RU2436802C2 - Method of producing polybutadiene - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: method involves cis-1,4-polymerisation of 1,3-butadiene first, followed by syndiotactic 1,2-polymerisation of the obtained product in the formed polymerisation system in the presence of a catalyst containing a cobalt compound, an alkylaluminium compound and a sulphur compound. In order to stop polymerisation, a halogen-containing acid or salt of a halogen-containing acid is added, where both have the general formula given below (I): M' (X'O_q)_rZ'_s (I) , where M' is a metal atom or a hydrogen atom, X' is a halogen atom selected from chlorine, bromine and iodine, O is an oxygen atom, q is a whole number from 1 to 4; Z' is an anion capable of bonding with an M' atom, r is a whole number equal to or greater than 1, and the sum r+s is the oxidation number of M'.

EFFECT: obtaining polybutadiene with less smell.

10 cl, 19 ex, 2 tbl

Description

FIELD OF THE INVENTION

The present invention relates to a method for producing, by polymerization of 1,3-butadiene, a reinforced polybutadiene with reduced odor (hereinafter referred to as VCR polymer), comprising a cis-1,4 polymer and a syndiotactic 1,2 polymer.

State of the art

JP-B-1974-17666 (Patent Literature 1) and JP-B-1974-17667 (Patent Literature 2) describe, as a method for producing a VCR polymer, a method which involves cis-1,4 polymerization 1, 3-butadiene in an inert organic solvent using a catalyst obtained from water, a soluble compound of cobalt and chloride of an organoaluminum compound with the general formula AlR _n X _3-n , and then carrying out in the polymerization system the syndiotactic 1,2-polymerization of 1,3-butadiene in the presence of a syndiotactic 1,2-poly a sterilization process obtained from a soluble cobalt compound, an organoaluminum compound with the general formula AlR ₃ and carbon disulfide.

In addition, as a method of producing a VCR polymer in patents JP-B-1987-171 (patent literature 3), JP-B-1988-36324 (patent literature 4), JP-B-1990-37927 (patent literature 5), JP-B-1990-38081 (Patent Literature 6) and JP-B-1991-63566 (Patent Literature 7) describe, for example, a method that involves 1,3- cis-1,4 polymerization of VCR polymer butadiene in the presence or absence of carbon disulfide or after receiving the VCR polymer in the separation of 1,3-butadiene from carbon disulfide for reuse and circulation in the separation of 1,3-butadiene , essentially free of carbon disulfide and an inert organic solvent. Moreover, JP-B-1992-48815 (Patent Literature 8) describes a VCR polymer which exhibits a low degree of swelling of the extrudable melt upon conversion to compound, and upon vulcanization of the compound is excellent in terms of tensile stress and multiple fracture resistance bending and is suitable for the production of tire side surfaces.

JP-A-2000-44633 (Patent Literature 9) provides a method for producing a new VCR polymer, which consists in cis-1,4-polymerizing 1,3-butadiene in an inert organic solvent, consisting mainly of fraction C4 using a catalytic system comprising a halogen-containing organoaluminum compound, a soluble cobalt compound and water, and in the resulting polymerization reaction mixture the syndiotactic 1,2-polymerization of 1,3-butadiene in the presence of a syndiotactically catalyst and 1,2-polymerization obtained from a soluble cobalt compound, a trialkylaluminum compound and carbon disulfide. Moreover, it is disclosed that the obtained VCR polymer is a VCR composition containing from 3 to 30 wt.% A substance insoluble in boiling n-hexane, which is syndiotactic 1,2-polybutadiene, in the form of dispersed short fibrous crystals, and from 97 to 70 wt.% Soluble in boiling n-hexane substance, which has a cis structure containing 90% or more cis-1,4-polybutadiene.

Patents JP-A-2000-154215 (Patent Literature 10) and JP-A-2000-159836 (Patent Literature 11) provide a method for producing a new VCR polymer, which involves the cis-1,4 polymerization of 1,3-butadiene using a catalyst obtained from (A) a complex compound of a transition metal of the metallocene type, and (B) an ionic compound formed by not forming coordination bonds with the anion and cation and / or alumoxane, and in carrying out the syndiotactic 1,2 reaction mixture resulting from polymerization polymerization of 1,3-butadiene and in the presence of a catalyst obtained by at least one compound selected from (E) a cobalt compound, (F) an isocyanic acid compound and carbon disulfide.

However, when syndiotactic 1,2-polymerization of 1,3-butadiene is observed, depending on the polymerization conditions used, there are cases of unpleasant odor from the sulfur compound used, which requires improvement.

US Pat. No. 6,956,093 (Patent Literature 12) discloses a method for producing a rubber composition with a reduced odor, which comprises treating with hydrogen peroxide the syndiotactic 1,2-polybutadiene obtained using a catalyst containing carbon disulfide as a catalytic component. However, this method is not preferred since hydrogen peroxide can oxidize the polybutadiene double bond or the remaining butadiene monomer.

Patent Literature 1: JP-B-1974-17666

Patent Literature 2: JP-B-1974-17667

Patent Literature 3: JP-B-1987-171

Patent Literature 4: JP-B-1988-36324

Patent Literature 5: JP-B-1990-37927

Patent Literature 6: JP-B-1990-38081

Patent Literature 7: JP-B-1991-63566

Patent Literature 8: JP-B-1992-48815

Patent Literature 9: JP-A-2000-44633

Patent Literature 10: JP-A-2000-154215

Patent Literature 11: JP-B-2000-159836

Patent literature 12: patent US 6956093

Disclosure of invention

The problem to which the present invention is directed, is to provide a method for the polymerization of 1,3-butadiene-reinforced polybutadiene with reduced odor (hereinafter, often referred to as the polymer VCR), including cis-1,4-polymer and syndiotactic 1 , 2 polymer.

The present invention relates to a method for producing polybutadiene with a reduced odor, which consists in cis-1,4-polymerizing 1,3-butadiene, and then carrying out syndiotactic 1,2-polymerization of the reaction product in the resulting polymerization system, the method being characterized in that that after polymerization, a halogen-containing acid or a salt of a halogen-containing acid is introduced, both are represented by the following general formula (I):

M '(X'O _q ) _r Z' _s (I)

(where M 'is a metal atom or a hydrogen atom, X' is a halogen atom selected from chlorine, bromine and iodine, O is an oxygen atom, q is an integer from 1 to 4, Z 'is an anion capable of forming a bond with atom M ', r is an integer of 1 or more, and the sum r + s is the oxidation state of M').

Preferably, in the present invention, the X 'atom in the compound represented by general formula (I) is chlorine.

Preferably, in the present invention, the compound represented by general formula (I) is hypochlorous acid or a hypochlorous acid salt.

The present invention can be used as a method for producing a reduced odor reinforced polybutadiene rubber using the polybutadiene obtained by the following method. Namely, firstly, a reinforced polybutadiene rubber with a reduced odor can be obtained using polybutadiene obtained using a cis-1,4 polymerization catalyst as a catalyst, including a cobalt compound, an organoaluminum compound and water. Secondly, a reduced odor reinforced polybutadiene rubber can be obtained using polybutadiene obtained by cis-1,4 polymerization of 1,3-butadiene using a catalyst obtained from a metallocene-type transition metal complex and an ionic compound formed without coordination bonds anion and cation and / or alumoxane. Thirdly, a reduced odor reinforced polybutadiene rubber can be obtained using polybutadiene obtained using cis-1,4 polymerization as a catalyst obtained from (A) a yttrium compound, (B) an ionic compound formed not forming coordination bonds anion and cation; and (B) an organometallic compound of an element selected from the 2nd group, the 12th group and the 13th group of the Periodic table.

First, for the method of the present invention, when using polybutadiene obtained using a cis-1,4 polymerization catalyst as a catalyst comprising a cobalt compound, an organoaluminum compound and water, it is preferable that the organoaluminum compound is a trialkylaluminum compound of the formula R ¹ ₃ Al (where the R ¹ group is a hydrocarbon group having from 1 to 10 carbon atoms) and a halogen-containing aluminum compound of the formula R ² _3-n AlX _n (where the R ² group is a hydrocarbon group, having from 1 to 10 carbon atoms, X is a halogen atom, and n is a number from 1 to 2).

It is also preferred that the cis-1,4 polymerization catalyst be a catalyst obtained by extracting components selected from a metal compound of the 3rd group of the Periodic Table, a compound consisting of an aluminum hydride of aluminum, butadiene, methylaluminoxane and a chlorine-containing compound.

Secondly, it is also preferable that the cis-1,4 polymerization catalyst be a catalyst obtained from a metallocene-type transition metal complex compound, an ionic compound formed by anion and cation not forming coordination bonds, an organometallic compound of an element of groups 1 to Of the 3rd Periodic Table and water [(organometallic compound of the element of groups 1 through 3 of the periodic table) / (water) = from 0.66 to 5 (molar ratio)].

Preferably, when using a catalyst containing a yttrium compound, a yttrium compound with a bulky ligand represented by the following general formula can be used:

[Formula 1]

(where each of the groups R ¹ , R ² and R ³ is a hydrogen atom or a hydrocarbon group with the number of carbon atoms from 1 to 12, O is an oxygen atom, and Y is a yttrium atom).

In this case, it is preferable that the syndiotactic 1,2-polymerization catalyst consist of a cobalt compound, an alkyl aluminum compound, and a sulfur compound.

The present invention also relates to a method for producing a reduced odor reinforced polybutadiene, wherein the polybutadiene is a reinforced polybutadiene containing (1) from 3 to 30 wt.% Insoluble in boiling n-hexane and (2) from 97 to 70 wt.% Soluble in boiling n-hexane substance.

The present invention provides a method for producing a reduced odor reinforced polybutadiene rubber comprising a cis-1,4 polymer and a syndiotactic 1,2 polymer by introducing after polymerization a 1,3-butadiene of a halogen-containing acid or a salt of a halogen-containing acid.

BEST MODE FOR CARRYING OUT THE INVENTION

The present invention provides a method for producing polybutadiene, which involves the cis-1,4 polymerization of 1,3-butadiene, and then the syndiotactic 1,2-polymerization of the reaction product in the resulting polymerization system, the substance introduced after polymerization to reduce the odor is a halogen-containing acid or a salt of a halogen-containing acid, both represented by the following general formula (I):

M '(X'O _q ) _r Z' _s (I)

(where M 'is a metal atom or a hydrogen atom, X' is a halogen atom selected from chlorine, bromine and iodine, O is an oxygen atom, q is an integer from 1 to 4, Z 'is an anion capable of forming a bond with atom M ', r represents an integer equal to 1 or more, and the sum of r + s represents the oxidation state of M'). As the atom M ', atoms of hydrogen, lithium, sodium, potassium, magnesium, calcium, strontium, barium, yttrium, vanadium, iron, cobalt, nickel, copper, zinc, boron, aluminum, etc. can be mentioned. Preferably, M ′ is a hydrogen, lithium, sodium, potassium, magnesium, calcium or aluminum atom, hydrogen, sodium, potassium, magnesium or calcium atoms are particularly desirable, and even more preferably when it is a sodium or calcium atom.

As the X 'atom, chlorine, bromine and iodine atoms can be mentioned. Among them, a chlorine atom is preferred.

q is an integer from 1 to 4, preferably 1 or 2, particularly preferably 1.

The anion Z 'is an anion different from the halogen-containing acid ion, and there are no particular restrictions on it, provided that it can bind, compensating for the positive charge M', remaining without sufficient compensation by the halogen-containing acid ion. Mention may be made, for example, of halogen ions such as chlorine, bromine, iodine and the like, hydroxide ion, oxide ion, nitric acid ion, nitrous acid ion, sulfuric acid ion, phosphoric acid ion, phosphoric acid ion, boric acid ion , a carboxylic acid ion, and an alkoxy ion. Among them, chlorine ion and hydroxide ion are particularly preferred.

r is the number of halogen-containing acid ions bonded to the atom M 'and represents a positive amount not exceeding the oxidation state M'.

s is the number of anions Z 'bonded to the atom M'. Therefore, the sum r + s represents the oxidation state of M '.

As specific examples of the halogen-containing acid or salt of the halogen-containing acid, mention may be made of hypochlorous acid, perchloric acid, hypochlorous acid, perchloric acid, hydrobromic acid, bromic acid, hydrobromic acid, perbromic acid, hypochlorous acid, iodic acid, iodic acid, iodic acid, iodic acid, iodic acid, iodic acid, iodic acid, iodic acid, iodic acid, iodic acid, iodic acid, iodic acid, iodic acid, iodic acid, iodic acid, iodic acid, iodic acid, iodic acid, iodide acid , sodium hypochlorite, magnesium hypochlorite, calcium hypochlorite, calcium chloride hypochlorite, and calcium hypochlorite. Preferred are sodium hypochlorite, calcium hypochlorite, calcium chloride hypochlorite and calcium hydroxide hypochlorite, and sodium hypochlorite is particularly desirable.

As the solvent used in the preparation of the polybutadiene of the present invention, mention may be made of hydrocarbon solvents such as a straight chain aliphatic hydrocarbon such as n-hexane, butane, heptane or pentane, a cyclic aliphatic hydrocarbon such as cyclopentane or cyclohexane, a C4 series olefinic hydrocarbon such like 1-butene, cis-2-butene or trans-2-butene, white spirit, solvent naphtha, kerosene and the like, halogenated hydrocarbon solvents such as methylene chloride and the like, and so on e. They can be used alone or as a mixture. Among them, a cyclohexane-containing solvent is preferably used. A mixture of cyclohexane and a C4 hydrocarbon (e.g. cis-2-butene or trans-2-butene) is used particularly preferably.

As the first cis-1,4 polymerization catalyst, a catalyst comprising a cobalt compound, an organoaluminum compound and water can be used. As the organoaluminum compound, a mixture of a trialkylaluminum compound with the formula R ¹ ₃ Al (where the R ¹ group is a hydrocarbon group having from 1 to 10 carbon atoms) and a halogen-containing aluminum compound with the formula R ² _3-n AlX _n (where the group R ² is a hydrocarbon group having from 1 to 10 carbon atoms, X is a halogen atom, and n is a number from 1 to 2).

As the cobalt compound in the cis-1,4 polymerization catalyst, a salt or cobalt complex is preferably used. Particularly preferred cobalt compounds include cobalt salts, such as cobalt chloride, cobalt bromide, cobalt nitrate, cobalt octylate, cobalt naphthenate, cobalt acetate, cobalt malonate and the like, cobalt bisacetylacetone cobalt acetate, triacetalacetate acetate, triacetalacetate acetate its trialkylphosphine complex, its complex with an organic base, such as its complex with pyridine or its complex with picoline, or its complex with ethyl alcohol, etc.

As the trialkylaluminum compound of the formula R ¹ ₃ Al (where the R ¹ group is a hydrocarbon group having from 1 to 10 carbon atoms, preferably having from 2 to 8 carbon atoms), mention may be made of triethylaluminum, trimethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum and so on .d. Among them, triethylaluminum is preferred.

As a halogen-containing aluminum compound of the formula R ² _3-n AlX _n (where the R ² group is a hydrocarbon group having from 1 to 10 carbon atoms, preferably having from 2 to 8 carbon atoms, the X atom is a halogen atom, and n represents a number from 1 to 2) mention may be made of dialkyl aluminum halides such as dialkyl aluminum chloride, dialkyl aluminum bromide and the like, alkyl aluminum sesquichalides such as alkyl aluminum sesquichloride, alkyl aluminum sesquioxides and the like, alkyl aluminum dihalides, such such as alkylaluminum dichloride, alkylaluminum dibromide and the like, etc. As specific compounds, diethylaluminum monochloride, diethylaluminum monobromide, dibutylaluminum monochloride, ethylaluminum sesquichloride, ethylaluminum dichloride, dicyclohexylaluminum monochloride, diphenylaluminum monochloride, etc. can be mentioned. Among them, diethylaluminum monochloride is preferred.

The amount of cobalt compound used is usually from 1 × 10 ^-7 to 1 × 10 ^-4 mol, preferably from 1 × 10 ^-6 to 1 × 10 ^-5 mol, per 1 mol of butadiene used.

The amount of trialkyl aluminum used is usually from 10 to 5000 mol, preferably from 50 to 1000 mol, per 1 mol of cobalt compound used.

The amount of halogen-containing aluminum compound used is from 0 to 1, preferably from 0.1 to 0.9, particularly preferably from 0.25 to 0.75, in terms of the ratio (X / Al) of the amount of X atom in the halogen-containing aluminum compound to the amount of atom Al in trialkylaluminium and a halogen-containing aluminum compound.

The amount of water used is from 0.1 to 1.45 mol, preferably from 0.2 to 1.2 mol, per 1 mol of aluminum compound.

With regard to the order of introduction of the catalytic components, there are no particular restrictions. However, it is preferred that the trialkylaluminum and the halogen-containing aluminum compound are mixed and incubated in an inert solvent and then used. It is desirable that the holding time is from 0.1 hours to 24 hours, and it is preferable that the holding temperature is in the range from 0 to 80 ° C.

Preferably, water is added to the mixture after exposure followed by further exposure. Preferably, the holding time is from 0.1 hours to 24 hours, and it is desirable that the holding temperature is in the range from 0 to 80 ° C.

As a catalyst for cis-1,4 polymerization, you can also use catalysts obtained by extracting components selected from a metal compound of the 3rd group of the Periodic Table, a compound consisting of an aluminum alkyl halide, butadiene, methylaluminoxane and a chlorine-containing compound.

A metal atom that is part of a metal compound of the 3rd group of the Periodic Table, which is a component of the above catalyst system, is an atom of the 3rd group of the Periodic Table and includes elements of a number of lanthanides, elements of a number of actinides, etc. A rare earth metal atom is preferred. Specifically, mention may be made of neodymium, praseodymium, cerium, lanthanum, gadolinium, or mixtures thereof. A neodymium atom is particularly preferred.

As a metal compound of the 3rd group of the Periodic Table, mention may be made of a metal carboxylate of the 3rd group of the Periodic table, its alkoxide, its complex with β-diketone, its phosphate or its phosphite, etc. Among them, carboxylate and phosphate are preferred, and carboxylate is particularly desirable.

The metal carboxylate of the 3rd group of the Periodic Table is a compound with the general formula (RCO ₂ ) ₃ M (where the M atom is a metal atom of the 3rd group of the Periodic Table and the R group is a hydrocarbon group with the number of carbon atoms from 1 to 20) .

The group R is a saturated or unsaturated alkyl group, which is a straight chain, branched chain or is cyclic. The carboxyl group of CO ₂ is bound to a primary, secondary or tertiary carbon atom. Specifically, mention may be made of salts of octanoic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, benzoic acid, naphthenic acid, Versatic acid (a trademark of Shell Chemical; a carboxylic acid in which a carboxyl group is attached to a tertiary carbon atom) and t .d. Among them, 2-ethylhexanoic acid and Versatic acid are preferred.

The metal alkoxide of the 3rd group of the Periodic Table is a compound with the general formula (RO) ₃ M (wherein the R group and the M atom are defined in the same manner as described above). As examples of an alkoxy group represented as RO, mention may be made of a 2-ethylhexyloxy group, an oleyloxy group, a stearyloxy group, a phenoxy group, and a benzyloxy group. Among them, a 2-ethylhexyloxy group and a benzyloxy group are preferred.

As the metal complex of the 3rd group of the Periodic Table with β-diketone, mention may be made, for example, of the metal complex of the 3rd group of the Periodic Table with acetylacetone, benzoylacetone, propionitrile acetone, valeryl acetone or ethyl acetoacetone. Among them, a complex with acetylacetone and a complex with ethyl acetoacetone are preferred.

As the phosphate or phosphite of the metal of the 3rd group of the Periodic Table, mention may be made of bis (2-ethylhexyl) phosphate of the metal of the 3rd group of the Periodic table, its bis (1-methylheptylphosphate), its bis (paranylphenyl) phosphate, bis (polyethylene glycol- para-nonylphenyl) phosphate, its (1-methylheptyl) (2-ethylhexyl) phosphate, its (2-ethylhexyl) (paranylphenyl) phosphate, its mono-2-ethylhexyl-2-ethylhexylphosphonate, its mono-2-nonylphenyl- 2-ethylhexylphosphonate, its bis (2-ethylhexyl) phosphinate, its bis (1-methylheptyl) phosphinate, its bis (paranylphenyl) phosphinate, its (1-methylheptyl) (2-these hexyl) phosphinate, its (2-ethylhexyl) (p-nonylphenyl) phosphinate, etc. Among them, preferred are metal bis (2-ethylhexyl) phosphate of the 3rd group of the Periodic Table, its bis (1-methylheptyl) phosphate, its mono-2-ethylhexyl-2-ethylhexylphosphonate, its bis (2-ethylhexyl) phosphinate, etc. d.

Of the above compounds, neodymium phosphate or neodymium carboxylate is particularly desirable, and carboxylic acid salts, for example 2-ethylhexanoic acid neodymium salt and Versatic acid neodymium salt, are most preferred.

As the alkyl aluminum hydride compound of the above catalyst system, diethyl aluminum hydride, dipropyl aluminum hydride, di-n-butyl ethyl aluminum hydride, diisobutyl aluminum hydride, diphenyl aluminum hydride, etc. can be mentioned.

As the chlorine-containing compound of the above catalyst system, mention may be made of alkyl aluminum chloride. In particular, mention may be made of a dialkylaluminum halide such as dialkylaluminum chloride, dialkylaluminum bromide or the like, one-and-a-half alkylaluminum halide, one-and-a-half alkylaluminum chloride or the like, an alkylaluminum dihalide, such as etc. As specific compounds, diethylaluminum monochloride, diethylaluminum monobromide, dibutylaluminum monochloride, ethylaluminum sesquichloride, ethylaluminum dichloride, dichlorohexylaluminum monochloride, diphenylaluminum monochloride, etc. can be mentioned.

It is preferred that the relative contents of the individual components of the above catalyst system are as follows:

(compound representing alkyl aluminum hydride): (metal compound of the 3rd group of the Periodic Table) = from 1: 1 to 100: 1 (molar ratio);

(butadiene) :( metal compound of the 3rd group of the Periodic table) = from 0.5: 1 to 200: 1 (molar ratio);

(methylaluminoxane) :( metal compound of the 3rd group of the Periodic table) = from 1: 1 to 1000: 1 (molar ratio);

(chlorine-containing compound) :( metal compound of the 3rd group of the Periodic table) = from 1: 1 to 10: 1 (molar ratio).

Preferably, the above catalyst system is used after exposure. It is desirable that the exposure time was from 1 minute to 150 minutes. Preferably, the holding temperature is in the range from −10 ° C. to 60 ° C.

As a second cis-1,4 polymerization catalyst, a catalyst obtained from (a) a metallocene-type transition metal complex compound and (b) an ionic compound formed by non-coordinating anion and cation and / or alumoxane compounds, or a catalyst prepared from (a) a complex compound of a transition metal of a metallocene type, (b) an ionic compound formed by anion and cation not forming coordination bonds, (c) an organometallic compound of an element of groups 1 through 3 of Pe the periodic table and (d) water [(c) / (d) = 0.65 to 5 (molar ratio)].

As the complex compound of the transition metal of the metallocene type, which is component (a), we can mention the complex of the compound of the transition metal of groups 4 through 8 of the Periodic table of the metallocene type.

Mention may be made, for example, of a transition metal complex of the 4th group of the Periodic Table, such as titanium or zirconium, of a metallocene type (e.g. CpTiCl ₃ ), of a transition metal complex of the 5th group of the Periodic Table, such as vanadium, niobium or tantalum, of a metallocene type , a transition metal complex of the 6th group of the Periodic table, such as chromium, metallocene type, as well as a transition metal complex of the 8th group of the Periodic table, such as cobalt or nickel, metallocene type.

Among them, a transition metal complex of the 5th group of the metallocene type periodic table is preferably used.

As a transition metal complex of the 5th group of the periodic table of the metallocene type, mention may be made of compounds with the following general formulas:

(1) RM · L _a

(2) R _n MX _2-nL L _a

(3) R _n MX _3-nL L _a

(4) RMX ₃ · L _a

(5) RM (O) X ₂ · L _a

(6) R _n MX _3-n (NR ') L _a

(where n is 1 or 2, and a is 0, 1 or 2).

Among them, it is preferable to mention RM · L _a , RMX ₃ · L _a , RM (O) X ₂ · L _a , etc.

Preferably, M is a transition metal compound of the 5th group of the Periodic Table. In particular, M is vanadium (V), niobium (Nb) or tantalum (Ta), with vanadium being preferred.

The R group is a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a fluorenyl group or a substituted fluorenyl group.

As a substituent in a substituted cyclopentadienyl group, a substituted indenyl group or a substituted fluorenyl group, for example, straight or branched aliphatic hydrocarbon groups such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl can be mentioned , hexyl and the like, aromatic hydrocarbon groups such as phenyl, tolyl, naphthyl, benzyl and the like, as well as silicon atoms containing hydrocarbon groups, such like trimethylsilyl and the like. In addition, such groups include groups in which the cyclopentadienyl ring is bonded to group X via a linking group such as dimethylsilyl, dimethylmethylene, methylphenylmethylene, diphenylmethylene, ethylene, substituted ethylene and the like.

As specific examples of the substituted cyclopentadienyl group, mention may be made of a methylcyclopentadienyl group, a 1,2-dimethylcyclopentadienyl group, a 1,3-dimethylcyclopentadienyl group, a 1,3-di (tert-butyl) cyclopentadienyl group, and a 1,2,3-trimethylcyclopentadienyl group.

Group X represents a hydrogen atom, a halogen atom, a hydrocarbon group with the number of carbon atoms from 1 to 20, an alkoxy group or an amino group. All groups X may be the same or different from each other.

As a group X, a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, methyl, ethyl, butyl, methoxy, ethoxy, dimethylamino, diethylamino, etc. are preferred.

Compound L is a Lewis base and is a common inorganic or organic compound such as a Lewis base that can form a coordination bond with a metal. Particularly preferred is a compound that does not have an active hydrogen atom. As specific examples, mention may be made of ether, ester, ketone, amine, phosphine, silyloxy compound, olefin, diene, aromatic compound, as well as alkine.

NR 'is an imide group. R 'is a hydrocarbon group with the number of carbon atoms from 1 to 25.

As component (a), i.e. a complex compound of a transition metal of the 5th group of the periodic table of the metallocene type, it is preferable in which M is vanadium, that is, a vanadium compound. For example, RV · L _a , RVX · L _a , R ₂ V · L _a , RVX ₂ · L _a , R ₂ VX · L _a , RVX ₃ · L _a and RV (O) X ₂ · L _a are desirable . Compounds RV · L _a and RVX ₃ · L _{a are} particularly preferred.

As RM · L _a , i.e., compounds of a transition metal of the 5th group of the Periodic Table with an oxidation state of +1 with one cycloalkadienyl group as a ligand, mention may be made of cyclopentadienyl (benzene) vanadium, cyclopentadienyl (toluene) vanadium, cyclopentadienyl (xylene) vanadium , cyclopentadienyl (trimethylbenzene) vanadium, cyclopentadienyl (hexamethylbenzene) vanadium, cyclopentadienyl (ferrocene) vanadium, methylcyclopentadienyl (benzene) vanadium, etc.

The compound represented by the formula R _n MX _2-n · L _a , where n is 1, that is, this compound has one cycloalkadienyl group as a ligand, may include, as other ligands, a ligand forming a σ-bond, a hydrogen atom, a halogen atom, such as a chlorine atom, a bromine atom, an iodine atom or the like, a hydrocarbon group such as a methyl group, a phenyl group, a benzyl group, a nonopentyl group, a trimethylsilyl group, a bistrimethylsilylmethyl group or the like, a hydrocarbonoxy group such as a methoxy group , an ethoxy group, an isopropoxy group or the like, and a hydrocarbonamino group such as a dimethylamino group, a diethylamino group, a diisopropylamino group, a dioctylamino group or the like.

In addition, as another ligand, the compound may include a non-charge Lewis base such as an amine, amide, phosphine, ether, ketone, ester, olefin, diene, aromatic hydrocarbon, alkine or the like. A Lewis base that does not contain an active hydrogen atom is preferred.

The compound represented by the formula R _n MX _2-n · L _a , where n is 2, that is, this compound has two cycloalkadienyl groups as a ligand, includes those compounds in which two cycloalkadienyl rings are linked to each other via a bridging group, such as Me ₂ Si group, dimethylethylene group, methylphenylmethylene group, diphenylmethylene group, ethylene group, substituted ethylene group or the like.

As specific examples of the compound represented by the formula R _n MX _2-n · L _a in which n = 1, that is, a transition metal compound of the 5th group of the Periodic table with an oxidation state of +2 with one cycloalkadienyl group as a ligand, mention may be made of Chlorocyclopentadienyl (tetrahydrofuran) vanadium, Chlorocyclopentadienyl (trimethylphosphine) vanadium and Chlorocyclopentadienylbis (trimethylphosphine) vanadium.

As specific examples of the compound represented by the formula R _n MX _2-n · L _a in which n = 2, that is, a transition metal compound of the 5th group of the Periodic table with an oxidation state of +2 with two cycloalkadienyl groups as a ligand, mention may be made of biscyclopentadienyl vanadium, bis (methylcyclopentadienyl) vanadium, bis (1,2-dimethylcyclopentadienyl) vanadium and bis (1,3-dimethylcyclopentadienyl) vanadium.

As specific examples of the compound represented by the formula R _n MX _3-n · L _a , in which n = 1, mention may be made of cyclopentadienyl vanadium dichloride, methyl cyclopentadienyl vanadium dichloride, (1,3-dimethyl cyclopentadienyl) vanadium dichloride and (1-butyl-3- dichloride methylcyclopentadienyl) vanadium. As specific examples of the compound represented by the formula R _n MX _3-n · L _a , in which n = 2, mention may be made of dicyclopentadienyl vanadium chloride and bis (methylcyclopentadienyl) vanadium chloride.

As specific examples of the compound represented by the formula RMX ₃ , the following compounds may be mentioned.

(i) Mention may be made of cyclopentadienyl vanadium trichloride. Mention may be made of monosubstituted cyclopentadienyl vanadium trichlorides, for example methyl cyclopentadienyl vanadium trichloride, ethyl cyclopentadienyl vanadium trichloride and propyl cyclopentadienyl vanadium trichloride.

(ii) Mention may be made of 1,2-dibasic cyclopentadienyl vanadium trichlorides, for example (1,2-dimethylcyclopentadienyl) vanadium trichloride, (1-ethyl-2-methylcyclopentadienyl) vanadium trichloride, (1-methyl-2-propylcyclopentadienyl) vanadium trichloride 1-butyl-2-methylcyclopentadienyl) vanadium and (1-methyl-2-bis (trimethylsilyl) methylcyclopentadienyl) vanadium trichloride.

(iii) Mention may be made of 1,2,3-trisubstituted cyclopentadienyl vanadium trichlorides, for example (1,2,3-trimethylcyclopentadienyl) vanadium trichloride.

As specific examples of the compound represented by the formula RM (O) X ₂ , mention may be made of cyclopentadieniloxovanadium dichloride and methylcyclopentadieniloxovanadium dichloride. In addition, methyl substituted compounds obtained by replacing the chlorine atom in each of the above compounds with a methyl group can be mentioned.

Mention may be made of cyclopentadienyl oxovanadium dimethoxide, cyclopentadienyl oxovanadium diisopropoxide, cyclopentadienyl oxovanadium di-tert-butoxide, cyclopentadienyl oxovanadium diphenoxide, cyclopentadieniloxovanadium methoxychloride cyclopentadienyl oxo-phenyl butadiene-phenyl butadiene-phenyl butadiene-phenyl butadiene-phenyl butadiene-phenyl butadiene-phenyl butadiene-phenyl butadiene-phenyl-butoxy-phenyl-butadiene-phenyl-butoxy-phenyl-butyl-cyclo-cyclo-pentadienyl-phenyl-cyclo-cyclo-pentadienyl-cyclo-cyclohexylanediophenyl-cycloheated In addition, methyl substituted compounds obtained by replacing the chlorine atom in each of the above compounds with a methyl group can be mentioned.

As a specific example of the compound represented by the formula R _n MX _3-n (NR ′), mention may be made of vanadium cyclopentadienyl (methylimide) dichloride.

As the anion that does not form coordination bonds, which is part of component (b), i.e., the ionic compound formed by the anion and cation not forming coordination bonds, we can mention, for example, tetra (phenyl) borate, tetra (fluorophenyl) borate, tetrakis ( difluorophenyl) borate, tetrakis (trifluorophenyl) borate, tetrakis (tetrafluorophenyl) borate, tetrakis (pentafluorophenyl) borate and tetrakis (3,5-bistrifluoromethylphenyl) borate.

Moreover, as a cation, mention may be made of a carbonium cation, an oxonium cation, an ammonium cation, a phosphonium cation, a cycloheptatrienyl cation containing a transition metal atom, a cation such as ferrocenium, etc.

As specific examples of the carbonium cation, trisubstituted carbonium cations such as triphenylcarbonium cation, tris (substituted phenyl) carbonium cation and the like can be mentioned. As specific examples of the tris (substituted phenyl) carbonium cation, the tri (methylphenyl) carbonium cation and the tris (dimethylphenyl) carbonium cation may be mentioned.

As specific examples of the ammonium cation, mention may be made of trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tripropylammonium cation, tributylammonium cation, tri-n-butylammonium cation and the like, as well as N, N-dimethylanilinium cation.

As specific examples of the phosphonium cation, triarylphosphonium cations such as triphenylphosphonium cation, tri (methylphenyl) phosphonium cation, tri (dimethylphenyl) phosphonium cation and the like can be mentioned.

Preferably, any combination of one of the above non-coordinating anions and one of the above cations can be used as the ionic compound.

Preferred as ionic compounds are tetrakis (pentafluorophenyl) triphenylcarbonium borate, tetrakis (fluorophenyl) triphenylcarbonium borate, tetrakis (pentafluorophenyl) borate N, N-dimethylanilinium, tetrakis (pentafluorophenyl) borate 1,1'-dimerfen etc.

The ionic compound can be used alone or as a combination of two or more types.

As component (b), alumoxane can be selected. Alumoxane is prepared by reacting an organoaluminum compound with a condensation reagent. Mention may be made of a linear type aluminoxane or cyclic aluminoxane, both represented by the general formula (-Al (R ') O-) _n , where the R' group is a hydrocarbon group having from 1 to 10 carbon atoms and may be partially substituted by a halogen atom and / or alkoxygroup, n represents the degree of polymerization and is 5 or more, preferably 10 or more. As the group R ′, mention may be made of a methyl group, an ethyl group, a propyl group and an isobutyl group, with a methyl group being an ethyl group being preferred. As the organoaluminum compound used as the starting material for the production of aluminoxane, mention may be made, for example, of trialkylaluminum compounds such as trimethylaluminum, triethylaluminum, triisobutylaluminum and the like, as well as mixtures thereof.

Preferably, when you can use alumoxane obtained using a mixture of trimethylaluminum with tributylaluminum as the starting material.

With respect to a condensation inducing reagent, water may be mentioned as a typical condensation inducing reagent. In addition, any condensation-causing reagent in the presence of which trialkylaluminum can undergo a condensation reaction, for example, water and the like adsorbed by an inorganic compound, as well as a diol, can be mentioned.

As component (c), an organometallic compound of an element of a group from the 1st to the 3rd periodic table can be introduced. Mention may be made, for example, of an organoaluminum compound, an organolithium compound, an organomagnesium compound, an organozinc compound and an organoboron compound.

As specific compounds, mention may be made of methyl lithium, butyllithium, phenyl lithium, benzyl lithium, neopentyl lithium, bistrimethylsilylmethyl lithium, dibutyl magnesium, dihexyl magnesium, diethyl zinc, trimethyl aluminum, etc.

In addition, component (c) encompasses organometallic halides such as ethylmagnesium chloride, butylmagnesium chloride, diethylaluminium chloride, diethylaluminium chloride, ethylaluminum dichloride, and the like, organometallic hydrides such as diethylaminoethyl aluminum hydrides and the like.

As component (c), an organoaluminum compound, that is, an organometallic compound of an element of the 1st to 3rd group of the Periodic Table, is preferred. Specific examples of the organoaluminum compound have been mentioned above and encompass trialkylaluminum compounds such as trimethylaluminum, triethylaluminum, triisobutylaluminum and the like, organoaluminum halides such as dimethylaluminum chloride, diethylaluminium chloride, dichloride such as aluminum diethylaluminum hydride, sesquiolumine hydride and the like. The aforementioned alumoxane may be used. The above organometallic compound may be used as a combination of two or more types.

Preferably, the molar ratio of the amount of component (a), i.e. the metallocene type complex, to the amount of component (b), i.e. the ionic compound, is from 1: 0.1 to 1:10, more preferably from 1: 0.2 to 1: 5.

Preferably, the molar ratio of the amount of component (a), i.e. the metallocene type complex, to the amount of component (c), i.e. the organometallic compound, is from 1: 0.1 to 1: 1000, more preferably from 1:10 to 1: 1000, even more preferably from 1:10 to 1: 500.

Preferably, water is added to the aforementioned catalyst components as component (d). It is desirable that the molar ratio of the amount of component (c), i.e., the organometallic compound, to the amount of component (d), i.e. water, is 0.66: 5, more preferably from 0.7 to 1.5, even more preferably from 0 , 8 to 1.5.

With regard to the order of introduction of the above catalyst components, there are no particular restrictions. However, the introduction can be carried out, for example, in the following order. Component (d) is added to the monomer to be polymerized, or to a mixture of this monomer with a solvent, component (c) is added, then component (a) and component (b) are introduced in the desired order. Alternatively, component (d) and component (c) are added to the monomer to be polymerized as a conjugated diene compound, or to a mixture of this monomer with a solvent, then component (a) and component (b) are introduced in the desired order.

In this document, the monomer to be polymerized as a conjugated diene compound may comprise all or part of the monomer. When it forms part of the monomer, the above catalytic mixture can be mixed with the remaining monomer or the remaining monomer solution.

In the polymerization in the first step, the molecular weight of the resulting polymer is controlled by polymerizing a conjugated diene compound using the above catalyst, preferably in the presence of hydrogen.

Preferably, the amount of hydrogen present is 500 mmol or less or 12 liters or less at a temperature of 20 ° C and a pressure of 1 atmosphere per 1 mol of conjugated diene, more preferably 50 mmol or less or 1.2 liters or less at a temperature of 20 ° C and a pressure of 1 atmosphere, even more preferably from 0.005 mmol to 20 mmol or from 0.00001 to 0.48 liters at a temperature of 20 ° C and a pressure of 1 atmosphere. Or else, hydrogen can be introduced continuously into the polymerization reactor.

Preferably, the polymerization temperature is from -100 to 120 ° C., Particularly preferably from -50 to 100 ° C. The duration of the polymerization is from 10 minutes to 12 hours, particularly preferably from 30 minutes to 6 hours. To further inhibit gelling during polymerization, a known gelling inhibitor can be used.

Using the second catalytic system allows to obtain polybutadiene with a characteristic viscosity of from 0.1 to 20, measured at a temperature of 30 ° C in toluene. In this case, it is possible to obtain matrix polybutadiene, which has a weight average molecular weight of 10,000 to 4,000,000, determined by gel permeation chromatography using polystyrene as a standard substance, and a Mooney viscosity (ML1 + 4, 100 ° C, here and hereinafter referred to as ML) from 10 to 130, preferably from 15 to 80, and which does not have a significant gel fraction.

As the third cis-1,4 polymerization catalyst, a catalyst obtained from (A) yttrium compounds, (B) an ionic compound formed by non-coordinating anion and cation compounds, and (B) an organometallic compound of an element selected from the 2nd can be used group, 12th group and 13th group of the Periodic table.

Preferably, as component (A), i.e., a yttrium compound of the above catalyst system, a yttrium salt or a yttrium complex is used. Particularly preferred compounds include yttrium salts such as yttrium trichloride, yttrium tribromide, yttrium triiodide, yttrium nitrate, yttrium sulfate, yttrium trifluoromethanesulfonate, yttrium acetate, yttrium trifluoroacetate, yttrium malonate, yttrium nitrate, yttrium, yttrium neodecanoate and the like, alkoxides such as yttrium trimethoxide, yttrium triethoxide, yttrium triisopropoxide, yttrium tributoxide, yttrium triphenoxide and the like, organo yttrium compounds lacetanatoyttrium, tris (hexanedionato) yttrium, tris (heptanedionato) yttrium, tris (dimethylheptanedionato) yttrium, tris (tetramethylheptanedionato) yttrium, trisacetoacetatoitrium, dichloride dichloride, cyclotentadienyltrityl dichloride , the picolinic complex of yttrium salt and the like, yttrium salt hydrates, alcohol complexes of yttrium salts, etc.

In addition, the following yttrium compound may be used.

[Formula 2]

(In the above formula, each of the groups R ₁ , R _2, and R ₃ is a hydrogen atom or a hydrocarbon group with the number of carbon atoms from 1 to 12, O represents an oxygen atom, and Y represents a yttrium atom.)

As specific examples of the groups R ₁ , R ₂ and R ₃ , mention may be made of a hydrogen atom, methyl group, ethyl group, vinyl group, n-propyl group, isopropyl group, 1-propenyl group, allyl group, n-butyl group, sec- butyl group, isobutyl group, tert-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 th group, decyl group, undecyl group, dodecyl group, cyclohexyl group, methylcyclohexyl group, ethylcyclohexyl group, phenyl group, benzyl group, toluilnuyu group and ethoxyphenyl group. In addition, those groups are included in which any of the above groups is substituted at any position by a hydroxyl group, a carboxy group, a carbomethoxy group, a carbethoxy group, an amide group, an amino group, an alkoxy group, a phenoxy group or the like.

Preferably, the yttrium salt or yttrium complex is used as the yttrium compound. Particularly preferred yttrium compounds are tris (acetylacetonato) yttrium, tris (hexanedionato) yttrium, tris (heptanedionato) yttrium, tris (dimethylheptanedionato) yttrium, tris (trimethylheptanedionato) yttrium, tris (tetramethylheptanedtanthanthato ) yttrium, trisacetoaceto-yttrium, etc.

In component (B) of the aforementioned catalyst system, i.e., the ionic compound between a non-coordination bond anion and a cation, mention may be made, for example, of a 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 (toluyl tetra boron, borate, borate pentafluorophenyl) borate, tris (ne taftorfenil) (phenyl) borate, tridekagidrid-7,8-dikarbundekaborat, tetrafluoroborate and hexafluorophosphate.

In addition, the cation can include carbonium cation, oxonium cation, ammonium cation, phosphonium cation, cycloheptatrienyl cation, ferrocenium cation, etc.

As specific examples of the carbonium cation, trisubstituted carbonium cations such as triphenylcarbonium cation, tri (substituted phenyl) carbonium cation and the like can be mentioned. As specific examples of a tri (substituted phenyl) carbonium cation, a tri (methylphenyl) carbonium cation and a tri (dimethylphenyl) carbonium cation may be mentioned.

As specific examples of the ammonium cation, mention may be made of trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tripropylammonium cation, tributylammonium cation, tri (n-butyl) ammonium cation and the like, N, N-dialkylanilinium cations, such as N cation, dimethylanilinium, an N, N-diethylanilinium cation, an N, N-2,4,6-pentamethylanilinium cation and the like, and dialkylammonium cations such as di (isopropyl) ammonium cation and the like.

As specific examples of the phosphonium cation, mention may be made of arylphosphonium cations, such as triphenylphosphonium cation, tetraphenylphosphonium cation, tri (methylphenyl) phosphonium cation, tetra (methylphenyl) phosphonium cation, tri (dimethylphenyl) phosphonium cation, tetra (im) phenylphosphonium.

Preferably, any combination of one of the above non-coordinating anions and one of the above cations can be used as the ionic compound.

As the ionic compound, tetrakis (pentafluorophenyl) triphenylcarbonium borate, tetrakis (fluorophenyl) triphenylcarbonium borate, tetrakis (pentafluorophenyl) borate N, N-dimethylanilinium, tetrakis (pentafluorophenyl) borate 1,1'-dimerfer etc. are preferred. The ionic compound can be used alone or as a combination of two or more types.

As component (B), alumoxane can be selected. Alumoxane is prepared by reacting an organoaluminum compound with a condensation reagent. Mention may be made of the linear type aluminoxane and cyclic aluminoxane, both represented by the general formula (-Al (R ') O-) _n , where the R' group is a hydrocarbon group having from 1 to 10 carbon atoms and may be partially substituted by a halogen atom and / or alkoxygroup, n represents the degree of polymerization and is 5 or more, preferably 10 or more. As the group R ′, mention may be made of a methyl group, an ethyl group, a propyl group and an isobutyl group, with a methyl group being preferred. As the organoaluminum compound used as the starting material for the production of aluminoxane, mention may be made, for example, of trialkylaluminum compounds such as trimethylaluminum, triethylaluminum, triisobutylaluminum and the like, as well as mixtures thereof.

Preferably, when aluminoxane obtained using a mixture of trimethylaluminum with tributylaluminum as the starting material can be used.

As for the condensation causing reagent, water may be mentioned as a typical condensation causing reagent. In addition, any condensation-causing reagent in the presence of which trialkylaluminum can undergo a condensation reaction, for example, water and the like adsorbed by an inorganic compound, as well as a diol, can be mentioned.

As component (B) of the above catalytic system, i.e., an organometallic compound of an element of the 2nd, 12th or 13th groups of the Periodic Table, for example, an organomagnesium, organozinc or organoaluminum compound can be used. 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 sesquichromide, alkyl aluminum dichloride, dialkyl hydride etc. are preferred.

As specific compounds, 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 iodide can be mentioned.

In addition, dialkyl magnesium compounds such as dimethyl magnesium, diethyl magnesium, dibutyl magnesium, dihexyl magnesium, dioctyl magnesium, ethyl butyl magnesium, ethyl hexyl magnesium and the like can be mentioned.

In addition, dialkylzinc compounds such as dimethylzinc, diethylzinc, diisobutylzinc, dihexylzinc, dioctylzinc, didecylzinc and the like can be mentioned.

In addition, trialkylaluminum compounds such as trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum and the like can be mentioned.

In addition, mention may be made of organoaluminum halides, such as dialkylaluminum chlorides, such as dimethylaluminum chloride or diethylaluminum chloride, ethylaluminum sesquichloride, ethylaluminum dichloride and the like, organoaluminum hydrides such as diethylaluminium aluminum hydride, diisobutyl hydride and diisobutyl hydride.

Such organometallic compounds of elements of the 2nd, 12th and 13th groups of the Periodic Table can be used on their own or as a combination of two or more types.

In the third method, as a molecular weight regulator of the obtained polybutadiene, a compound selected from (1) hydrogen, (2) a metal hydride compound, and (3) an organometallic hydride can be used.

As the metal hydride of compound (2) used as a molecular weight regulator, mention may be made of lithium hydride, sodium hydride, potassium hydride, magnesium hydride, calcium hydride, boron hydride, aluminum hydride, gallium hydride, germanium hydride, lithium borohydride, sodium borohydride lithium aluminum hydride, sodium aluminum hydride, etc.

As the hydride of the organometallic compound (3) used as a molecular weight regulator, mention may be made, for example, of alkyl borans such as methyl borane, ethyl borane, propyl borane, butyl borane, phenyl borane and the like, dialkyl boranes such as dimethyl borane, diethyl borane, dipropyl borane, dibutyl borane diphenylborane and the like, alkylaluminum dihydrides such as methylaluminum dihydride, ethylaluminum dihydride, propylaluminum dihydride, butylaluminum dihydride, phenylaluminum dihydride and the like, dialkylaluminum hydrides, and such as dimethylaluminum hydride, diethylaluminum hydride, dipropylaluminum hydride, dibutylaluminum hydride, diphenylaluminum hydride and the like, silanes such as methylsilane, ethylsilane, propylsilane, butylsilane, phenylsilane sillyl, diphenylsilane, dimethylsilane, diphenyl, silane, tri tributylsilane, triphenylsilane and the like, as well as germans such as methylgerman, ethylgerman, propylgerman, butylgerman, phenylgerman, dimethylgerman, diethylgerman, dipropylgerman, dibutylgerman, diphenylge Man, trimetilgerman, trietilgerman, tripropilgerman, tributilgerman, trifenilgerman and the like.

Among them, diisobutylaluminum hydride and diethylaluminum hydride are preferred, and diethylaluminum hydride is particularly desirable.

With respect to the order of introduction of the catalytic components, there are no particular restrictions, however, the introduction can be carried out according to the following order.

(1) Component (B) is introduced in an inert organic solvent in the absence or presence of butadiene monomer to be polymerized, and component (A) and component (B) are introduced in any desired order.

(2) Component (B) is introduced in an inert organic solvent in the absence or presence of a butadiene monomer to be polymerized, the above molecular weight regulator is added, and then component (A) and component (B) are added in any desired order.

(3) Component (A) is introduced in an inert organic solvent in the absence or presence of the butadiene monomer to be polymerized, component (B) and the above molecular weight regulator are added in any desired order, and then component (B) is introduced.

(4) Component (B) is introduced in an inert organic solvent in the absence or presence of the butadiene monomer to be polymerized, component (B) and the above molecular weight regulator are added in any desired order, and then component (A) is introduced.

(5) Component (B) is introduced in an inert organic solvent in the absence or presence of the butadiene monomer to be polymerized, component (A) and component (B) are added in any desired order, and then the above molecular weight regulator is introduced.

Before use, individual components can be aged. In particular, it is preferred that component (A) and component (B) be aged.

Regarding the exposure conditions, component (A) and component (B) are mixed in an inert solvent in the presence or absence of butadiene monomer to be polymerized. The holding temperature is from -50 to 80 ° C, preferably from -10 to 50 ° C, and the holding time is from 0.01 hours to 24 hours, preferably from 0.05 hours to 5 hours, particularly preferably from 0.1 hour up to 1 hour.

In the present invention, individual catalytic components can be used by placing them on an inorganic compound or an organic polymer compound.

In the manufacture of polybutadiene using the first or second catalyst, a known molecular weight regulator, for example hydrogen, a non-conjugated diene, such as cyclooctadiene or allen, or an α-olefin, such as ethylene, propylene or butene-1, can be used.

In the polymerization of polybutadiene using the first catalyst, it is preferable that the polymerization temperature is from -30 to 100 ° C, particularly preferably from 30 to 80 ° C. Preferably, the polymerization time is from 10 minutes to 12 hours, particularly preferably from 30 minutes to 6 hours. The polymerization is carried out at normal pressure or at elevated pressure up to about 10 atmospheres (gauge pressure). Preferably, the cis-1,4 polymerization is carried out so that the polymer concentration after cis-1,4 polymerization is from 5 to 26% by weight. As for the polymerization reactor, a single reactor or two or more connected reactors is used. The polymerization is carried out by mixing the solution in a polymerization reactor (polymerization unit). As the polymerization reactor, you can use a polymerization reactor with a device for mixing a solution of high viscosity, for example, the installation described in JP-B-1965-2645.

To further inhibit gelling during polymerization, a known gelling inhibitor can be used. The obtained polybutadiene usually has a cis-1,4-unit content of 90% or more, in particular 95% or more, Mooney viscosity (ML1 + 4, 100 ° C, hereinafter referred to as ML) from 10 to 130 , preferably from 15 to 80, and essentially does not contain a gel fraction.

1,3-Butadiene can be added to the cis-1,4-polymerization reaction mixture obtained as described above, or it can be omitted. After that, syndiotactic 1,2-polymerization is carried out in this polymerization system.

As for the polymerization process using a third catalyst, there are also no particular restrictions on it. It is possible to carry out bulk polymerization using 1,3-butadiene per se as a solvent for polymerization, solution polymerization, etc. As a solvent in the polymerization in solution, mention may be made of aliphatic hydrocarbons such as butane, pentane, hexane, heptane and the like, alicyclic hydrocarbons such as cyclopentane, cyclohexane and the like, aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene and the like, olefinic hydrocarbons such as the aforementioned olefinic compounds, cis-2-butene, trans-2-butene and the like, and so on.

Among them, benzene, toluene, cyclohexane, a mixture of cis-2-butene with trans-2-butene, etc., are preferably used.

Preferably, the polymerization temperature is from -30 to 150 ° C., Particularly preferably from 30 to 100 ° C. Preferably, the polymerization time is from 1 minute to 12 hours, particularly preferably from 5 minutes to 5 hours.

After the polymerization is carried out for a predetermined period of time, the internal pressure in the polymerization reactor is relieved as necessary and post-processing actions such as washing, drying and the like are carried out.

As the polybutadiene obtained in this way, cis-1,4-polybutadiene with a content of cis-1,4-units, preferably 90% or higher, more preferably 92% or higher, especially 96% or higher, can be mentioned. The value [η] of the conjugated diene polymer can be adjusted to a value of preferably from 0.1 to 10, more preferably from 1 to 7, particularly preferably from 1.5 to 5.

Preferably, when the cis-1,4 polymerization is carried out so that the polymer concentration after the cis-1,4 polymerization is carried out is from 5 to 26% by weight. As for the polymerization reactor, a single reactor or two or more connected reactors is used. The polymerization is carried out by mixing the solution in a polymerization reactor (polymerization unit). As the polymerization reactor, you can use a polymerization reactor with a device for mixing a solution of high viscosity, for example, the installation described in patent JP-B-1965-2645.

To further inhibit gelling during polymerization, a known gelling inhibitor can be used. Typically, the resulting polybutadiene has a cis-1,4-unit content of 90% or more, in particular 95% or more, and a Mooney viscosity (ML) of 10 to 130, preferably 15 to 80, and preferably substantially free gel fraction.

As a syndiotactic 1,2-polymerization catalyst, a catalytic system comprising a trialkylaluminum compound of the formula R ¹ ₃ Al (for which the R ¹ group is a hydrocarbon group having from 1 to 10 carbon atoms), a sulfur compound and, if necessary, a compound can be used cobalt.

As the sulfur compound, carbon disulfide, phenyl isothiocyanate, xanthogen acid compound, etc. can be mentioned. Among them, carbon disulfide is preferred. As the trialkylaluminum compound of the formula R ¹ ₃ Al (for which the R ¹ group is a hydrocarbon group having from 1 to 10 carbon atoms) and cobalt compounds, the aforementioned compounds used in cis-1,4 polymerization can be mentioned.

The trialkylaluminum compound is used in an amount of 0.1 mmol or more, in particular from 0.5 mmol to 50 mmol or more, per 1 mol of 1,3-butadiene. There are no particular restrictions on the sulfur compound, but it is preferred that it does not contain water. The concentration of the sulfur compound is 20 mmol / L or less, particularly preferably when it is in the range of 0.01 to 10 mmol / L.

The 1,2-polymerization temperature of 1,3-butadiene is from 0 ° C to 100 ° C, preferably it is in the range from 10 to 100 ° C, more preferably from 20 to 100 ° C. In the polymerization system in which 1,2-polymerization is to be carried out, 1,3-butadiene can be introduced in an amount of from 1 weight part to 50 mass parts, preferably from 1 mass part to 20 mass parts, per 100 mass parts of a mixture in which cis polymerization is carried out, thereby causing the possibility of increasing the yield of 1,2-polybutadiene during 1,2-polymerization. Preferably, the polymerization time (average residence time) is from 10 minutes to 2 hours. Preferably, when the 1,2-polymerization is carried out so that the concentration of the polymer after the 1,2-polymerization is from 9 to 29 wt.%. As for the polymerization reactor, a single reactor or two or more connected reactors is used. The polymerization is carried out by mixing the polymerization solution in a polymerization reactor (polymerization unit). As the polymerization reactor used for the implementation of 1,2-polymerization, you can use a polymerization reactor with a device for mixing a solution of high viscosity, for example, the installation described in patent JP-B-1965-2645, since the viscosity of the solution during 1.2- polymerization becomes higher and the polymer shows a tendency to adhesion.

When the desired conversion is achieved during the polymerization reaction, the aforementioned halogen-containing acid or a salt of the halogen-containing acid is introduced to terminate the polymerization. Preferably, the halogen-containing acid or salt of the halogen-containing acid is administered as a solution, especially an aqueous solution or an alcohol solution, such as a methanol or ethanol solution. In addition, to improve the degree of dispersion in the polymer solution, the presence of a surfactant can be allowed.

The amount of halogen-containing acid or salt of halogen-containing acid added is from 0.001 mol to 10 mol, preferably from 0.002 mol to 5 mol, more preferably from 0.005 mol to 2 mol, per 1 mol of sulfur compound. The duration of mixing after administration is from 5 seconds to 1 hour, preferably from 10 seconds to 30 minutes, more preferably from 20 seconds to 10 minutes.

In addition, a known antioxidant may be administered according to a conventional method. As an antioxidant, mention may be made of 2,6-di-tert-butyl-para-cresol (BHT) as a phenolic compound, trinonyl phenyl phosphite (TNP) as a phosphorus-containing compound, dilauryl-3,3'-thiodipropionate (TPL) as a sulfur-containing compound etc. An antioxidant can be used individually or as a combination of two or more types. The amount of antioxidant administered is from 0.001 parts by weight to 5 parts by weight per 100 parts by weight of VCR polymer. Then, a reagent inhibiting the reaction is introduced into the polymerization system to stop the polymerization. The introduction is carried out according to a known method per se, for example, a method for feeding a polymerization solution into a reactor to terminate the polymerization after the polymerization reaction is carried out and a large amount of a polar solvent is introduced therein, such as alcohol, for example methanol or ethanol, water or the like, or a method for introducing into the polymerization a solution of an inorganic acid such as hydrochloric acid or sulfuric acid, an organic acid such as acetic acid or benzoic acid, or gaseous x orovodoroda. The resulting VCR polymer is then separated, washed and dried according to conventional methods.

In this case, when a halogen-containing acid or a salt of a halogen-containing acid remains in the reaction system before separation and purification, the remaining halogen-containing acid or a salt of a halogen-containing acid is deactivated by interaction with an aqueous solution containing a reducing reagent, such as sulfurous acid, a sulfuric acid salt, a thiosulfuric acid salt , a salt of nitrous acid, oxalic acid, a salt of oxalic acid and the like. Thereby, oxidation of the obtained VCR polymer can be prevented.

To prevent oxidation by the remaining halogen-containing acid or halogen-containing acid salt, the VCR polymer can also be protected from oxidation by the addition of an effective auxiliary reagent, for example, an auxiliary reagent (e.g., an antioxidant), typically added to the rubber composition. As an antioxidant, a known antioxidant such as sterically shielded phenol or the like can be used.

In this way, the obtained VCR polymer contains (1) from 3 to 30 wt.% Insoluble in boiling n-hexane substance (H.I.) and (2) from 97 to 70 wt.% Soluble in boiling n-hexane. The soluble substance in boiling n-hexane is cis-1,4-polybutadiene with a microstructure characterized by a content of cis-1,4-units of 80% or more. Substance H.I. is a syndiotactic 1,2-polybutadiene (SPBD) with a melting point in the range from 180 to 215 ° C. The VCR polymer has an ML value ranging from 20 to 150, preferably from 25 to 100, at a temperature of 100 ° C. In the VCR polymer, the syndiotactic 1,2-polybutadiene is uniformly dispersed in the cis-1,4-polybutadiene matrix in the form of fine crystals. VCR polymer has a low odor compared to traditional VCR polymers.

The VCR polymer obtained according to the present invention is separately compounded or mixed with another synthetic rubber or natural rubber, filled with process oil if necessary, then mixed with a filler (e.g. carbon black), a crosslinking agent, a vulcanization accelerator and other conventional compounding agents and vulcanized. The resulting product is used in rubbers-related applications that require the necessary mechanical properties and abrasion resistance, such as those associated with tire manufacturing (for example, in the manufacture of treads, side walls, stiffeners, side gaskets, inner lining and frames) and various other industrial products (e.g. hoses and belts). VCR can also be used as a modifier for plastics.

EXAMPLES

In the following examples and comparative examples, measurements for each butadiene rubber were performed according to the points below as follows.

Reduced viscosity of n-hexane insoluble substance

25 g of butadiene rubber were placed in 1000 ml of boiling n-hexane and the mixture was heated to reflux, whereby the polybutadiene rubber was separated into a substance soluble in boiling n-hexane and insoluble in n-hexane. 0.2 g of a substance insoluble in boiling n-hexane was dissolved in 100 ml of tetralin, and the viscosity of the solution was measured at a temperature of 130 ° C using a Ubbelode viscometer.

Melting point of n-hexane insoluble substance

It was determined by the endothermic curve obtained by differential scanning calorimetry.

Determination of the weight average molecular weight of a substance soluble in n-hexane

25 g of polybutadiene rubber was placed in 1000 ml of boiling n-hexane and the mixture was refluxed. The insoluble in boiling n-hexane substance was separated by filtration to isolate a solution of n-hexane. n-Hexane was removed from the n-hexane solution to obtain a substance soluble in n-hexane. A n-hexane soluble substance was dissolved in tetrahydrofuran. The solution was analyzed using gel permeation chromatography to determine molecular weight using polystyrene as a standard, and M _{w of} a n-hexane-soluble substance was calculated from these data. The measurements were carried out under the following conditions.

Device: model HLC-802A (manufactured by Tosoh Corporation), speakers: GMH 6000, two in parallel; eluent: tetrahydrofuran; eluent flow rate: 1.0 ml / min; temperature at which the measurement was carried out: collective casing of the column 40 ° C, detector 40 ° C; sample concentration: 0.25 g / l; amount of sample introduced: 0.5 ml.

Microstructure of a substance soluble in n-hexane

The boiling n-hexane-soluble substance obtained as described above was analyzed using infrared spectroscopy, and the microstructure of the boiling n-hexane-soluble substance was obtained from the ratio of the intensities of the absorption bands of the corresponding cis-1,4 structure at 740 cm ^{- 1} , the trans-1,4 structure at 967 cm ^-1 and the 1,2 structure (vinyl) at 911 cm ^-1 .

The viscosity of a solution of a substance soluble in n-hexane in toluene (T-cp)

The soluble in boiling n-hexane obtained as described above was dissolved in toluene so as to obtain a solution with a concentration of 5 wt.%. The viscosity of the solution was measured at 25 ° C. using a Cannon-Fenske viscometer.

Mooney viscosity of n-hexane-soluble substance and compound

Determined according to the procedure specified in JIS K 6300.

Residual odor control

The resulting product was checked to control the degree of residual odor. In addition, since the odor-transmitting substance is mainly present in the volatile components of the product, the amount of volatile components was used as an indicator reflecting an objective knowledge of the level of smell. Therefore, the amount of volatile components was determined under the following conditions. This amount was compared with the level of odor obtained through organoleptic control, and comprehensively judged the level of residual odor. In this case, the result of measuring the amount of volatile components was expressed as a relative value from the number of volatile components defined in comparative example 1, which was assumed to be 100, and it is shown in table 1, which is shown below.

2.5 g of rubber obtained in each example was carefully weighed in 20 ml of sample container and heated at 170 ° C. for 30 minutes. Then, using a gas chromatograph with a flame photometric detector (FPD), measurements were made using 1 ml of the vapor fraction from the sample container under the following conditions.

FPD gas chromatograph: Agilent 6890 model

Column model: HP-1, 60 m (length) × 0.32 mm (inner diameter) × 5.0 μm (film thickness)

Conditions in the column: holding at a temperature of 40 ° C for 5 minutes, then raising the temperature to 250 ° C at a speed of 15 ° C per minute, and finally holding at a temperature of 250 ° C for 11 minutes

Duration of measurement: 30 minutes

Example 1

Cis-1,4 polymerization

A volume of 2.0 L (capacity volume) of the autoclave was purged with nitrogen. A 1 L solution (FB) of cyclohexane (350 ml), cis-2-butene (340 ml) and 1,3-butadiene (310 ml) was injected into it, followed by stirring for 30 minutes. Then, 19 mg of carbon disulfide and 26 mg of water (H ₂ O) were added, followed by stirring for 30 minutes to dissolve. Diethyl aluminum chloride (DEAC) was then introduced so that its concentration was 2.9 mmol / L. After 3 minutes, 8 mg of dilauryl thiodipropionate and 1.45 ml of cyclooctadiene were administered. The mixture was heated to a temperature of 50 ° C. Then 0.6 ml of cobalt octylate [Co (Oct) ₂ ] (a solution in toluene with a concentration of 30 mg / ml) was introduced and matrix polymerization was carried out at a temperature of 50 ° C for 20 minutes.

(Syndiotactic 1,2-polymerization)

Next, triethylaluminum (TEM) was introduced so that the concentration was 3.5 mmol / L, followed by stirring for 5 minutes. Then 0.6 ml of a solution of cobalt octylate in toluene (30 ml / l) was introduced and polymerization was carried out for 20 minutes.

After polymerization was completed, 1.26 ml of an aqueous sodium hypochlorite solution (0.05 mol / L) was added to terminate the polymerization reaction. After that, the polymerization mixture was processed according to the usual method for the isolation of polybutadiene rubber.

The yield of polybutadiene rubber obtained was 95.7 g, and its Mooney viscosity was 49.4 (ML1 + 4, 100 ° C). In an organoleptic test, this rubber was essentially odorless.

This rubber contained 13% by weight of a substance insoluble in boiling n-hexane and 87% by weight of a substance insoluble in boiling n-hexane. The n-hexane insoluble substance had a peak in the endothermic curve obtained by differential scanning calorimetry at a temperature of 201.3 ° C.

Example 2

The polymerization was carried out in the same manner as in Example 1, except that the injected amount of an aqueous solution of sodium hypochlorite was 3.72 ml. The yield of polybutadiene rubber obtained was 99.2 g, and its Mooney viscosity was 48.9 (ML1 + 4, 100 ° C). Essentially, this rubber was odorless.

This rubber contained 13.5% by weight of a substance insoluble in boiling n-hexane and 86.5% by weight of a substance soluble in boiling n-hexane. The n-hexane insoluble substance had a peak in the endothermic curve obtained by differential scanning calorimetry at a temperature of 201.1 ° C.

Comparative Example 1

The polymerization was carried out in the same manner as in Example 1, except that when the polymerization was stopped, water was introduced instead of the aqueous sodium hypochlorite solution. The yield of polybutadiene rubber obtained was 99.7 g, and its Mooney viscosity was 48.5 (ML1 + 4, 100 ° C). This rubber had an unpleasant odor.

This rubber contained 12.9% by weight of a substance insoluble in boiling n-hexane and 87.1% by weight of a substance soluble in boiling n-hexane. The n-hexane insoluble substance had a peak in the endothermic curve obtained by differential scanning calorimetry at a temperature of 201.3 ° C.

(Cis-1,4 polymerization)

Example 3

A volume of 1.5 L (tank volume) of the autoclave was purged with nitrogen. 700 ml of a mixture solution was introduced into it containing 33% (wt.) Butadiene, 16% (wt.) Cyclohexane and 51% (wt.) 2-butene. At room temperature, water was introduced so that the concentration was 3.7 mmol / L, and carbon disulfide and 1,5-cyclooctadiene were introduced so that the concentration of the former was 30 mg / L and the concentration of the latter was 10.2 mmol / L. Intensive mixing was carried out at a speed of 700 rpm for 30 minutes. 2.4 ml of a solution of diethylaluminum chloride (DEAC) and triethylaluminum (TEA) in cyclohexane [DEAC: TEA = 2: 1 (molar ratio), Al concentration = 1 mol / L] were added, followed by stirring at room temperature for 5 minutes. The mixture was heated to a temperature of 60 ° C and 1.8 ml of a solution of cobalt octylate [Co (Oct) ₂ ] in toluene (0.005 mol / L) was added. The polymerization was initiated and carried out at a temperature of 70 ° C for 15 minutes.

(Syndiotactic 1,2-polymerization)

Then, 4.2 ml of a solution of triethylaluminum (TEM) in cyclohexane (1 mol / L) was introduced there. One after another, 140 ml of 1,3-butadiene, 36 mg of water and 1.05 ml of a solution of cobalt octylate [Co (Oct) ₂ ] in toluene (0.05 mol / L) were added. The polymerization was carried out at a temperature of 60 ° C for 15 minutes.

To terminate the polymerization reaction, 2 ml of an aqueous sodium hypochlorite solution (0.2 mol / L) was added, followed by stirring for 5 minutes. After that, the polymerization mixture was processed according to the usual method for the isolation of polybutadiene rubber.

The yield of polybutadiene rubber obtained was 113 g, and its Mooney viscosity was 72 (ML1 + 4, 100 ° C). Essentially, this rubber was odorless.

This rubber contained 16.6% by weight of a substance insoluble in boiling n-hexane and 83.4% by weight of a substance soluble in boiling n-hexane. The insoluble substance in boiling n-hexane had a reduced viscosity of 1.4 and a peak in the endothermic curve obtained by differential scanning calorimetry at a temperature of 201.2 ° C. The soluble in boiling n-hexane substance had a Mooney viscosity of 32 (ML1 + 4, 100 ° C), a solution viscosity in toluene of 82, a weight average molecular weight of 400,000, and contained 98.5% of cis-1 units. 4-structure, 0.7% of units with trans-1,4-structure and 0.8% of units with 1,2-structure.

Example 4

Polybutadiene was synthesized in the same manner as described in Example 3, except that upon termination of the polymerization, an aqueous 3% (w / w) suspension of powdered bleach [CaCl (OCl)] was introduced. Essentially, the resulting rubber did not have a smell.

Example 5

Polybutadiene was synthesized in the same manner as that described in Example 3, except that upon termination of the polymerization, an aqueous 3% (wt.) Suspension of high-quality hypochlorite (calcium hypochlorite) was introduced. Essentially, the resulting rubber did not have a smell.

Example 6

Polybutadiene was synthesized in the same manner as that described in example 3, except that upon termination of the polymerization was introduced an aqueous 3% (wt.) Solution of potassium chlorate. Essentially, the resulting rubber did not have a smell.

Reference Example 2

Polybutadiene was synthesized in the same manner as that described in example 3, except that upon termination of the polymerization was not introduced an aqueous solution of sodium hypochlorite. The resulting rubber had an unpleasant odor.

Example 7

Catalyst exposure

5.2 ml of cyclohexane, 1.5 mmol of diisobutylaluminum hydride (0.75 ml of solution in cyclohexane), 0.31 mmol of butadiene and 0.05 mmol of NDV ₃ (Versatate neodymium) (as a solution in cyclohexane) were mixed. The mixture was kept at a temperature of 50 ° C for 5 minutes. 0.15 mmol of diethylaluminium chloride (as a solution in cyclohexane) was added, followed by stirring for 25 minutes.

(Cis-1,4 polymerization)

A solution of butadiene containing 25% (wt.) 1,3-butadiene and 75% (wt.) Cyclohexane was introduced into a 2-liter autoclave (tank volume), the volume of which was purged with nitrogen gas. 2.5 mmol of diisobutylaluminum hydride (1.25 ml of the solution in cyclohexane), as well as the total amount of the previously aged catalyst solution obtained, were introduced into it. The polymerization was carried out at a temperature of 60 ° C for 30 minutes.

(Syndiotactic 1,2-polymerization)

To the mixture obtained, as indicated above, in which cis polymerization was carried out, 15 mg of carbon disulfide, 3.5 mmol of triethyl aluminum and 35 mg of cobalt octylate were introduced. The mixture was stirred at 60 ° C. for 15 minutes to syndiotactically 1,2-polymerize the remaining 1,3-butadiene.

To terminate the polymerization reaction, 2 ml of an aqueous sodium hypochlorite solution (0.2 mol / L) was added, followed by stirring for 5 minutes. After that, the polymerization mixture was processed according to the usual method for the isolation of polybutadiene rubber.

The yield of polybutadiene rubber obtained was 97 g, and its Mooney viscosity was 51 (ML1 + 4, 100 ° C). Essentially, this rubber was odorless.

This rubber contained 14% by weight of a substance insoluble in boiling n-hexane and 86% by weight of a substance soluble in boiling n-hexane. The insoluble substance in boiling n-hexane had a reduced viscosity of 1.6 and a peak on the endothermic curve obtained by differential scanning calorimetry at a temperature of 202.4 ° C. The soluble in boiling n-hexane substance had a Mooney viscosity of 23 (ML1 + 4, 100 ° C), a solution viscosity in toluene of 91, a weight average molecular weight of 600,000, and 98.2% of cis-1 units 4-structure, 0.9% of the links with trans-1,4-structure and 0.9% of the links with 1,2-structure.

Reference Example 3

Polybutadiene was synthesized in the same manner as that described in example 7, except that upon termination of the polymerization was not introduced an aqueous solution of sodium hypochlorite. The resulting rubber had an unpleasant odor.

Example 8

Cis-1,4 polymerization

A volume of 5.0 l (capacity volume) of the autoclave was purged with nitrogen. A 3 L solution (FB) containing cyclohexane (900 ml), cis-2-butene (1200 ml) and 1,3-butadiene (900 ml) was added thereto, followed by stirring for 30 minutes. Then, the water content in the mixture was controlled using a Karl Fischer water-measuring instrument to obtain an average water content of 10 ppm. The same operation was repeated and 3 liters of FB solution were loaded into the autoclave. 340 ml (volume at a temperature of 20 ° C and a pressure of 1 atmosphere) of hydrogen gas were introduced into it using an integrating mass flow meter. Then, 45 mg of carbon disulfide and 56 mg of water (H ₂ O) were added, followed by stirring for 30 minutes to dissolve. Next, 6 ml of triethylaluminium was introduced (as a solution in toluene with a concentration of 1 mmol / L). After 3 minutes, 3 ml of cyclopentadienyl vanadium trichloride (CpVCl ₃ ) was added (as a solution in toluene with a concentration of 0.005 mmol / ml), and 12 ml of triphenylcarbenium tetrakis (pentafluorophenyl) borate [Ph ₃ CB (C ₆ F ₅ ) ₄ ] ( in the form of a solution in toluene with a concentration of 0.0025 mmol / ml). Matrix polymerization was carried out at a temperature of 40 ° C for 30 minutes.

(Syndiotactic 1,2-polymerization)

Next, 1.7 ml of cobalt octoate (as a solution in toluene with a concentration of 0.1 mmol / ml) was introduced, followed by polymerization for 30 minutes. After polymerization, to terminate the polymerization reaction was introduced 2 ml of an aqueous solution of sodium hypochlorite (0.2 mol / l). Then stirring was continued for 5 minutes. The polymerization mixture was treated according to a conventional method for isolating polybutadiene rubber.

The yield of polybutadiene rubber obtained was 190 g, and its Mooney viscosity was 38 (ML1 + 4, 100 ° C). Essentially, this rubber was odorless.

This rubber contained 6% by weight of a substance insoluble in boiling n-hexane and 94% by weight of a substance soluble in boiling n-hexane. The insoluble substance in boiling n-hexane had a reduced viscosity of 1.5 and a peak in the endothermic curve obtained by differential scanning calorimetry at a temperature of 204 ° C. The soluble in boiling n-hexane substance had a Mooney viscosity of 27 (ML1 + 4, 100 ° C) and a solution viscosity in toluene of 84, and also contained 88.9% units with a cis-1,4 structure, 0 , 8% of links with a trans-1,4 structure and 10.5% of links with a 1,2 structure.

Example 9

Polybutadiene was synthesized in the same manner as that described in example 8, except that upon termination of the polymerization was introduced an aqueous 3% (wt.) Suspension of powdered bleach [CaCl (OCl)]. Essentially, the resulting rubber did not have a smell.

Example 10

Polybutadiene was synthesized in the same manner as that described in Example 8, except that upon termination of the polymerization, an aqueous 3% (wt.) Suspension of high-quality hypochlorite (calcium hypochlorite) was introduced. Essentially, the resulting rubber did not have a smell.

Example 11

Polybutadiene was synthesized in the same manner as that described in example 8, except that upon termination of the polymerization was introduced an aqueous 3% (wt.) Solution of potassium chlorate. Essentially, the resulting rubber did not have a smell.

Reference Example 4

Polybutadiene was synthesized in the same manner as that described in example 8, except that upon termination of the polymerization was not introduced an aqueous 3% (wt.) Solution of sodium hypochlorite. The resulting rubber had an unpleasant odor.

Example 12

Cis-1,4 polymerization

A volume of 2 l (capacity volume) of the autoclave was purged with nitrogen. A solution containing 390 ml of toluene and 210 ml of butadiene was introduced into it. The temperature of the solution was set equal to 30 ° C. Then, 0.90 ml of a solution of diethylaluminum hydride (DEAH) in toluene (2 mol / L) was added, followed by stirring at a speed of 550 rpm for 3 minutes. Then 1.8 ml of a solution of tris (2,2,6,6-tetramethylheptane-3,5-dionato) yttrium in toluene (20 mmol / L) was added. The mixture was heated to a temperature of 40 ° C. Stirring was carried out for 4 minutes. Then, 0.18 ml of a solution of triphenylcarbenium tetrakispentafluorophenylborate in toluene (0.43 mol / L) was introduced and polymerization was initiated. The polymerization was carried out at a temperature of 40 ° C for 30 minutes.

(Syndiotactic 1,2-polymerization)

Next, 1.8 ml of a solution of triethylaluminum (TEA) in toluene (1 mol / L) was added. Then water was introduced so that its content was 0.5 mmol / L. 1.8 ml of a solution of cobalt octylate [Co (Oct) ₂ ] in toluene (0.05 mol / L) and 0.36 ml of a solution of carbon disulfide in toluene (1 mol / L) were added, followed by polymerization at 40 ° C in for 10 minutes.

To terminate the polymerization reaction, 2 ml of an aqueous solution of sodium hypochlorite (0.2 mol / L) was added, followed by stirring for 5 minutes. The polymerization mixture was treated according to a conventional method for isolating polybutadiene rubber.

The yield of the obtained polybutadiene rubber was 100 g, and its Mooney viscosity was 82 (ML1 + 4, 100 ° C). Essentially, this rubber was odorless.

This rubber contained 11.2% by weight of a substance insoluble in boiling n-hexane and 88.8% by weight of a substance soluble in boiling n-hexane. The substance insoluble in boiling n-hexane had a peak in the endothermic curve obtained by differential scanning calorimetry at a temperature of 203.9 ° C.

Example 13

Polybutadiene was synthesized in the same manner as that described in example 12, except that upon termination of the polymerization was introduced an aqueous 3% (wt.) Suspension of powdered bleach [CaCl (OCl)]. Essentially, the resulting rubber did not have a smell.

Example 14

Polybutadiene was synthesized in the same manner as described in Example 12, except that upon termination of the polymerization, an aqueous 3% (wt.) Suspension of high-quality hypochlorite (calcium hypochlorite) was introduced. Essentially, the resulting rubber was odorless.

Example 15

Polybutadiene was synthesized in the same manner as that described in example 12, except that upon termination of the polymerization was introduced an aqueous 3% (wt.) Solution of potassium chlorate. Essentially, the resulting rubber did not have a smell.

Reference Example 5

Polybutadiene was synthesized in the same manner as that described in example 12, except that upon termination of the polymerization was not introduced an aqueous solution of sodium hypochlorite. The resulting rubber had an unpleasant odor.

Table 1 Example or comparative example The number of volatile components Example or comparative example The number of volatile components Example 1 6 Example 8 6 Example 2 5 Example 9 6 Comparative Example 1 one hundred Example 10 four Example 3 four Example 11 10 Example 4 8 Reference Example 4 93 Example 5 5 Example 12 3 Example 6 9 Example 13 5 Reference Example 2 112 Example 14 3 Example 7 5 Example 15 8 Reference Example 3 88 Reference Example 5 82

The results of determining the content of volatile components shown in table 1 are in good agreement with the results of the test for smell through olfactory sensation.

In the following examples and comparative examples, each polybutadiene rubber obtained with the addition of Irganox 1520 after termination of the polymerization, which is known as an antioxidant, was analyzed for oxidation degradability and the results were reported. The length of time required for the manifestation of the destruction during oxidation was determined, and used it as a characteristic of the ability to destruction during oxidation.

Determination of oxidation degradability

The polymer, placed in a control instrument for testing by differential scanning calorimetry, was held at a predetermined temperature in the atmosphere of the air and the time interval until heat evolution manifested due to polymer destruction during oxidation was determined. A longer period of time before the manifestation of heat evolution indicates that degradation during oxidation is less likely.

Reference Example 6

The polymerization was carried out in the same manner as that used in comparative example 1, except that 1000 ppm of Irganox 1520 (antioxidant) was added to the polymer after termination of the polymerization. The oxidation degradability for the obtained polybutadiene rubber was analyzed at a temperature of 140 ° C, 145 ° C and 150 ° C. The measurement results are shown in table 2.

Example 16

The polymerization was carried out in the same manner as that used in Example 1, except that 1000 ppm of Irganox 1520 (antioxidant) was added to the polymer after termination of the polymerization caused by the introduction of an aqueous solution of sodium hypochlorite. The oxidation degradability for the obtained polybutadiene rubber was analyzed at a temperature of 140 ° C, 145 ° C and 150 ° C. The measurement results are shown in table 2.

Example 17

The polymerization was carried out in the same manner as that used in Example 16, except that 1350 ppm of Irganox 1520 was added to the polymer. The oxidation degradability of the resulting polybutadiene rubber was analyzed at a temperature of 140 ° C., 145 ° C. and 150 ° C. The measurement results are shown in table 2.

Example 18

The polymerization was carried out in the same manner as that used in Example 16, except that 1700 ppm of Irganox 1520 was added to the polymer. The oxidation degradability of the obtained polybutadiene rubber was analyzed at a temperature of 140 ° C., 145 ° C. and 150 ° C. The measurement results are shown in table 2.

Example 19

The polymerization was carried out in the same manner as that used in Example 16, except that 2000 ppm of Irganox 1520 was added to the polymer. The oxidation degradability of the resulting polybutadiene rubber was analyzed at a temperature of 140 ° C., 145 ° C. and 150 ° C. The measurement results are shown in table 2.

table 2 Antioxidant
(millionths) The time required for the manifestation of destruction during oxidation (min) 140 ° C 145 ° C 150 ° C Reference Example 6 1000 59.7 20,0 12.6 Example 16 1000 48,4 15.8 7.9 Example 17 1350 60.3 32.1 13,2 Example 18 1700 72.1 46.2 18.5 Example 19 2000 81.8 59.8 22.6

The above results reflect the following. In the case where the amount of antioxidant administered was insufficient, as in Example 16, the time required for the manifestation of oxidation degradation was approximately the same or slightly less than that obtained in Example 6, in which the antioxidant was administered in the same amount, but was not administered an aqueous solution of sodium hypochlorite; however, when a sufficient amount of antioxidant was introduced, as in the examples from the 17th to the 19th, the effect of preventing the destruction was obvious compared to the case when an aqueous solution of sodium hypochlorite was not introduced.

Industrial applicability

The VCR polymer obtained according to the present invention has an extremely low odor and therefore can be used alone or compounded with other rubber, as well as various additives, if necessary, for various applications, for example, rubber related applications that require necessary mechanical properties and abrasion resistance, such as the production of tires and various other industrial products (for example, hoses and belts). VCR can also be used as a modifier for plastics. Accordingly, the present invention provides a method useful to industry.

Claims (10)

1. The method of producing polybutadiene, including, firstly, the cis-1,4-polymerization of 1,3-butadiene and the subsequent syndiotactic 1,2-polymerization of the obtained product in the resulting polymerization system in the presence of a catalyst containing a cobalt compound, an aluminum alkyl compound and a sulfur compound, characterized in that in order to stop the polymerization, a halogen-containing acid or a salt of a halogen-containing acid is introduced, where both are represented by the following general formula (I):
M '(X'O _q ) _r Z' _s (I)
(where M 'represents a metal atom or a hydrogen atom, X' represents a halogen atom selected from chlorine, bromine and iodine, O represents an oxygen atom, q is an integer from 1 to 4; Z 'represents an anion capable of binding with an atom M ', r is an integer of 1 or more, and the sum r + s is the oxidation state of M'). 2. The method of producing polybutadiene according to claim 1, where X 'represents chlorine. 3. The method of producing polybutadiene according to claim 1, where the compound represented by the general formula (I) is hypochlorous acid or a salt of hypochlorous acid. 4. The method of producing polybutadiene according to claim 1, where the catalyst used for cis-1,4 polymerization is a catalyst containing a cobalt compound, an organoaluminum compound and water. 5. The method of producing polybutadiene according to claim 4, where the aluminum-aluminum compound is a trialkylaluminum compound represented by the formula R ¹ ₃ Al (where the R ¹ group is a hydrocarbon group having from 1 to 10 carbon atoms) and a halogen-containing aluminum compound represented by the formula R ² _3-n AlX _n , (where the R ² group is a hydrocarbon group having from 1 to 10 carbon atoms, X is halogen, and n is a number from 1 to 2). 6. The method of producing polybutadiene according to claim 1, where the catalyst used for cis-1,4 polymerization is a catalyst obtained by extracting components selected from a metal compound of the 3rd group of the Periodic Table, a compound consisting of aluminum alkyl hydride, butadiene methylaluminoxane and a chlorine-containing compound. 7. The method of producing polybutadiene according to claim 1, where the catalyst used for cis-1,4 polymerization is a catalyst obtained from a complex compound of a transition metal of the metallocene type, an ionic compound formed by non-coordinating anion and cation, an organometal compound the element of the group from the 1st to the 3rd group of the Periodic table and water with a molar ratio: (organometallic compound of the element from the 1st to 3rd group of the Periodic table) / (water) = from 0.66 to 5. 8. The method of producing polybutadiene according to claim 1, where the catalyst used for cis-1,4 polymerization is a catalyst obtained from (A) a yttrium compound, (B) an ionic compound formed by non-coordinating anions and cations, and (C) an organometallic compound of an element selected from the 2nd group, the 12th group and the 13th group of the Periodic table. 9. The method of producing polybutadiene according to claim 8, where the compound of yttrium (A) uses a compound of yttrium with a bulky ligand represented by the following general formula:

[Formula 1]
(where each of the groups R ¹ , R ² and R ³ represents hydrogen or a hydrocarbon group having from 1 to 12 carbon atoms, O represents an oxygen atom, and Y represents a yttrium atom). 10. The method of producing polybutadiene according to claim 1, where the polybutadiene is a polybutadiene comprising (1) from 3 to 30 wt.% Insoluble in boiling n-hexane and (2) from 97 to 70 wt.% Soluble in boiling n- hexane substances.