gadolinium (Gd (dpm) 3) was added, 0.4 ml of a solution of 20 mmol / L of triphenylcarbenium tetrakis (pentafluorophenyl) borate (Ph3 CB (C6 F5) 4) obtained in 3 was added. 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, ethanol was added to the polymerization solution to recover polybutadiene. Subsequently, the recovered polybutadiene was vacuum-dried at 70 ° C. for 3 hours to obtain 24.3 g of polybutadiene. The polymerization results are shown in Table 2.

(Synthesis Example 14) Tb-based catalyst The inside of an autoclave having an internal volume of 1.5 L was purged with nitrogen, and a solution consisting of 250 ml of cyclohexane solvent and 250 ml of butadiene was charged. Then, 1.0 ml of a cyclohexane solution (2 mol / L) of triethylaluminum (TEAL) was added. Next, 0.2 ml of a cyclohexane solution (0.01 mol / L) of tris (2,2,6,6-tetramethyl-3,5-heptanedionato) terbium (Tb (dpm) 3) was added, followed by 0.2 ml of a solution of 20 mmol / L of triphenylcarbenium tetrakis (pentafluorophenyl) borate (Ph3 CB (C6 F5) 4) obtained in 3 was added. After polymerization at 50 ° 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, ethanol was added to the polymerization solution to recover polybutadiene. The recovered polybutadiene was then vacuum dried at 80 ° C. for 3 hours to obtain 34.5 g of polybutadiene. The polymerization results are shown in Table 2.

(Synthesis Example 15) Nd catalyst The inside of an autoclave having an internal volume of 1.5 L was purged with nitrogen, and a solution consisting of 245 ml of cyclohexane solvent and 250 ml of butadiene was charged. Then, 1.0 ml of a cyclohexane solution (2 mol / L) of triethylaluminum (TEAL) was added. Next, after adding 0.2 ml of a cyclohexane solution (0.01 mol / L) of neodymium versatate (Nd (Ver) ₃ ), triphenylcarbenium tetrakis (pentafluorophenyl) borate obtained in Example 3 ( 0.2 ml of a solution of 20 mmol / L of Ph3CB (C6 F5) 4) was added. After polymerization at 50 ° 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, ethanol was added to the polymerization solution to recover polybutadiene. The recovered polybutadiene was then vacuum dried at 80 ° C. for 3 hours to obtain 8.7 g of polybutadiene. The polymerization results are shown in Table 2.

(Synthesis Example 16) The inside of an autoclave having a La-based catalyst internal volume of 1.5 L was purged with nitrogen, and a solution consisting of 245 ml of cyclohexane solvent and 250 ml of butadiene was charged. Then, 1.0 ml of a cyclohexane solution (2 mol / L) of triethylaluminum (TEAL) was added. Next, 0.2 ml of a toluene solution (0.01 mol / L) of tris (2,2,6,6-tetramethyl-3,5-heptanedionato) lanthanum (La (dpm) ₃ ) was added, followed by 0.2 ml of a solution of 20 mmol / L of triphenylcarbenium tetrakis (pentafluorophenyl) borate (Ph3CB (C6F5) 4) obtained in 3 was added. After polymerization at 50 ° 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, ethanol was added to the polymerization solution to recover polybutadiene. Next, the recovered polybutadiene was vacuum-dried at 80 ° C. for 3 hours to obtain 13.6 g of polybutadiene. The polymerization results are shown in Table 2.

(Synthesis Example 17) Dy catalyst The inside of an autoclave having an internal volume of 1.5 L was purged with nitrogen, and a solution consisting of 245 ml of cyclohexane solvent and 250 ml of butadiene was charged. Then, 1.0 ml of a cyclohexane solution (2 mol / L) of triethylaluminum (TEAL) was added. Next, after adding 0.4 ml of a toluene solution (0.005 mol / L) of tris (2,2,6,6-tetramethyl-3,5-heptanedionato) dysprosium (Dy (dpm) ₃ ), Examples 0.2 ml of a solution of 20 mmol / L of triphenylcarbenium tetrakis (pentafluorophenyl) borate (Ph3CB (C6F5) 4) obtained in 3 was added. After polymerization at 50 ° 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, ethanol was added to the polymerization solution to recover polybutadiene. The recovered polybutadiene was then vacuum dried at 80 ° C. for 3 hours to obtain 33.5 g of polybutadiene. The polymerization results are shown in Table 2.

  The present invention can provide a polymerization catalyst system using a uniform solution of pentafluorophenyl borate salt in a wide concentration range. Moreover, according to the present invention, it is also possible to provide a polymerization catalyst system using a uniform solution of pentafluorophenyl borate salt that gives an excellent polymer with less foreign matters compared to a suspension or a high concentration solution. The polymerization catalyst system using the homogeneous solution of pentafluorophenyl borate salt of the present invention contributes to downsizing of the solution tank and the solvent recovery process and improvement of the polymer quality.

The present invention relates to a polymerization process using co-diene polymerization catalyst solution and it using high concentration solution of pentafluorophenyl borate salt.

The present invention provides a method for preparing a solution of a pentafluorophenyl borate salt, which comprises using an aromatic hydrocarbon and a halogenated hydrocarbon in combination as a solvent. This enables the solution polymerization by homogeneous solution, and density unevenness in the reaction system to suppress the localized abnormal reaction, can provide a co-diene polymers foreign matter Ru excellent fewer mechanical properties.

Claims (9)

A catalyst for the polymerization of olefins and conjugated dienes, which comprises using, as a catalyst component, a solution of an aromatic hydrocarbon and a pentafluorophenyl borate salt using a halogenated hydrocarbon in combination as a solvent.   2. The catalyst for olefin and conjugated diene polymerization according to claim 1, wherein the aromatic hydrocarbon is an alkylbenzene substituted with an alkyl group having 1 to 12 carbon atoms.   2. The olefin / conjugated diene polymerization catalyst according to claim 1, wherein the aromatic hydrocarbon is a compound selected from toluene, ethylbenzene, and xylene.   The olefin / conjugated diene polymerization catalyst according to any one of claims 1 to 3, wherein the halogenated hydrocarbon is 1,2-dichlorobenzene.   The olefin / conjugated diene polymerization catalyst according to any one of claims 1 to 3, wherein the pentafluorophenyl borate salt is triphenylcarbenium tetrakis (pentafluorophenyl) borate.   The olefin / conjugated diene polymerization catalyst according to any one of claims 1 to 3, wherein the solution concentration of the pentafluorophenyl borate salt is higher than 5 mmol / liter.   The olefin / conjugated diene polymerization catalyst according to claim 6, wherein the pentafluorophenyl borate salt is triphenylcarbenium tetrakis (pentafluorophenyl) borate. 8. The catalyst for polymerization of olefin and conjugated diene according to claim 7, wherein the solution concentration of triphenylcarbenium tetrakis (pentafluorophenyl) borate is higher than 5 mmol / liter and lower than 430 mmol / liter.   A method for polymerizing an olefin and a conjugated diene, wherein the polymerization catalyst according to any one of claims 1 to 8 is used.