JP3504229B2 - Catalyst for hydrolyzing conjugated diene polymers - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an improved catalyst used for hydrolyzing a conjugated diene polymer obtained by polymerizing or copolymerizing a conjugated diene monomer (for example, butadiene or isoprene).
The present invention relates to a catalyst having a particularly good activity, a high selectivity and a low cost for hydrolyzing a conjugated diene polymer. The present invention also relates to a method for producing a hydrolyzed conjugated diene polymer excellent in weather resistance, heat resistance and anti-oxidation using the catalyst.

[0002]

2. Description of the Related Art It is industrially widely applied to produce a synthetic rubber by polymerizing or copolymerizing a conjugated diene (for example, butadiene or isoprene). Generally, the above polymers are emulsion methods (free radical polymerization methods).
Alternatively, it is prepared by a solution method (anionic polymerization method). By these methods, a conjugated diene polymer (copolymer) having an unsaturated double bond in the main chain of the polymer can be obtained. The strength can be improved by vulcanizing the unsaturated double bond, but since the unsaturated double bond is easily oxidized,
It has the drawback of lacking stability in high temperature conditions and outdoors exposed to sunlight (exposed to ultraviolet rays and ozone). Especially when styrene / conjugated diene block copolymers (eg SBS, SIS) are used as thermoplastic elastomers without vulcanization, as impact modifiers or compound compatibilizers, their thermal stability and weather resistance are improved. Is required to do.

Thermal stability and weather resistance are improved by removing or reducing unsaturated double bonds in the polymer chain. That is, a more stable polymer is obtained by hydrolyzing an aliphatic olefinic unsaturated double bond to form an aliphatic structure. In general, a heterogeneous or homogeneous catalyst can reduce unsaturated double bonds, but a heterogeneous catalyst requires high temperature and pressure during the reaction due to its low hydrolytic activity, and it is uneconomical because it is used in large amounts. Not only that, but due to harsh reaction conditions, not only the olefin double bond but also the aromatic double bond may be hydrolyzed. As a result, an unnecessary polymer structure can be obtained, and an unnecessary cyclone structure is obtained. It has a hexyl group (hydrogenated benzene ring on the main chain of the polymer) and exhibits unfavorable semi-crystalline properties.
Therefore, there is a demand for the development of a highly active and highly selective homogeneous catalyst system (which does not hydrolyze aromatic double bonds) that can be used for the hydrolysis of a conjugated diene polymer in the industry.

Biscyclopentadienyltitanium compounds are known as effective reaction catalysts in the homogeneous hydrolysis reaction (MFSloan et al. In the Journal of Ame).
rican Chemical Society 1965, 85, 4014-
4018; Y. Tajima, et al. In the Journal of Org
anic Chemistry, 1968, 33, 1689-1690;
British Patent No. 2,134,909; JP 61-2850
No. 7). Although this catalyst system has good activity and extremely good selectivity for the hydrolysis of olefinic double bonds, it lacks the stability of the catalyst system itself and thus has a problem in reproducibility of the reaction.

In 1985, Kishimoto et al., US Pat. No. 4,
No. 501,857 discloses a method of hydrolyzing an olefinic double bond in the presence of at least one biscyclopentadienyl titanium compound and one hydrocarbon lithium compound. Also, in 1987, Kish
imoto et al., in U.S. Pat. No. 4,673,714, newly announced the use of biscyclopentadienyldiallyl titanium compounds without alkyllithium compounds for the hydrolysis of conjugated diene polymers. Both of the above two methods are considered to be very uneconomical because they use a high concentration of biscyclopentadienyl titanium compound as a catalyst. 1990, Teramo
to et al. in U.S. Pat. No. 4,980,421 announced that a similar hydrolytic activity can be obtained by using an alkoxy compound in combination with the same titanium compound. In 1991, Chamberlain et al. Proposed in US Pat. No. 5,039,755 a method in which an active chain was sealed with hydrogen gas and then a biscyclopentadienyl titanium compound was added to proceed a hydrolysis reaction. Since the sealing of the active chain terminal with hydrogen gas is not so effective, the reproducibility of the hydrolysis reaction is not good. 1992
In the year, Chamberlain et al. Presented a method of hydrolysis similar to US Pat. No. 5,173,537, in which the active chain ends were capped with hydrogen gas before the biscyclopentadienyl titanium compound and a corresponding catalyst promoter (methyl catalyst). It has been shown how the addition of benzoate) makes the hydrolysis of conjugated diene polymers more effective.

All of the above catalyst compositions activate the biscyclopentadienyltitanium compound with an alkyllithium (generated statics in situ lithium hydride) or alkoxylithium compound to more effectively hydrolyze the conjugated diene polymer. To do. One thing to note is that biscyclopentadienyl titanium compounds can be reduced from Ti (IV) to Ti (III) in the presence of lithium, resulting in decomposition of the catalyst component and its activity and stability. Is to decrease. Therefore, there is a demand for an economical catalyst system which prevents the decomposition of the reactive catalyst (biscyclopentadienyl titanium compound), and which is stable even in a small amount and provides an effective hydrolyzing effect.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a catalyst having high activity and excellent selectivity in hydrolyzing a conjugated diene polymer. Another object is to provide an effective catalyst with a minimum amount of catalyst, in addition to good activity and high selectivity.

A further object of the present invention is to provide a method for hydrolyzing a conjugated diene polymer having a high hydrolytic activity and high selectivity in the presence of a hydrocarbon lithium compound.

[0009]

The present invention provides a catalyst for hydrolyzing a conjugated diene polymer comprising the following (a) and (b), and a conjugated diene polymer and hydrogen are reacted in the presence of the catalyst. The present invention relates to a method for hydrolyzing a conjugated diene polymer. (A): at least one titanium compound represented by the following formula (a)

[0010]

[Chemical 6]

[In the formula, R ¹ and R ² may be the same or different and each represents a halogen atom, an alkyl group, an aryl group, an aralkyl group, a cycloalkyl group, an allyloxy group, an alkoxy group or a carbonyl group. . Cp ^*
Represents a cyclopentadienyl group which may have up to 5 substituents such as an alkyl group, an aralkyl group and an aryl group. ] (B): At least one silyl hydride selected from the following formulas (i) to (V)

[0012]

[Chemical 7]

[Wherein X ¹ , X ² and X ³ may be the same or different and each is a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an aralkyl group, a cycloalkyl group, an aryloxy group or an alkoxy group. Alternatively, it represents an acyloxy group. ]

[0014]

[Chemical 8]

[In the formula, R and R ^{3, which} may be the same or different, each represents a hydrogen atom, a halogen atom, an alkyl group,
It represents an aryl group, an aralkyl group, a cycloalkyl group, an allyloxy group, or an alkoxy group, and n ≧ 0.
However, when n = 0, R ³ represents a hydrogen atom. ]

[0016]

[Chemical 9]

[In the formula, R may be the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an aralkyl group, a cycloalkyl group, an aryloxy group, or an alkoxy group, and n = 2. 3, 4, or 5. ]

[0018]

[Chemical 10]

[In the formula, R ^a , R ^b and R ^c may be the same or different and each is a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an aralkyl group, a cycloalkyl group, an allyloxy group or an alkoxy group. Represents a group. ]

[0020]

BEST MODE FOR CARRYING OUT THE INVENTION One of the advantages of the catalyst of the present invention is that it has a high selectivity for hydrolyzing an olefinic double bond, so that the total amount of titanium compounds added during the reaction can be reduced, which is economical. It means that the process can be realized.
Another advantage of the present invention is that since the stability of the catalyst is improved, the olefinic double bond hydrolysis reaction of the conjugated diene polymer has a high conversion rate and a high selectivity. .

The present invention provides a catalyst for hydrolyzing a conjugated diene polymer excellent in high reactivity, selectivity and stability. In the catalyst of the present invention, a component such as silyl hydride that is easily available on the market can be used, the stability, activity and conversion of the catalyst are improved, and further, the total amount of the catalyst component can be reduced, so that the hydrolysis The cost of the process can be greatly reduced. Hereinafter, each component of the catalyst of the present invention will be described in detail.

<(A) Titanium Compound> Cp ^* in the above chemical formula (a) is a cyclopentadienyl group which may have up to 5 substituents such as an alkyl group, an aralkyl group and an aryl group. Represent. Suitable Cp ^{* includes} cyclopentadienyl group and pentamethylcyclopentadienyl group, but cyclopentadienyl group is industrially preferable.

A suitable titanium compound represented by the chemical formula (a) is biscyclopentadienyl titanium dichloride,
Titanium biscyclopentadienyl dibromide, titanium biscyclopentadienyl diiodide, titanium biscyclopentadienyl difluoride, biscyclopentadienyl dicarbonyl titanium, biscyclopentadienyl dimethyl titanium, biscyclopentadiene Enyldiethyltitanium, biscyclopentadienyldipropyltitanium (including isopropyl), biscyclopentadienyldibutyltitanium (n-butyl, sec-butyl, tert-
Butyl), biscyclopentadienyldibenzyltitanium, biscyclopentadienyldiphenyltitanium, biscyclopentadienyldimethoxytitanium, biscyclopentadienyldiethoxytitanium, biscyclopentadienyldipropoxytitanium, biscyclotitanium. Pentadienyldibutoxytitanium, Biscyclopentadienyldiphenoxytitanium, Biscyclopentadienylmethyl titanium chloride, Biscyclopentadienylmethyl titanium bromide, Biscyclopentadienylmethyliodide titanium, Biscyclopentadiene Included are those selected from the group consisting of titanium enylmethyl fluorinated, and mixtures thereof. In addition, bispentamethylcyclopentadienyldichlorotitanium, bispentamethylcyclopentadienyldibrominated titanium, bispentamethylcyclopentadienyldiiodide titanium, bispentamethylcyclopentadienyldifluorotitanium, bispenta Methyl cyclopentadienyl dicarbonyl titanium, bispentamethyl cyclopentadienyl dibutyl titanium (including n-butyl, sec-butyl, tert-butyl), bispentamethyl cyclopentadienyl dibenzyl titanium, bis pentamethyl cyclopenta Dienyldiphenyl titanium may also be mentioned.
Biscyclopentadienyldichlorotitanium is preferred because of its operational convenience, its stability in air and its ready commercial availability.

<(B) Cyril hydride> (b) is
At least one selected from the above-mentioned simple substance silyl hydride of the formula (i), polymer silyl hydride of the formula (ii), cyclosilyl hydride of the formula (iii), silazane compound of the formula (iv) and silazane analog of the formula (v). It is a kind of Cyril hydride.

In the chemical formula (i), suitable simple substance silyl compounds include methyldichlorosilane, ethyldichlorosilane, propyldichlorosilane, butyldichlorosilane, phenyldichlorosilane, dimethylchlorosilane, diethylchlorosilane, dipropylchlorosilane,
Dibutylchlorosilane, diphenylchlorosilane, dimethylmethoxysilane, dimethylethoxysilane, dimethylpropoxysilane, dimethylbutoxysilane, dimethylphenoxysilane, diethylmethoxysilane, diethylethoxysilane, diethylpropoxysilane, diethylbutoxysilane, diethylphenoxysilane, dipropylmethoxysilane , Dipropylethoxysilane, dipropylpropoxysilane, dipropylbutoxysilane,
Dipropylphenoxysilane, dibutylmethoxysilane, dibutylethoxysilane, dibutylpropoxysilane, dibutylbutoxysilane, dibutylphenoxysilane, diphenylmethoxysilane, diphenylethoxysilane, diphenylpropoxysilane, diphenylbutoxysilane, diphenylphenoxysilane, dimethylsilane, diethylsilane , Dipropylsilane, dibutylsilane, diphenylsilane, diphenylmethylsilane, diphenylethylsilane, diphenylpropylsilane, diphenylbutylsilane, trimethylsilane, triethylsilane, tripropylsilane, tributylsilane, triphenylsilane, methylsilane, ethylsilane, propylsilane , Butylsilane, phenylsilane, and methyldiacetoxysilane And the like.

In the chemical formula (ii), n ≧ 0, and preferably n is 0 to 100. Suitable polymerized silyl compounds in the chemical formula (ii) include polymethylhydrosiloxane, polyethylhydrosiloxane, polypropylhydrosiloxane, polybutylhydrosiloxane, polyphenylhydrosiloxane, 1,1,3,3-
Tetramethyldisiloxane may be mentioned.

Suitable silyl compounds in the chemical formula (iii) include methylhydrocyclosiloxane, ethylhydrocyclosiloxane, propylhydrocyclosiloxane, butylhydrocyclosiloxane,
Phenylhydrocyclosiloxane may be mentioned.

Suitable silazane compounds in the chemical formula (iv) include 1,1,3,3-tetramethyldisilazane,
Examples include 1,1,3,3-tetraethyldisilazane, 1,1,3,3-tetrapropyldisilazane, 1,1,3,3-tetrabutyldisilazane.

Suitable silazane analogs in formula (v) include compounds in which R ^a , R ^b and R ^c in formula (v) are all methyl groups.

Cyril hydride (b) in the present invention
Are of formulas (i), (ii), (iii), (iv) and (v)
Any of the above compounds can be used, preferably the compounds of formulas (i), (ii) and (iii), more preferably the compound of formula (ii).

The molar ratio of the silyl hydride (b) and the titanium compound (a) is (b) / (a) = 0.01 / 1-
200/1 is preferable, and 0.02 to 1 is more preferable.
100/1, more preferably 0.04 / 1 to 50/1
Is.

The silyl hydride (b) of the present invention improves the stability of the catalyst system to give a high conversion and a high selectivity of the olefinic double bond and good reproducibility of the hydrolysis. It is considered that the characteristic of the catalyst system having high hydrolytic activity and stability is that the biscyclopentadienyl titanium silyl hydride complex shown in the following formula is formed.

[0033]

[Chemical 11]

Where A ^* is a silicone group derived from silyl hydride (b).
One example is the following formula.

[0035]

[Chemical 12]

<(C) Metal compound> In the present invention, an organoaluminum compound, an organomagnesium compound, an organolithium compound, an organozinc compound, lithium hydride and LiOR ³ (wherein R ³ is an alkyl group, an aryl group, an aralkyl group or At least one metal compound (c) selected from the group (representing a cycloalkyl group) can be used in combination if necessary. The metal compound (c) is used for the purpose of reducing the negative influence of impurities in the conjugated diene polymer in the hydrolysis process, for example. Polar compounds such as tetrahydrofuran, triethylamine, N, N, N ', N'-tetramethylethylenediamine, and ethylene glycol dimethyl ether are likewise used as addition catalyst components.

Suitable organic aluminum compounds include trimethylaluminum, triethylaluminum, triisobutylaluminum, triphenylaluminum, diethylchloroaluminum, methylaluminum sesquichloride, ethylaluminum sesquichloride, diethylaluminum hydride, diisobutylaluminum hydride, Triphenylaluminum, and tri (2-
Ethylhexyl) aluminum.

Suitable organomagnesium compounds include:
Dimethyl magnesium, diethyl magnesium, methyl bromide, methyl chloromagnesium,
Mention may be made of magnesium ethyl bromide, magnesium methyl chloride, phenyl magnesium bromide, magnesium phenyl chloro, and magnesium dimethyl chloro.

Suitable organozinc compounds include diethyl zinc, biscyclopentadienyl zinc and diphenyl zinc.

Suitable LiOR ³ includes methoxylithium, ethoxylithium, n-propoxylithium, i-
Propoxy lithium, n-butoxy lithium, sec-butoxy lithium, t-butoxy lithium, pentyloxy lithium, hexyloxy lithium, hexyloxy lithium, octyloxy lithium, phenoxy lithium, 4-methylphenoxy lithium, 2,6-di-tert. -Butyl-4-methylphenoxylithium, and benzyloxylithium.

Suitable organolithium compounds include n-
Propyl lithium, isopropyl lithium, n-butyl lithium, sec-butyl lithium, t-butyl lithium, n
-Pentyllithium, benzyllithium, dilithium compounds (eg 1,4-dilithio-n-butane), and anionic living polymers having active lithium in the polymer chain.

The lithium hydride of the present invention may be used as it is or in the system (statics in s).
in situ), i.e., in the form of active conjugated diene polymers with active lithium ends sealed with hydrogen gas. Lithium hydride produced in statics in situ is preferred to give good hydrolytic activity.

The metal compound (c) is the titanium compound (a).
The amount is preferably 100 mol or less per mol, more preferably 0.5 to 25 mol, and further preferably 1 to 10 mol. If the amount of (c) exceeds 100 mol per 1 mol of (a), gel will be generated in the polymer, and other undesired reactions will occur to lower the catalytic activity.

<Catalyst> The catalyst of the present invention satisfying the above-mentioned (b) / (a) molar ratio and further (c) / (a) molar ratio exhibits high reactivity to olefinic double bonds. Therefore, the total amount of titanium components added during the reaction can be reduced, and an economically advantageous reaction process can be provided.

The catalyst of the present invention can be applied to polymers having all olefinically unsaturated double bonds, but is preferably applied to conjugated diene polymers. The conjugated diene polymer includes a homopolymer of conjugated diene, a copolymer of different conjugated dienes, and a copolymer of at least one conjugated diene and at least one olefin monomer. The conjugated dienes of these conjugated diene polymers used in the manufacture usually have from 4 to 12 carbon atoms, specific examples being 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene. 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, and 4,5-diethyl-
1,3-Butadiene can be mentioned. Among them, 1,3-butadiene and isoprene are industrially advantageous and can obtain excellent elastomer properties.

The conjugated diene polymer is prepared by using a radical or anion catalyst. This polymer can be made by bulk, solution, or emulsion polymerization techniques. Generally, when using the solution anion technique, the conjugated diene polymer is produced by simultaneously contacting one or more kinds of monomers for polymerization or by sequentially adding the monomers to an anionic polymerization initiator (for example, a Group IA metal and it). Alkyls, amides, silanolates (sila
Nolates), naphthalides, biphenyls, and anthracenyl derivatives) to polymerize. -150 ° C to 300 ° C in a solvent using an organic alkali metal compound
It is preferable to carry out in the temperature range of 0 ° C to 100 ° C.

The catalyst of the present invention is preferably applied to the hydrolysis of a copolymer obtained by copolymerizing at least one conjugated diene and at least one olefin monomer among the conjugated diene polymers. Preferred conjugated dienes for the production of this copolymer are as described above. As for the olefin monomer, any one that can be copolymerized with the conjugated diene can be used, but a vinyl-substituted aromatic hydrocarbon compound is preferable. Specific examples are styrene, tert-butylstyrene, α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylethylene, N, N-dimethyl-p-aminoethylstyrene, and N, N-diethyl. -P-aminoethylstyrene and the like can be mentioned, but styrene is most preferable. Specific examples of the copolymer of a conjugated diene and a vinyl-substituted aromatic hydrocarbon compound include a butadiene / styrene copolymer and an isoprene / styrene copolymer, and these two copolymers have high industrial value. Certain hydrolyzed copolymers can be provided.

Copolymers of conjugated dienes and vinyl-substituted aromatic hydrocarbon compounds are random copolymers, tapered block copolymers, complete block copolymers, and monomers in which the monomers are optionally distributed on the chain of the entire polymer. Including a graft copolymer. Among these polymers, block copolymers are particularly preferable for exhibiting the performance as a thermoplastic elastomer.

Such a block copolymer comprises at least one polymer block of (A) vinyl-substituted aromatic hydrocarbon compound and at least one polymer block of (B) conjugated diene. Preferably, the block copolymer has a polymer block containing styrene as a main component in an amount of 5 to 95.
% By weight and 95 to 5% by weight of a polymer block containing 1,3-butadiene and / or isoprene as a main component. Block (A) can contain some conjugated dienes, and block (B) can also contain some vinyl-substituted aromatic hydrocarbon compounds. The block copolymer includes not only a linear type but also a branched type, a radial type and a star type, which are obtained by coupling a linear type block polymer with a coupling agent. When the block copolymer which meets the above requirements is hydrolyzed, good elasticity is imparted to its olefin portion, an industrially useful copolymer is obtained, and its solution viscosity is low and the reaction solvent is low. And the hydrolyzed block copolymer can be produced more economically.

The conjugated diene polymer preferably has a 1,2-vinyl content of the structure of the diene portion of 6 to 80% by weight, and the block copolymer is 20 to 70% by weight.
It is preferable to have a polymer block of the conjugated diene.

Generally, the hydrolysis reaction of the conjugated diene polymer is carried out in a suitable solvent at a temperature of 0 ° C to 120 ° C (preferably at 50 ° C to 90 ° C) and a partial pressure of hydrogen gas of 1 psig to 12 ° C.
00 psig [7 kPa (gauge) to 8274 kPa
(Gage)], preferably 100 psig to 200 p
sig [690 kPa (gage) to 1389 kPa
(Gage)].

In the catalyst of the present invention, in the hydrolysis reaction of the conjugated diene polymer, the amount of the titanium compound in the catalyst is 0.001 mmol per 100 g of the conjugated diene polymer.
It is preferably used in a proportion of (mmol) to 20 mmol. Further, the contact time required for the hydrolysis is usually 10
~ 360 minutes.

The catalyst component of the present invention is added alone to the solution of the conjugated diene polymer, or it is added after mixing with some catalyst components in advance.

The hydrolysis reaction of the conjugated diene polymer is carried out in a stirred tank reactor or a loop reactor, and the hydrolyzed solution mixture is extracted from the reactor and pumped through a heat exchanger before being reacted again. And bring it into contact with hydrogen gas. The reaction is carried out continuously or batchwise. The catalyst of the present invention may be added as such into the reaction medium,
Alternatively, it is dissolved in the above-mentioned inert organic solvent and added.

The hydrolyzing process in the present invention is performed in a bulk system or a solution system. The inert solvent used in the anionic polymerization process in the solution system can be used directly without any special purification. The present invention provides a relatively simple reaction process, in which the anionic polymerization reaction and the hydrolysis reaction can proceed simultaneously in the same reaction medium. Any solvent commonly used to form conjugated diene polymers can be used, suitable are n-heptane, n-octane and the like and their alkyl-substituted derivatives, cyclopentane, cyclohexane, cyclohexane. Cycloaliphatic hydrocarbon compounds such as heptane and their alkyl-substituted derivatives, aromatic hydrocarbon compounds such as benzene, naphthalene, toluene, xylene and their alkyl-substituted derivatives, and hydrogenated aromatic hydrocarbon compounds such as tetralin and decalin And their derivatives, dimethyl ether, methyl ethyl ether,
Examples include linear and cyclic ethers such as diethyl ether and tetrahydrofuran, and their derivatives.

After the hydrolysis reaction, the reaction solution is cooled with an alcohol (eg, methanol, ethanol, or isopropanol) to precipitate the required hydropolymer. The precipitate is filtered and vacuum dried to obtain a polymer product of relatively high purity. Since the catalyst system of the present invention has high reactivity and is used in a small amount in the hydrolysis reaction, it is not necessary to perform a deashing process in the sense of removing the catalyst component.

Under suitable hydrolyzing conditions, the hydrolyzing catalysts of the present invention can quantitatively hydrolyze olefinically unsaturated double bonds and hydrolyze the double bonds to the required degree of hydrolysis. . In the hydrolysis of the conjugated diene polymer, the degree of hydrolysis is such that at least 50% (preferably at least 90%) of unsaturated double bonds of the conjugated diene unit are hydrolyzed. With respect to the copolymerization of the conjugated diene and the vinyl-substituted aromatic hydrocarbon compound, the hydrogenation is such that at least 50% (preferably 90%) of the unsaturated double bonds of the conjugated diene unit of the original copolymer are hydrolyzed. Double bonds in the aromatic portion of the original copolymer remain at 10% or less (preferably 5% or less) of hydrolyzation.

The degree of hydrolysis (%) of the olefinically unsaturated double bond is measured by infrared absorption spectrum. Ultraviolet absorption spectra and NMR of polymers containing aromatic rings
The spectrum is used together for measurement.

[0059]

EXAMPLES The present invention will be described in detail with reference to the following examples, but the examples of the present invention do not limit the scope of the present invention, and the scope of the present invention is based on the claims.

Example 1 Dimethyl titanocene (a) and chemical formulas (i), (ii),
The silyl hydride (b) of (iii) or (iv) is mixed in an inert solvent of Table 1 to obtain a light brown or brown solution. The catalyst is obtained by removing the volatile matter and drying in vacuum. The components (a) and (b) used are shown in Table 1 below.

[0061]

[Table 1]

(Note) * 1: Molecular weight 240 * 2: Molecular weight 420 * 3: Molecular weight 5000.

Example 2 A metal compound (c) (alkyllithium or alkylmagnesium) was mixed with a dichlorotitanocene (a) and a silyl hydride (b) of the chemical formula (i), (ii), (iii) or (iv). An active catalyst is obtained in addition to the inert solvent containing. The components (a), (b) and (c) used are shown in Table 2 below.

[0064]

[Table 2]

(Note) * 1: Molecular weight 240 * 2: Molecular weight 420 * 3: Molecular weight 5000.

Example 3 The catalyst component prepared in Example 1 is diluted with toluene or cyclohexane to obtain a 0.01 M catalyst solution (based on the Ti concentration). The obtained catalyst solution is directly used for hydrolyzing a styrene butadiene styrene (SBS) polymer. The SBS polymer (linear block copolymer, average molecular weight 100,000) is first subjected to anionic polymerization to seal the active chain with isopropanol, and then filtered.
Obtained by drying under vacuum overnight. The SBS polymer contains 30 wt% styrene units and 70 wt% butadiene units (including 25 wt% 1,2-vinyl structure). Then, an SBS / cyclohexane solution prepared by dissolving 15 g of SBS polymer in 125 ml of cyclohexane is directly used for the hydrolysis. That is, cyclohexane was used as a reaction solvent and H ₂ pressure of 2 was put in a 500 ml high-pressure pot.
00 psig [1379 kPa (gauge)], 60 ° C
The SBS polymer is hydrolyzed under the conditions of. The reaction is H ₂
Pressure 200 psig [1379 kPa (gauge)],
After continuing for 60 minutes under the condition of 60 ° C., the reaction solution is cooled with isopropanol. Filter and dry at 40 ° C. overnight to obtain the hydride. The obtained reaction product was analyzed by IR spectrum for the total conversion of olefinic double bonds. The results are shown in Table 3.

[0067]

[Table 3]

(Note) * 1 Conversion rate of catalyst: (number of converted butadiene moles) /
Calculated by (number of moles of catalyst) (the same applies hereinafter). * 2 Hydrolysis selectivity: [(Number of converted butadiene moles)
/ (Molar number of converted butadiene + Mole number of converted benzyl group double bond)] × 100 (%) (hereinafter the same).

Example 4 The catalyst component obtained in Example 2 was dissolved in toluene or cyclohexane to prepare a 0.01M catalyst solution (based on the Ti concentration). The obtained catalyst solution is directly used for hydrolyzing a styrene butadiene styrene (SBS) polymer. The SBS polymer is the same as that in Example 3. Cyclohexane was used as a reaction solvent, and H ₂ pressure was 200 psig [1379 kPa (gag
e)], The SBS polymer is hydrolyzed under the condition of 60 ° C. The reaction was conducted under H ₂ pressure of 200 psig [1379 kPa
(Gage)], after continuing for 60 minutes under the condition of 60 ° C., the reaction solution is cooled with isopropanol. Filter and dry at 40 ° C. overnight to obtain the hydride. The obtained reaction product was analyzed by IR spectrum for the total conversion of olefinic double bonds. The results are shown in Table 4.

[0070]

[Table 4]

Example 5 An SBS polymer obtained by anionic polymerization was not purified (SBS
The polymerization reaction was carried out in the same manner as in Example 4 except that the polymer solution still contained active lithium chain ends). The results of the hydrolysis are shown in the table below.

[0072]

[Table 5]

Example 6 Catalyst No. Hydrolysis reaction was carried out in the same manner as in Example 5 using 15, but the reaction conditions (reaction temperature, H ₂ pressure and reaction time) were changed as shown in Table 6. Table 6 shows the results of the hydrolysis.

[0074]

[Table 6]

Comparative Example 1 The same hydrolyzing reaction as in Example 3 was carried out, except that Cp ₂ Ti (C
Only H ₃ ) ₂ is used as reaction catalyst. The reaction is carried out with H ₂ pressure 2
00 psig [1379 kPa (gauge)], 60 ° C
After continuing for 60 minutes under the conditions of, the reaction solution is cooled with isopropanol. Filter and dry at 40 ° C. overnight to obtain the hydride. The total conversion of the olefinic double bond according to the IR spectrum was 45%, and the catalyst conversion of 725
Equivalent to 0.

Comparative Example 2 The same hydrolysis reaction as in Example 4 was carried out, except that Cp ₂ Ti (C
l) Only ₂ is used as reaction catalyst. The reaction is carried out with H ₂ pressure 2
00 psig [1379 kPa (gauge)], 60 ° C
After continuing for 60 minutes under the conditions of, the reaction solution is cooled with isopropanol. Filter and dry at 40 ° C. overnight to obtain the hydride. The total conversion of the olefinic double bond according to the IR spectrum was 28%, and the catalyst conversion of 450
Equivalent to 0.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Huang Cai Bao 219 Anxiang Street No. 26, No. 26, Anchang Street, Tainan City, Taiwan (72) Inventor Hiroaki Xiao, No. 229, Linan Road, Tainan City, Tainan, Taiwan (72) Inventor, Zhu Shinan, Tainan City, Taiwan Daidoji 2nd stage 61st street No. 16 13th floor (56) Reference JP-A-9-94462 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08F 8 / 00-8 / 50

Claims (18)

(57) [Claims] 1. A catalyst for hydrolyzing a conjugated diene polymer, which comprises the following (a) and (b): (A): at least one titanium compound represented by the following formula (a): [In the formula, R ¹ and R ² may be the same or different and each represents a halogen atom, an alkyl group, an aryl group, an aralkyl group, a cycloalkyl group, an aryloxy group, an alkoxy group or a carbonyl group. Cp ^* represents a cyclopentadienyl group which may have a substituent. ] (B): At least one silyl hydride selected from the following formulas (i) to (v): [Wherein, X ¹ , X ² and X ³ may be the same or different and each is a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an aralkyl group, a cycloalkyl group, an aryloxy group, an alkoxy group or an acyloxy group. Represents ] [Chemical 3] [Wherein R and R ^{3, which} may be the same or different, each represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an aralkyl group, a cycloalkyl group, an aryloxy group, or an alkoxy group, and when n ≧ 0, is there. However,
When n = 0, R ³ represents a hydrogen atom. ] [Chemical 4] [In the formula, R may be the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an aralkyl group, a cycloalkyl group, an aryloxy group, or an alkoxy group, and n = 2, 3, 4 or 5. ] [Chemical 5] [In the formula, R ^a , R ^b and R ^c may be the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an aralkyl group, a cycloalkyl group, an aryloxy group or an alkoxy group. . ] 2. The catalyst according to claim 1, wherein Cp ^* in the formula (a) is a cyclopentadienyl group. 3. The titanium compound is biscyclopentadienyldichlorotitanium, biscyclopentadienyldibrominated titanium, biscyclopentadienyldiiodinated titanium, biscyclopentadienyldifluorotitanium, biscyclopenta. Dienyl dicarbonyl titanium, biscyclopentadienyl dimethyl titanium, bis cyclopentadienyl diethyl titanium, bis cyclopentadienyl dipropyl titanium, bis cyclopentadienyl dibutyl titanium, bis cyclopentadienyl dibenzyl titanium, bis cyclo Pentadienyl diphenyl titanium, biscyclopentadienyl dimethoxy titanium, bis cyclopentadienyl diethoxy titanium,
Biscyclopentadienyldipropoxytitanium, Biscyclopentadienyldibutoxytitanium, Biscyclopentadienyldiphenoxytitanium, Biscyclopentadienylmethyl chlorotitanium, Biscyclopentadienylmethylbrominated titanium, Biscyclopenta A catalyst according to claim 1 or 2 selected from the group consisting of titanium dienylmethyliodide, biscyclopentadienylmethylfluorinated titanium, and mixtures thereof. 4. The simple substance silyl compound represented by the formula (i) is methyldichlorosilane, ethyldichlorosilane, propyldichlorosilane, butyldichlorosilane, phenyldichlorosilane, dimethylchlorosilane, diethylchlorosilane, dipropylchlorosilane, dibutyl. Chlorosilane, diphenylchlorosilane, dimethylmethoxysilane, dimethylethoxysilane, dimethylpropoxysilane, dimethylbutoxysilane, dimethylphenoxysilane, diethylmethoxysilane, diethylethoxysilane, diethylpropoxysilane, diethylbutoxysilane, diethylphenoxysilane, dipropylmethoxysilane, Dipropylethoxysilane, dipropylpropoxysilane, dipropylbutoxysilane, dipropylphenoxysilane, dibu Tylmethoxysilane, dibutylethoxysilane, dibutylpropoxysilane, dibutylbutoxysilane, dibutylphenoxysilane, diphenylmethoxysilane, diphenylethoxysilane, diphenylpropoxysilane, diphenylbutoxysilane, diphenylphenoxysilane, dimethylsilane, diethylsilane, dipropylsilane, Dibutylsilane, diphenylsilane, diphenylmethylsilane, diphenylethylsilane, diphenylpropylsilane, diphenylbutylsilane, trimethylsilane, triethylsilane, tripropylsilane, tributylsilane, triphenylsilane, methylsilane, ethylsilane, propylsilane, butylsilane, phenylsilane , And methyldiacetoxysilane. 1. 3 according to any one of the catalyst. 5. The polymerizable silyl compound represented by the formula (ii) is polymethylhydrosiloxane, polyethylhydrosiloxane, polypropylhydrosiloxane, polybutylhydrosiloxane, polyphenylhydrosiloxane, and 1,1,3. The catalyst according to any one of claims 1 to 4, which is selected from the group consisting of 3,3-tetramethyldisiloxane. 6. The cyclic silyl compound represented by formula (iii) is selected from the group consisting of methylhydrocyclosiloxane, ethylhydrocyclosiloxane, propylhydrocyclosiloxane, butylhydrocyclosiloxane, and phenylhydrocyclosiloxane. The catalyst according to claim 1. 7. A silazane compound represented by the formula (iv):
1,1,3,3-tetramethyldisilazane, 1,1,3,3-tetraethyldisilazane, 1,1,3,3-tetrapropyldisilazane, and 1,1,3,3-tetrabutyldisilazane A catalyst according to any one of claims 1 to 6 selected from the group consisting of silazanes. 8. The number average molecular weight of the conjugated diene polymer is 50.
The catalyst according to any one of claims 1 to 7, which is 0 to 1,000,000. 9. The catalyst according to claim 1, wherein the conjugated diene polymer is a polymer or copolymer of 1,3-butadiene and / or isoprene. 10. The conjugated diene polymer is 5 to 95% by weight of a polymer block containing styrene as a main component and 95 to 5% by weight of a polymer block containing 1,3-butadiene and / or isoprene as a main component. The catalyst according to any one of claims 1 to 9, which is a block copolymer containing 10% by weight. 11. The catalyst according to claim 1, wherein the conjugated diene polymer has a polymer block of a conjugated diene having a 1,2-vinyl content of 6 to 80% by weight. 12. The molar ratio of the titanium compound (a) and the silyl hydride (b) is (b) / (a) = 0.01 / 1.
The catalyst according to any one of claims 1 to 11, which is about 200/1. 13. (c) Organoaluminum compound, organomagnesium compound, organolithium compound, organozinc compound, lithium hydride and LiOR ³ (wherein R ³
Represents an alkyl group, an aryl group, an aralkyl group or a cycloalkyl group), and at least one metal compound selected from the group consisting of (a) 1 mol
The catalyst according to any one of claims 1 to 12, which is contained in a ratio of not more than 00 mol. 14. The catalyst according to claim 13, wherein the metal compound (c) is selected from the group consisting of an organolithium compound and an organomagnesium compound. 15. The organolithium compound has methyllithium, ethyllithium, n-propyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, t-butyllithium, phenyllithium, benzyllithium, and active lithium. 15. A catalyst according to claim 13 or 14 selected from the group consisting of active conjugated diene polymers. 16. A method for hydrolyzing a conjugated diene polymer, which comprises reacting a conjugated diene polymer with hydrogen in the presence of the catalyst according to any one of claims 1 to 15. 17. The amount of the titanium compound in the catalyst is 0.001 mmo based on 100 g of the conjugated diene polymer.
The method of hydrolyzing according to claim 16, wherein the catalyst is used so as to have a concentration of 1 to 20 mmol. 18. (a) and (b) according to claim 1,
(C) Organoaluminum compound, organomagnesium compound, organolithium compound, organozinc compound, lithium hydride and LiOR ³ (wherein R ³ is an alkyl group,
A catalyst for hydrolyzing a conjugated diene polymer, which comprises at least one metal compound selected from the group consisting of an aryl group, an aralkyl group and a cycloalkyl group.