CN101829600A - Hydrogenation catalyst composition and hydrogenation method thereof - Google Patents

Abstract

The present invention provides a specific catalyst composition for hydrogenating a conjugated diene polymer and a method for selectively hydrogenating a conjugated diene polymer using the same, which comprises reacting a conjugated diene polymer dissolved in an inert organic solvent with hydrogen in the presence of a hydrogenation catalyst composition to selectively hydrogenate hydrogenUnsaturated double bonds of conjugated diene units in the conjugated diene polymer are converted. The hydrogenation catalyst composition of the present invention comprises a titanium compound; (b) a compound represented by the formula (II)Formula (II) wherein R⁵Is C₁～C₁₂Alkyl, alkenyl, amino, ether, ketone or ester groups of R³And R⁶Is C₁～C₁₂Alkyl or alkenyl of, R⁴And R⁷Is C₁～C₁₂N is more than or equal to 1 and less than or equal to 3, and m is more than or equal to 1 and less than or equal to 3; and (c) an alkyl aluminum compound.

Description

Hydrogenation catalyst composition and hydrogenation method thereof

technical field

The invention relates to a hydrogenation catalyst composition and a hydrogenation reaction method thereof, in particular to a special catalyst composition for hydrogenating conjugated diene polymers and a method for selectively hydrogenating conjugated diene polymers using the special catalyst composition.

Background technique

In industry, conjugated diene (conjugated diene) monomers are usually used for single polymerization or copolymerization to obtain polymers containing unsaturated ethylenic groups in the polymer molecular chain. This polymer is quite favorable for vulcanization, but because of the presence of a large number of unsaturated double bonds, it will cause poor weather resistance, heat resistance, oxidation resistance and other properties. In particular, the thermoplastic rubber used for the polymerization of conjugated diene and vinyl aromatic hydrocarbon (vinyl aromatic hydrocarbon) as a monomer is a polymer with physical crosslinking, and the situation is more obvious. If it is used in styrene resin, Modifiers for olefin resins and impact-resistant materials are even more unfavorable. Compared with the application field of outdoor materials, it is strongly restricted due to its poor performance such as weather resistance, heat resistance, and oxidation resistance.

Copolymers polymerized with conjugated dienes and vinyl aromatic hydrocarbons as monomers can improve their weather resistance, heat resistance, and oxidation resistance by hydrogenation to greatly eliminate unsaturated double bonds. Many catalysts are known for the hydrogenation of polymers containing unsaturated double bonds, and these catalysts can be divided into two categories:

(1) Heterogeneous catalysts usually have to be deposited on a carrier as appropriate, such as carbon, silica, alumina, calcium carbonate, etc., and the metal is usually a compound composed of Ni, Pd, and Pt.

(2) Homogeneous catalysts, such as: (a) Ziegler-Natta (Ziegler-Natta) catalysts, which are organic salts of Ni, Co, Fe, Cr, etc. and a reducing agent (such as organoaluminum compounds) Combination; (b) a single composition of Ru, Rh, Ti, La organometallic compound.

Heterogeneous catalysts are widely used in industry, but compared with homogeneous catalysts, their activity is lower. Therefore, in order to achieve the desired hydrogenation, a large amount of catalyst must be used, and it must be carried out under higher temperature and pressure. In contrast, homogeneous catalysts are generally more active, a small amount of catalyst is sufficient, and the hydrogenation reaction can be carried out under relatively moderate pressure and temperature conditions.

In the method using a heterogeneous catalyst, the polymer to be hydrogenated is first dissolved in a suitable solvent and then contacted with hydrogen in the presence of the heterogeneous catalyst. The viscosity of the polymer is quite high. Due to the steric barrier of the polymer and the high adsorption of the polymer (once it is hydrogenated, it tends to stay on the surface of the catalyst), it is easy to interfere with the activation center close to the hydrogenated polymer, so the reaction between the reactants and the catalyst Contact is quite difficult. At the same time, the activity of this type of catalyst often drops sharply when the polymer is hydrogenated, which must be carried out under high temperature and high pressure, and the reaction heat of hydrogenation is very high. Hydrogenation at high temperature will cause the reaction temperature to rise sharply, making the polymer easy to Break down or form a gel. Therefore, under such operating conditions, it is extremely difficult to selectively hydrogenate the unsaturated double bond of the conjugated diene unit in the copolymer when it is desired to hydrogenate the copolymer polymerized by the conjugated diene and vinyl aromatic hydrocarbon. of. The reason is that under such high temperature and high pressure, the benzene ring core in the vinyl aromatic hydrocarbon unit is often hydrogenated. Another difficult operational situation is that it is quite difficult to separate the catalyst from the hydrogenated polymer solution, since the polymer is strongly adsorbed on the heterogeneous catalyst, and it is impossible to completely remove it.

In the method using the Ziegler-Natta catalyst hydrogenation system, the hydrogenation reaction essentially occurs on a homogeneous medium, so the hydrogenation of the copolymer can be carried out under moderate pressure and temperature conditions. Furthermore, by sufficiently selecting the hydrogenation conditions, it is possible to selectively hydrogenate the double bond of the conjugated diene unit without hydrogenating the aromatic ring of the vinyl aromatic hydrocarbon unit. However, the amount of catalyst used is relatively high (higher catalyst concentration is required), and it is not easy to completely remove the catalyst from the obtained product. A catalyst removal process is required for subsequent treatment, thus causing product instability and catalyst removal process. The resulting energy consumption.

The above-mentioned shortcomings of the Ziegler-Natta catalytic hydrogenation system can be solved by using a cyanocene-based hydrogenation catalyst. Traditionally, the method of hydrogenating conjugated diene unit polymers using a homogeneous catalyst of a cyanocene hydrogenation catalyst is introduced as follows:

For example, U.S. Patent No. 4,980,421 discloses the selective hydrogenation reaction of unsaturated double bonds of conjugated diene unit polymers, which is based on the use of bis(cyclopentadienyl)titanium (+4) compounds, lithium alkoxides (LiOR), And hydrogenation catalysts of organometallic compounds (such as aluminum, zinc, magnesium compounds) for hydrogenation. The hydrogenation catalyst is highly active, so a small amount of hydrogenation catalyst can achieve an effective hydrogenation effect without deashing (deash) step, and can be carried out under mild conditions.

U.S. Patent No. 5,270,274 publishes a hydrogenation catalyst composition which includes a bis(cyclopentadienyl)titanium (+4) compound, a polar compound containing a carbonyl group (carbonyl) and an epoxy group (epoxy), and an organolithium compound, It can preferentially hydrogenate the unsaturated double bonds of conjugated diene polymers, and the hydrogenated polymers have excellent physical properties and weather resistance.

U.S. Patent No. 5,244,980 discloses that the active conjugated diene polymer is terminated with hydrogen, and an organic alkali metal (especially an organic lithium metal) is added, and a Tebbe catalyst is added. Said to have a good hydrogenation effect.

The catalyst combination disclosed in U.S. Patent 5,886,108 has an active conjugated diene polymer, and under the condition of adding a hydroxyl group (hydroxyl), a carbonyl group or an ester group (ester), at least one bis(cyclopentadienyl) The compound Tebbe (Tebbe) catalyst formed by the long-term reaction of titanium (+4) compound and trimethylaluminum is said to have good hydrogenation efficiency if the compound participates in the hydrogenation reaction.

The catalyst combination published in U.S. Patent No. 5,985,995 has an active conjugated diene unit polymer, and under the condition of adding an alkyl silicon halide or an alkyl tin halide, there is at least dibenzyloxy bis (cyclopentadienyl) titanium It is said that under this combination of catalysts, there will be quite good hydrogenation efficiency.

U.S. Patent No. 5,948,869 publishes the selective hydrogenation reaction of unsaturated double bonds of conjugated diene unit polymers, and its catalyst combination is at least two (cyclopentadienyl) titanium (+4) compounds, at least zinc or magnesium alkane base, and some solvents with ester groups and aromatic groups are added as accelerators. It is said that this catalyst combination is quite helpful for improving hydrogenation efficiency.

The catalyst combination of European patent application 0434469A2 relates to a biscyclopentadienyl titanium compound and one of aluminum or magnesium and an alkali metal in the presence of alkoxides of alkali metals and ethers, ketones and other types of polar compounds Composition of an organometallic compound, the catalyst system has the ability to hydrogenate conjugated diene polymers and copolymers thereof.

European Patent Application No. 0544304A describes the use of catalyst compositions comprising: (a) a bis(cyclopentadienyl) transition metal compound; (b) at least one polar compound which is a carbonyl-containing compound or Compounds containing epoxy groups, such as esters of monobasic or dibasic acids, lactone compounds, lactam compounds, or epoxy compounds; (c) organolithium compounds; and (d) reduced organometallic compounds, such as aluminum compounds , zinc compounds and magnesium compounds, specific examples such as triethylaluminum. This combination of catalysts is quite helpful for the improvement of hydrogenation efficiency.

U.S. Patent 6,313,230 and the People's Republic of China Patent CN1324867 published the selective hydrogenation reaction of unsaturated double bonds in conjugated diene polymers. Its catalyst combination is at least two (cyclopentadienyl) titanium (+4) compounds, and contains Trisubstituted silane compound with Si-H functional group, it is reported that this catalyst combination is quite helpful for improving hydrogenation efficiency. However, since the compound has hydrogen atoms, it is easy to cause hydrolysis, and it is easy to react with oxygen atoms or strong polar functional groups, so it is not easy to store at normal temperature. In addition, from the examples of this patent, it can be seen that the maximum temperature of the hydrogenation reaction is about 60°C, and the hydrogenation reaction cannot be continuously carried out in a high temperature environment, and this catalyst combination is easily deactivated during the high temperature hydrogenation reaction, so it must be used during the hydrogenation reaction. Remove a large amount of heat of reaction, otherwise the hydrogenation rate is not good, and the catalyst combination is not stored for a long time in nitrogen environment, and the catalyst activity is easy to decline. Suitable for continuous process production.

As mentioned above, although many kinds of catalyst compositions are available for the hydrogenation of conjugated diene polymers, the amount of catalyst used is still relatively high, resulting in unstable products and cumbersome catalyst removal problems. In order to solve the above problems and meet the needs of the market, the team of the present invention has developed a new hydrogenation method after in-depth research and analysis, and countless experiments and improvements. It has a stable and easy-to-storage catalyst composition, and uses this low-dosage catalyst combination. can successfully hydrogenate conjugated diene polymers without removing the catalyst from the hydrogenated compound, and this catalyst combination still has a relatively high catalytic activity at a relatively high reaction temperature, which is very suitable for commercialization. Produce.

Contents of the invention

The object of the present invention is to provide a method for hydrogenating conjugated diene polymers and its catalyst composition, which can successfully hydrogenate conjugated diene polymers only by using a small amount of hydrogenation catalyst composition, and shows considerable activity. Since the catalyst concentration used is very low, there is no need to remove the catalyst from the hydrogenated polymer, which greatly improves the economic efficiency. Furthermore, the hydrogenation reaction of the present invention is very rapid and has good reproducibility of results under a wide range of temperatures and pressures.

To achieve the above object, the present invention provides a stable and easy-to-storage catalyst composition, ie, a method for hydrogenating conjugated diene polymer using the catalyst composition.

The hydrogenation catalyst composition of the present invention comprises the following hydrogenation catalysts:

(a) Titanium compounds or mixtures thereof:

The preferred titanium compound can be shown in formula (I):

Formula (I)

Wherein R ¹ and R ² are the same or different substituents, and are hydrogen, halogen atom, C ₁ ~C ₈ alkyl, C ₁ ~C ₈ alkoxy, C ₆ ~C ₁₂ cycloalkyl, benzene radical, phenoxy, C ₇ ～C ₁₀ arylalkoxy, C ₇ ～C ₁₀ aralkyl, carboxyl, -CH ₂ P(phenyl) ₂ , -CH ₂ Si(C ₁ ～C ₅ alkyl ) ₃ or -P(phenyl) ₂ ; Cp* represents cyclopentadienyl, fluorenyl, indenyl or derivatives thereof; said derivatives are on the ring of fluorenyl, indenyl or cyclopentadienyl One or more hydrogens of is replaced by a substituent;

(b) Compounds as shown in formula (II):

The hydrogenation catalyst (b) of the present invention is to at least comprise the compound shown in formula (II):

Formula (II)

Wherein R ⁵ is C ₁ ~ C ₁₂ alkyl, alkenyl, amino, ether, ketone or ester group, R ³ and R ⁶ are C ₁ ~ C ₁₂ alkyl or alkenyl, R ⁴ and R ⁷ is an alkyl group, alkenyl group, amino group, ether group, ketone group or ester group of C ₁ to C ₁₂ , 1≤n≤3, 1≤m≤3; and

(c) aluminum alkyl compounds;

The preferred aluminum alkyl compound can be shown in formula (III):

Formula (III)

Wherein R ⁸ , R ⁹ and R ¹⁰ may be the same or different substituents, and are C ₁ -C ₁₂ alkyl groups, C ₆ -C ₁₂ aryl groups, hydrogen atoms or halogen atoms.

According to the present invention, the preferred molar ratio of the hydrogenation catalyst (b) to the hydrogenation catalyst (a) is 0.1 to 50, and the preferred molar ratio of the hydrogenation catalyst (c) to the hydrogenation catalyst (a) is 0.1 to 50.

The hydrogenation catalyst combination of the present invention is a stable and easy-to-storage catalyst composition. In particular, the hydrogenation catalyst (b) whose composition is shown in the formula (II) can cooperate with the composition of (a) and (c) catalysts to improve the overall hydrogenation efficiency and stabilize the activity of other catalysts, so it can be used as the catalyst of the present invention When the composition is added to the conjugated diene polymer, it can be stored for a long period of time, and the activity of the catalyst still has good stability and reproducibility, which is quite economical.

Another object of the present invention is to provide a method for producing a catalyst composition for hydrogenation of a conjugated diene polymer, the conjugated diene polymer is a homopolymer or a conjugated diene A copolymer of olefin and vinyl aromatic hydrocarbon as a monomer, dissolved in an inert organic solvent or an inert organic solvent containing some ethers and amines polar compounds, the conjugated diene polymer in the hydrogenation catalyst (a), (b), and (c) react with hydrogen in the presence of the composition to selectively hydrogenate the unsaturated double bond of the conjugated diene unit in the conjugated diene polymer; the hydrogenation catalyst composition includes the following The hydrogenation catalyst:

(a) Titanium compounds or mixtures thereof:

Titanium compound as shown in formula (I):

Formula (I)

Wherein R ¹ and R ² are the same or different substituents, and are hydrogen, halogen atom, C ₁ ~C ₈ alkyl, C ₁ ~C ₈ alkoxy C ₆ ~C ₁₂ cycloalkyl, phenyl , phenoxy, C ₇ ～C ₁₀ arylalkoxy, C ₇ ～C ₁₀ aralkyl, carboxyl, -CH ₂ P(phenyl) ₂ , -CH ₂ Si(C ₁ ～C ₅ alkyl) ₃ or -P(phenyl) ₂ ; Cp* represents cyclopentadienyl, fluorenyl, indenyl or derivatives thereof; said derivatives are on the ring of fluorenyl, indenyl or cyclopentadienyl One or more hydrogens are replaced by a substituent;

(b) Compounds as shown in formula (II):

Formula (II)

Wherein R ⁵ is C ₁ ~ C ₁₂ alkyl, alkenyl, amino, ether, ketone or ester group, R ³ and R ⁶ are C ₁ ~ C ₁₂ alkyl or alkenyl, R ⁴ and R ⁷ is an alkyl group, alkenyl group, amino group, ether group, ketone group or ester group of C ₁ to C ₁₂ , 1≤n≤3, 1≤m≤3; and

(c) Alkyl aluminum compounds:

Alkyl aluminum compounds as shown in formula (III):

Formula (III)

Wherein R ⁸ , R ⁹ and R ¹⁰ may be the same or different substituents, and are C ₁ -C ₁₂ alkyl groups, C ₆ -C ₁₂ aryl groups, hydrogen atoms or halogen atoms.

According to the present invention, the method for hydrogenating a conjugated diene polymer, the conjugated diene polymer used is a homopolymer or a copolymer of a conjugated diene, and the hydrogenation reaction is carried out at a reaction temperature of 0°C to 200°C Between, the hydrogen pressure is in the range of 1kg/cm ² to 90kg/cm ² . In addition, the hydrogenation catalyst (a) is used in an amount of 0.0001 to 50 mmol relative to 100 g of the conjugated diene polymer.

In order to make the structure, method of operation and features of the present invention more obvious and easy to understand, the preferred embodiments are specially cited below, and in conjunction with the accompanying drawings, they are described in detail as follows:

Description of drawings

Fig. 1 is an infrared spectrum of a styrene-butadiene-styrene polymer before and after hydrogenation according to an embodiment of the present invention.

Fig. 2 is the infrared spectrum of the styrene-butadiene-styrene polymer before and after hydrogenation of a comparative example of the present invention.

Detailed ways

The hydrogenation catalyst composition of the present invention comprises hydrogenation catalysts (a) to (c), wherein:

Hydrogenation catalyst (a) titanium compound or its mixture:

Including titanium compounds or mixtures thereof shown in formula (I):

Formula (I)

Wherein R ¹ and R ² are the same or different substituents, and are hydrogen atom, halogen atom, C ₁ -C ₈ alkyl, C ₁ -C ₈ alkoxy, C ₆ -C ₁₂ cycloalkyl, Phenyl, phenoxy, C ₇ -C ₁₀ arylalkoxy, C ₇ -C ₁₀ arylalkyl, carboxy, -CH ₂ P(phenyl) ₂ , -CH ₂ Si(C ₁ ~C ₅ alkyl) ₃ or -P(phenyl) ₂ ; Cp* represents cyclopentadienyl, fluorenyl, indenyl or the above derivatives; the derivatives are fluorene One or several hydrogens on the ring of yl, indenyl or cyclopentadienyl are replaced by a substituent.

According to the present invention, Cp* can be, for example, C ₅ R ¹¹ R ¹² R ¹³ R ¹⁴ R ¹⁵ (cyclopentadienyl or its derivatives), wherein R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ can be The same or different substituents, and can be selected from hydrogen, halogen atom, alkyl, aromatic hydrocarbon group, or carboxyl (carboxyl), -CH ₂ P (phenyl) ₂ , -CH ₂ Si (C ₁ ~C ₅ alkyl) ₃ or -P(phenyl) ₂ .

The hydrogenation catalyst (a) suitable for the present invention is the compound shown in formula (I), wherein with respect to the halide compound of bis(cyclopentadienyl and derivatives thereof) titanium, such specific embodiments include bis( Cyclopentadienyl) titanium difluoride [bis (cyclopentadienyl) titanium difluorides], bis (cyclopentadienyl) titanium dichloride [bis (cyclopentadienyl) titanium dichlorides], bis [(2,4-diphenyl Phosphinated cyclopentadienyl)] titanium difluoride [bis (2,4-diphenylphosphinecyclopentadienyl) titanium difluorides], bis [(2,4-dimethylphosphine cyclopentadienyl)] titanium difluoride [ bis(2,4-dimethylphosphine cyclopentadienyl)titanium difluorides], bis[(2,4-diphenylphosphine cyclopentadienyl)]titanium dichloride [bis(2,4-diphenylphosphinecyclopentadienyl)titanium dichlorides], bis (Methoxycyclopentadienyl) titanium dichloride [bis(dimethoxycyclopentadienyl) titanium dichloride], bis [(2,4-diethylphosphinocyclopentadienyl)] titanium dichloride [bis(2 , 4-diethylphosphine cyclopentadienyl) titanium dichlorides], bis (cyclopentadienyl) titanium dibromide [bis (cyclopentadienyl) titanium dibromides], bis [(2,4-diphenylphosphine cyclopentadienyl)] Titanium dibromide [bis(2,4-diphenylphosphinecyclopentadienyl)titanium dibromides], bis[(2,4-dimethylphosphinecyclopentadienyl)]titanium dibromide [bis(2,4-dimethylphosphinecyclopentadienyl)titanium dibromides], bis(ethylcyclopentadienyl) titanium dichloride [bis(ethylcyclopentadienyl) titanium dichlorides], bis(n-propylcyclopentadienyl) titanium dichloride [bis(n-propylcyclopentadienyl) Titanium dichlorides], bis(n-butylcyclopentadienyl) titanium dichloride [bis(n-butylcyclopentadienyl)t itanium dichlorides] or bis(2-ethylhexyl cyclopentadienyl) titanium dichloride [bis(2-ethylhexyl cyclopentadienyl) titanium dichlorides]. The hydrogenation catalyst (a) according to the present invention is a compound shown in formula (I), wherein with respect to the alkoxy or alkyl organic compound of bis(cyclopentadienyl and its derivatives) titanium, such specific Examples include dimethyl bis (cyclopentadienyl) titanium [bis (cyclopentadienyl) titanium dimethyl], dimethoxy bis (cyclopentadienyl) titanium [bis (cyclopentadienyl) titanium dimethoxy], dimethoxy bis [(2,4-diphenylphosphine cyclopentadienyl)]titanium[bis(2,4-diphenylphosphine cyclopentadienyl)titaniumdimethoxy], dimethoxy bis[(2,4-dimethylphosphine cyclopentadienyl) Dienyl)] titanium [bis (2,4-dimethylphosphinecyclopentadienyl) titanium dimethoxy], diethoxy bis (cyclopentadienyl) titanium [bis (cyclopentadienyl) titanium dimethoxy], diethoxy bis [(2, 4-diphenylphosphinecyclopentadienyl)]titanium [bis(2,4-diphenylphosphinecyclopentadienyl)titanium dimethoxy], diethoxybis[(2,4-dimethylphosphinecyclopentadienyl) ]Titanium[bis(2,4-dimethylphosphinecyclopentadienyl)titanium dimethoxy], diphenoxybis[(2,4-diphenylphosphinecyclopentadienyl)]titanium[bis(2,4-diphenylphosphinecyclopentadienyl)titanium diphenoxy ], diphenoxybis[(2,4-dimethylphosphine cyclopentadienyl)]titanium [bis(2,4-dimethylphosphine cyclopentadienyl)titanium diphenoxy].

The hydrogenation catalyst (a) according to the present invention is a compound shown in formula (I), wherein with regard to bis(fluorenyl, indenyl or derivatives thereof) titanium halides, such specific examples include bis(1 -Fluorenyl)titanium dichlorides [bis(1-fluorenyl)titaniumdichlorides], bis(1-indenyl)titanium dichlorides], bis(dimethoxyfluorenyl)dichlorides Titanium dichloride [bis (dimethoxyfluorenyl) titanium dichlorides], bis (indenyl) titanium dichloride [bis (indenyl) titanium dichlorides], bis (fluorenyl) titanium difluoride [bis (fluorenyl) titanium difluorides], bis (indenyl) ) titanium difluoride [bis (indenyl) titanium difluorides], bis (dimethoxyfluorenyl) titanium difluoride [bis (dimethoxy fluorenyl) titanium difluorides], bis (indenyl) titanium difluoride [bis (indenyl) itanium difluorides], bis (fluorenyl) titanium dibromide [bis (fluorenyl) titanium dibromides], bis (indenyl) titanium dibromide [bis (indenyl) titanium dibromides], bis (dimethoxyfluorenyl) titanium [bis (dimethoxyfluorenyl) titanium], bis (indenyl) titanium dibromide [bis (indenyl) titanium dibromides]. According to the alkoxy or alkyl organic compounds of bis(fluorenyl, indenyl or derivatives thereof) titanium, such specific examples include dimethyl bis(fluorenyl)titanium [bis(fluorenyl)titanium dimethyl ], dimethoxy bis (fluorenyl) titanium [bis (fluorenyl) titanium dimethoxy], dimethoxy bis (indenyl) titanium [bis (indenyl) titanium dimethoxy], dimethoxy bis (dimethoxy fluorene Base) titanium [bis (dimethoxyfluorenyl) titanium dimethoxy], diphenoxy bis (fluorenyl) titanium [bis (fluorenyl) titanium diphenoxy], diphenoxy bis (indenyl) titanium [bis (indenyl) titanium diphenoxy], Diphenoxybis(dimethoxyfluorenyl)titanium [bis(dimethoxyfluorenyl)titanium diphenoxy], diphenoxybis(indenyl)titanium[bis(indenyl)titanium diphenoxy]. The so-called derivatives here mean that one or several hydrogens on the ring of fluorenyl, indenyl or cyclopentadienyl are replaced by a substituent, such as methyl, methoxy, p- - a group such as tert-butylphenyl, pentafluorophenyl, trifluorophenyl, difluorophenyl or 3,5-(tert-butyl)-4-methoxyphenyl. An example of a preferable hydrogenation catalyst (a) is bis(cyclopentadienyl)titanium dichloride.

The hydrogenation catalyst (b) of the present invention comprises the compound shown in formula (II):

Formula (II)

Wherein R ⁵ is C ₁ ~ C ₁₂ alkyl, alkenyl, amino, ether, ketone or ester group, R ³ and R ⁶ are C ₁ ~ C ₁₂ alkyl or alkenyl, R ⁴ and R ⁷ is a C ₁ -C ₁₂ alkyl group, alkenyl group, amino group, ether group, ketone group or ester group, 1≤n≤3, 1≤m≤3.

According to the above idea, R ³ and R ⁶ in the hydrogenation catalyst (b) are C ₁ -C ₈ alkyl groups, R ⁴ , R ⁷ and R ⁵ are all selected from C ₁ -C ₈ alkyl groups, amino groups , ether or ketone groups.

According to the idea above, R ³ and R ⁶ in the hydrogenation catalyst (b) are C ₁ -C ₄ alkyl groups, R ⁴ and R ⁷ are C ₁ -C 6 alkyl groups, and R ⁵ is C ₁ -C ₆ alkyl groups. ₈ alkyl.

According to the idea above, R ³ and R ⁶ in the hydrogenation catalyst (b) are C ₁ -C ₄ alkyl groups, R ⁴ and R ⁷ are C ₁ -C ₆ alkyl groups, and R ⁵ is R ¹¹ R ¹² R ¹³ N, R ¹¹ , R ¹² and R ¹³ are C ₁ -C ₆ alkyl groups or one of them is a hydrogen atom.

According to the idea above, R ³ and R ⁶ in the hydrogenation catalyst (b) are C ₁ -C ₄ alkyl groups, R ⁴ and R ⁷ are C ₁ -C ₆ alkyl groups, and R ⁵ is R ¹⁴ -OR ¹⁵ , R ¹⁴ and R ¹⁵ are C ₁ -C ₆ alkyl groups.

R¹⁶及R¹⁷为C₁～C₆的烷基。According to the above idea, R ³ and R ⁶ in the hydrogenation catalyst (b) are C ₁ -C ₄ alkyl groups, R ⁴ and R ⁷ are C ₁ -C ₆ alkyl groups, and R ⁵ is

R ¹⁶ and R ¹⁷ are C ₁ -C ₆ alkyl groups.

According to the idea above, R ³ and R ⁶ in the hydrogenation catalyst (b) are C ₁ -C ₄ alkyl groups, R ⁴ and R ⁷ are C ₁ -C 6 alkyl groups, and R ⁵ is C ₁ -C ₆ alkyl groups. ₆ alkyl or R ¹¹ -NH-R ¹² , R ¹¹ and R ¹² are C ₁ -C ₄ alkyl.

According to above-mentioned idea, hydrogenation catalyst (b) is to comprise the compound shown in formula (II), and when n=1, m=1, the concrete example of this type includes bis(methoxydimethylsilyl)ethane ( bis(methoxydimethylsilyl)ethane), bis(methoxydimethylsilyl)hexane (bis(methoxydimethylsilyl)hexane), bis(methoxydimethylsilylpropyl)amine (bis(methoxydimethylsilylpropyl)amine), Bis(methoxydiethylsilyl)ethane (bis(methoxydiethylsilyl)ethane), bis(methoxydiethylsilyl)hexane (bis(methoxydiethylsilyl)hexane), bis(methoxydiethylsilyl)hexane Silylpropyl) amine (bis(methoxydiethylsilylpropyl)amine), bis(ethoxydimethylsilyl)ethane (bis(ethoxydimethylsilyl)butane), bis(ethoxydimethylsilyl)hexane (bis (ethoxydimethylsilyl)hexane), bis(ethoxydimethylsilylpropyl)amine (bis(ethoxydimethylsilylpropyl)amine), bis(ethoxydiethylsilyl)ethane (bis(ethoxydiethylsilyl)ethane), bis (ethoxydiethylsilyl) hexane (bis(ethoxydiethylsilyl)hexane), bis(ethoxydiethylsilylpropyl)amine (bis(ethoxydiethylsilylpropyl)amine), bis(propoxydimethylsilyl)amine Silyl) ethane (bis (propyldimethylsilyl) ethane), bis (propoxydimethylsilyl) hexane (bis (propoxydimethylsilyl) hexane), bis (propoxydimethylsilyl propyl) amine (bis (propoxydimethylsilylpropyl)amine), bis(propoxydiethylsilyl)ethane (bis(propoxydiethylsilyl)ethane), bis(propoxydiethylsilyl)hexane (bis(propoxydiethylsilyl)hexane), bis( Propoxydiethylsilylpropyl)amine (bis(propoxydiethylsilylpropyl)amine), bis(isopropoxydimethylsilyl)ethane (bis(isopropoxydimethylsilyl)hexane), bis(isopropoxydimethylsilyl) silylpropyl) Amine (bis(isopropoxydimethylsilylpropyl)amine), bis(isopropoxydiethylsilyl)ethane (bis(isopropoxydiehtylsilyl)ethane), bis(isopropoxydiethylsilyl)hexane (bis(isopropoxydiethylsilyl) hexane), bis(isopropyldiethylsilylpropyl)amine (bis(isopropoxydiethylsilylpropyl)amine), bis(isopropyldiethylsilylpropyl)amine (bis(isopropoxydiethylsilylpropyl)amine);

According to the above idea, the hydrogenation catalyst (b) is to comprise the compound shown in the formula (II), when n=1, m=2, such specific examples include (dimethoxymethylsilyl) (methoxy Dimethylsilyl) ethane ((dimethoxymethylsilyl) (methoxydimethylsilyl) ethane), (dimethoxymethylsilyl) (methoxydimethylsilyl) hexane ((dimethoxymethylsilyl) (methoxydimethylsilyl) hexane), [(Dimethoxymethylsilyl)propyl]-[(methoxydimethylsilyl)propyl]amine[(dimethoxymethylsilyl)propyl]-[(methoxydimethylsilyl)propyl]amine, (dimethoxy Ethylsilyl) (methoxydiethylsilyl) ethane ((dimethoxyethylsilyl) (methoxydiethylsilyl) ethane), (dimethoxyethylsilyl) (methoxydiethylsilyl) hexane ( (dimethoxyethylsilyl)(methoxy diethylsilyl)hexane), [(dimethoxyethylsilyl)propyl]-[(methoxydiethylsilyl)propyl]amine[(dimethoxyethylsilyl)propyl]-[(methoxydiethylsilyl )propyl]amine, (diethoxymethylsilyl) (ethoxydimethylsilyl) ethane ((diethoxymethylsilyl) (ethoxydimethylsilyl) ethane), (diethoxymethylsilyl) (ethoxy (diethoxymethylsilyl)(ethoxydimethylsilyl)hexane), [(diethoxymethylsilyl)propyl]-[(ethoxydimethylsilyl)propyl]amine[ (diethoxymethylsilyl)propyl]-[(ethoxydimethylsilyl)propyl]amine, (diethoxyethylsilyl)(ethoxydiethylsilyl)ethane ((diethoxyethylsilyl)(ethoxydiethylsilyl)ethane), (diethoxy (Diethoxyethylsilyl)(ethoxydiethylsilyl)hexane ((diethoxyethylsilyl)(ethoxydiethylsilyl)hexane), [(diethoxyethylsilyl)propyl]-[(ethoxydiethylsilyl) base silyl) propyl] amine [(diethoxyethylsilyl) prop yl]-[(ethoxy diethylsilyl)propyl]amine, (dipropoxymethylsilyl)(propoxydimethylsilyl)ethane ((dipropoxymethylsilyl)(propoxydimethylsilyl)ethane), (dipropoxymethylsilyl) (dipropoxymethylsilyl)(propoxydimethylsilyl)hexane ((dipropoxymethylsilyl)(propoxydimethylsilyl)hexane), [(dipropoxymethylsilyl)propyl]-[(propoxydimethylsilyl) Base) propyl] amine [(dipropoxymethylsilyl) propyl]-[(propoxydimethylsilyl) propyl]amine, (dipropoxyethyl silyl) (propoxy diethyl silyl) ethane ((dipropoxyethylsilyl) (propoxydiethyl silyl) )ethane), (dipropoxyethylsilyl) (propoxydiethylsilyl) hexane ((dipropoxyethylsilyl) (propoxydiethylsilyl) hexane), [(dipropoxyethylsilyl) propyl] -[(propoxydiethylsilyl)propyl]amine[(dipropoxyethylsilyl)propyl]-[(propoxydiethylsilyl)propyl]amine; when n=1, m=3, specific examples of this class include (methoxy (methoxydimethylsilyl)(trimethoxysilyl)ethane ((methoxydimethylsilyl)(trimethoxysilyl)ethane), (methoxydimethylsilyl)(trimethoxysilyl)hexane ((methoxydimethylsilyl)( trimethoxysilyl) hexane), [(methoxydimethylsilyl) propyl]-[(trimethoxysilyl) propyl] amine [(methoxydimethylsilyl) propyl]-[(trimethoxysilyl) propyl]amine, (methoxy (methoxydiethylsilyl)(trimethoxysilyl)ethane ((methoxydiethylsilyl)(trimethoxysilyl)ethane), (methoxydiethylsilyl)(trimethoxysilyl)hexane ((methoxydiethylsilyl)( trimethoxysilyl)hexane), [(methoxydiethylsilyl)propyl]-[(trimethoxysilyl)propyl]amine[(methoxydiethylsilyl)propyl]-[(trimethox ysilyl)propyl]amine, (ethoxydimethylsilyl) (triethoxysilyl) ethane ((ethoxydimethylsilyl) (triethoxysilyl) ethane), (ethoxydimethylsilyl) (triethoxy (ethoxydimethylsilyl)(triethoxysilyl)hexane), [(ethoxydimethylsilyl)propyl]-[(triethoxydimethylsilyl)propyl]amine[(ethoxydimethylsilyl)propyl] -[(triethoxysilyl)propyl]amine, (ethoxydiethylsilyl)(triethoxysilyl)ethane ((ethoxy diethylsilyl)(triethoxysilyl)ethane), (ethoxydiethylsilyl) (Triethoxysilyl) hexane ((ethoxydiethylsilyl)(triethoxysilyl)hexane), [(ethoxydiethylsilyl)propyl]-[(triethoxysilyl)propyl]amine[( ethoxydiethylsilyl)propyl]-[(triethoxysilyl)propyl]amine, (propoxydimethylsilyl)(tripropoxysilyl)ethane (propoxydimethylsilyl)(tripropoxysilyl)ethane, (propoxydimethylsilyl) ) (tripropoxysilyl) hexane (propoxydimethylsilyl) (tripropoxysilyl) hexane, [(propoxydimethylsilyl) propyl] - [(tripropoxysilyl) propyl] amine [(propoxydimethylsilyl )propyl]-[(tripropoxysilyl)propyl]amine, (propoxydiethylsilyl)(tripropoxysilyl)ethane (propoxydiethylsilyl)(tripropoxysilyl)ethane, (propoxydiethylsilyl) (Tripropoxydiethylsilyl) hexane (propoxy diethylsilyl) (tripropoxysilyl) hexane, [(propoxydiethylsilyl) propyl] - [(tripropoxydiethylsilyl) propyl] amine [(propoxydiethylsilyl) )propyl]-[(tripropoxysilyl)propyl]amine; when n=2, m=2, specific examples of this class include bis(dimethoxymethylsilyl)ethane (bis(dimethoxymethylsilyl)ethane), bis (dimethoxymethylsilyl Alkyl) hexane (bis(dimethoxymethylsilyl)hexane), bis(dimethoxymethylsilylpropyl)amine (bis(dimethoxymethylsilylpropyl)amine), bis(dimethoxyethylsilyl)ethane (bis (dimethoxyethylsilyl)ethane), bis(dimethoxyethylsilyl)hexane, bis(dimethoxyethylsilylpropyl)amine , bis(diethoxymethylsilyl)ethane (bis(diethoxy methylsilyl)ethane), bis(diethoxymethylsilyl)hexane (bis(diethoxymethylsilyl)hexane), bis(diethoxymethylsilyl)hexane Methylsilylpropyl) amine (bis(diethoxy methylsilylpropyl)amine), bis(diethoxyethylsilyl)ethane (bis(diethoxyethylsilyl)ethane), bis(diethoxyethylsilyl)hexane Alkane (bis(diethoxyethylsilyl)hexane), bis(diethoxyethylsilylpropyl)amine (bis(diethoxyethylsilylpropyl)amine), bis(dipropoxymethylsilyl)ethane (bis(dipropoxymethylsilyl)ethane ), bis(dipropoxymethylsilyl)hexane (bis(dipropoxymethylsilyl)hexane), bis(dipropoxymethylsilylpropyl)amine (bis(dipropoxymethylsilylpropyl)amine), bis(dipropoxy Bis(dipropoxyethylsilyl)ethane, bis(dipropoxyethylsilyl)hexane, bis(dipropoxyethylsilylpropyl) Amine (bis(dipropoxyethylsilylpropyl)amine), bis(diisopropoxymethylsilyl)ethane (bis(diisopropoxymethylsilyl)ethane), bis(diisopropoxymethylsilyl)hexane (bis(diisopropoxymethylsilyl) hexane), bis(diisopropoxymethylsilylpropyl)amine (bis(diisopropoxymethylsilylpropyl)amine), bis(diisopropoxymethylsilylpropyl)amine Diisopropoxyethylsilyl) ethane (bis(diisopropoxyethylsilyl)ethane), bis(diisopropoxyethylsilyl)hexane (bis(diisopropoxyethylsilyl)hexane), bis(diisopropoxyethylsilyl)propane Base) amine (bis(diisopropoxyethylsilylpropyl)amine);

According to the above conception, the hydrogenation catalyst (b) is to comprise the compound shown in the formula (II), when n=2, m=3, such specific examples include (dimethoxymethylsilyl) (trimethoxy Silyl) ethane ((dimethoxymethylsilyl) (trimethoxy silyl) ethane), (dimethoxymethylsilyl) (trimethoxysilyl) hexane ((dimethoxymethylsilyl) (trimethoxysilyl) hexane), [(dimethoxy methylsilyl)propyl]-[(trimethoxysilyl)propyl]amine[(dimethoxymethylsilyl)propyl]-[(trimethoxysilyl)propyl]amine, (dimethoxyethylsilyl)(trimethoxy (dimethoxyethylsilyl)(trimethoxysilyl)ethane ((dimethoxyethylsilyl)(trimethoxysilyl)ethane), (dimethoxyethylsilyl)(trimethoxysilyl)hexane ((dimethoxyethylsilyl)(trimethoxysilyl)hexane), [(dimethoxy ethylethylsilyl)propyl]-[(trimethoxysilyl)propyl]amine[(dimethoxyethylsilyl)propyl]-[(trimethoxysilyl)propyl]amine, (diethoxymethylsilyl)(triethyl Oxysilyl) ethane ((diethoxymethylsilyl) (triethoxysilyl) ethane), (diethoxymethylsilyl) (triethoxysilyl) hexane ((diethoxymethylsilyl) (triethoxysilyl) hexane), [(two Ethoxymethylsilyl)propyl]-[(triethoxysilyl)propyl]amine[(diethoxymethylsilyl)propyl]-[(triethoxysilyl)propyl]amine, (diethoxyethylsilyl) (triethoxysilyl) ethane ((diethoxyethylsilyl) (triethoxysilyl) ethane), (diethoxyethylsilyl) (triethoxysilyl) hexane ((diethoxyethylsilyl) (triethoxysilyl) hexane), [(diethoxyethylsilyl)propyl]-[(triethoxysilyl)propyl]amine[(diethoxyethylsilyl)propyl]-[(triethoxysilyl)propyl]amine, (dipropoxymethyl Silyl) (tripropoxysilyl) ethane ((dipropoxymethyls ilyl)(tripropoxysilyl)ethane), (dipropoxymethylsilyl)(tripropoxysilyl)hexane ((dipropoxymethylsilyl)(tripropoxysilyl)hexane), [(dipropoxymethylsilyl)propane Base]-[(tripropoxysilyl)propyl]amine[(dipropoxymethylsilyl)propyl]-[(tripropoxysilyl)propyl]amine, (dipropoxyethylsilyl)(tripropoxysilyl)ethyl Alkane ((dipropoxyethylsilyl)(tripropoxysilyl)ethane), (dipropoxyethylsilyl) (tripropoxysilyl) hexane ((dipropoxyethylsilyl)(tripropoxysilyl) hexane), [(dipropoxyethylsilyl) Base) propyl] - [(tripropoxysilyl) propyl] amine [(dipropoxyethylsilyl) propyl] - [(tripropoxysilyl) propyl] amine;

According to above-mentioned design, hydrogenation catalyst (b) is to comprise the compound shown in formula (II), when n=3, when m=3, this kind of specific example includes two (trimethoxysilyl) ethane (bis(trimethoxysilyl) ethane (bis(trimethoxysilyl) )ethane), bis(trimethoxysilyl)hexane (bis(trimethoxy silyl)hexane), bis(trimethoxysilylpropyl)amine (bis(trimethoxysilylpropyl)amine), bis(triethoxysilyl) ) ethane (bis(triethoxysilyl)ethane), bis(triethoxysilyl)hexane (bis(triethoxysilyl)hexane), bis(triethoxysilylpropyl)amine (bis(triethoxysilylpropyl)amine), Bis(tripropoxysilyl)ethane (bis(tripropoxysilyl)ethane), bis(tripropoxysilyl)hexane (bis(tripropoxysilyl)hexane), bis(tripropoxysilylpropyl)amine (bis(tripropoxysilylpropyl)amine), bis(triisopropoxysilyl)ethane (bis(triisopropoxysilyl)ethane), bis(triisopropoxysilyl)hexane (bis(triisopropoxysilyl)hexane), bis( Triisopropoxysilylpropyl)amine (bis(triisopropoxysilylpropyl)amine).

The hydrogenation catalyst (c) of the present invention is an alkylaluminum compound:

Comprising compounds as shown in formula (III):

Formula (III)

Wherein R ⁸ , R ⁹ and R ¹⁰ may be the same or different substituents, and are C ₁ -C ₁₂ alkyl groups, C ₆ -C ₁₂ aryl groups, hydrogen atoms or halogen atoms.

According to the hydrogenation catalyst composition of the present invention, specific examples of the hydrogenation catalyst (c) include: trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tributylaluminum, tributylaluminum, (sec-butyl)aluminum, tri(isobutyl)aluminum, tri(n-pentyl)aluminum, tri(isopentyl)aluminum, tri(n-hexyl)aluminum, tri(isohexyl)aluminum, tri(1-methyl) Tris(2,5-dimethyloctyl)aluminum, tris(2,5-dimethyloctyl)aluminum, tris(2,6-dimethyloctyl)aluminum, tris(2-ethylhexyl)aluminum, triphenylaluminum, chlorine Diethylaluminum, ethylaluminum dichloride, tripropylaluminum chloride, dibutylaluminum chloride, diisobutylaluminum chloride, butylaluminum dichloride, etc. or a combination of the above organoaluminum compounds. A better choice is triethylaluminum, triisopropylaluminum, tributylaluminum or tri(isobutyl)aluminum, diethylaluminum chloride.

The hydrogenation method of the present invention is that the conjugated diene polymer dissolved in an inert organic solvent or an inert organic solvent containing part of ethers and amine polar compounds is mixed with hydrogen in the presence of the hydrogenation catalyst composition described in the present invention The reaction is carried out to selectively hydrogenate the unsaturated double bonds of the conjugated diene units in the conjugated diene polymer. The hydrogenation catalyst composition of the present invention comprises hydrogenation catalysts (a), (b) and (c). For example, gaseous hydrogen can be introduced into the conjugated diene polymer to be hydrogenated, and then the hydrogen and the polymer can be fully contacted by stirring or spraying. The hydrogenation reaction can be carried out in a batch or continuous manner.

The order of adding the hydrogenation catalysts (a), (b), and (c) is not limited. For example, the catalyst (b) can be added to the polymer solution first, and then the mixed solution of the catalysts (a) and (c) can be added. In addition, the catalyst (b) can also be added to the polymer solution first, and then the solution of the catalyst (a) and the solution of the catalyst (c) can be added separately. However, when all the catalysts are added to the polymer and stored in an inert atmosphere for a long period of time, the catalyst still has considerable activity. Therefore, the catalyst composition of the present invention is quite suitable for the needs of industrial mass production.

According to the present invention, the inert organic solvent used to dissolve the hydrogenation catalyst and the conjugated diene polymer may be a linear or branched hydrocarbon, such as pentane, hexane, heptane, octane, and the like; or It can be alicyclic hydrocarbons, such as cyclohexane, cycloheptane, and methylcycloheptane. Cyclohexane, n-hexane are suitable examples. Aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene can also be used as inert organic solvents.

The environment for preparing catalyst (a), (b) and (c) should be carried out under the conditions of inert gas and low water content, inert atmosphere means the inert gas of helium, neon, nitrogen, these gases can not participate in hydrogenation reaction, and Air and oxygen or excessive moisture will oxidize or decompose the hydrogenation catalyst, causing the catalyst to lose its activity. If the catalyst must be pre-mixed, the temperature is preferably 0-200°C. If the temperature is too high, the catalyst will be inactivated. If the temperature is too low, the catalyst itself will not lose its activity, but if the activity is too low, it will not have hydrogenation ability. .

According to the present invention, the conjugated diene polymer used for hydrogenation can be produced according to the following techniques, such as anionic polymerization, cationic polymerization, free radical polymerization, complex polymerization, solution polymerization or emulsion polymerization . During polymerization, it is preferable to use organolithium compounds as catalyst initiators to obtain active polymers, which have carbon lithium ions at the end of molecular chains, so that polymerization can be carried out after adding monomers to make molecular chains grow. Specific examples of organolithium compounds include n-propyllithium, isopropyllithium, n-butyllithium, isobutyllithium, t-butyllithium, n-pentyllithium, phenyllithium, tolyllithium and the like. Examples of dilithium hydrocarbons are 1,4-dilithium-n-butane, 1,5-dilithium-pentane, 1,2-dilithium-bisphenylethane, 1,4-dilithium-1 , 1,4,4 tetraphenylbutane, 1,3- or 1,4-bis(1-lithium-3 methylpentyl)benzene. The amount of organolithium compound is determined by the molecular weight of the polymer to be obtained.

The term "conjugated diene polymer" used in the present invention means a homopolymer or copolymer polymerized with conjugated diene as a monomer, and the end of the molecular chain has active groups or no active groups. Active groups refer to free radicals of carbon, anion groups of carbon alkali metal ions, and cation groups of carbon. The copolymer of conjugated diene can be random (random), block (block), graft (graft) copolymer of two or more conjugated diene monomers, or it can be at least one Random, block, and graft copolymers formed from the above conjugated diene monomers and at least one vinyl aromatic hydrocarbon monomer.

Conjugated diene monomers suitable for use in the present invention may be conjugated dienes having 4 to 12 carbon atoms. Specific examples include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene , 1,3-hexadiene, 4,5-diethyl-1,3-octadiene, 3-butyl-1,3-octadiene and their mixtures, of which 1,3-butadiene, Isoprene and (a mixture of 1,3-butadiene and isoprene) are preferred conjugated diene monomers.

The most preferred hydrogenated styrene/butadiene copolymers for use in the present invention are styrene-ethylene-butylene-styrene (SEBS) block copolymers or random hydrogenated styrene-ethylene-butylene rubber (HSBR) , The best hydrogenated styrene/isoprene copolymer is styrene-ethylene-propylene-styrene (SEPS) block copolymer or random hydrogenated styrene/isoprene rubber (HSIBR), hydrogenated styrene The most preferred /(butadiene/isoprene mixture) copolymers are styrene-ethylene-ethylene-propylene-styrene (SEEPS) block copolymers or random copolymers thereof.

The preferred molecular weight range of the conjugated diene polymer before hydrogenation according to the present invention is 1,000 to 1,000,000. The conjugated diene polymer has a conjugated diene unit content of 5% to 85%.

After the conjugated diene/vinyl aromatic copolymer of the present invention is hydrogenated, high-value thermoplastic elastomer or random copolymer can be obtained. Specific examples of vinyl aromatic hydrocarbon monomers suitable for use in the present invention include styrene, t-butylstyrene, alpha-methylstyrene, o-methylstyrene, p-methylstyrene, divinylbenzene , 1,1-bisphenylethylene, vinyl naphthalene, N,N-bismethyl-p-ethylamine styrene, N,N-bisethyl-p-ethylamine styrene. A preferred example is styrene. Specific examples of conjugated diene/vinyl aromatic copolymers are (1) butadiene/styrene copolymers and (2) isoprene/styrene copolymers (3) butadiene/isoprene /Styrene copolymers.

In addition, a tertiary amine compound or ether compound may be added to the conjugated diene polymer system to enhance the vinyl structure of the conjugated diene. Applicable compounds include general tertiary amine compounds, tetrahydrofuran or diethyl ether and the like.

In the present invention, the metering ratio of the hydrogenation catalyst (a) is enough to add 0.0001 to 50 mmol relative to 100 g of conjugated diene polymer. If it exceeds 50 mmol, it is not in line with economic benefits, and the added metering is too high, and it needs to be added. Procedure for catalyst removal. The hydrogenation catalyst (a) is preferably used in an amount of 0.001 to 50 mmol per 100 g of the conjugated diene polymer.

In the present invention, the molar ratio of the catalyst (b) to the catalyst (a) is preferably within the range of 0.1-50. If the molar ratio is less than 0.1, the hydrogenation catalyst cannot effectively enhance the hydrogenation activity, resulting in the stagnation of the final hydrogenation process and failing to achieve the desired goal. However, if the molar ratio is greater than 50, a step of removing the catalyst will be required, and unnecessary secondary reactions will easily occur, which hinders the hydrogenation reaction. The preferred molar ratio of catalyst (b) to catalyst (a) is between 0.1 and 50.

In the present invention, the molar ratio of the catalyst (c) to the catalyst (a) preferably falls between 0.1 and 50. If the molar ratio is lower than 0.1, the catalyst (a) cannot be activated, and its hydrogenation efficiency is relatively poor. If the molar ratio exceeds 50, unnecessary secondary reactants will be produced, which will cause a sharp drop in hydrogenation efficiency, and catalyst removal must still be performed.

The reaction temperature of the hydrogenation reaction of the present invention can be carried out within the temperature range of 0°C to 200°C. If the reaction temperature is lower than 0°C, the reaction rate will become low and inefficient, and the amount of catalyst (a) must be increased, which is not economical. If it is carried out at a temperature higher than 200°C, it will cause deactivation of the catalyst, thus reducing the activity of the catalyst, and the whole system is prone to side reactions, causing the polymer to decompose or form a gel. The preferred hydrogenation temperature is 40°C to 40°C. Between 150°C.

The preferred hydrogen pressure for hydrogenation is between 1Kg/cm ² and 90Kg/cm ² . If the hydrogenation pressure is less than 1Kg/cm ² , the reaction rate will become insignificant. If the hydrogen pressure exceeds 90Kg/cm ² , the hydrogenation temperature will rise and the hydrogenation reaction will be terminated quickly. The more preferable hydrogenation pressure is 2 to 50Kg/cm ² . Under the above-mentioned hydrogenation conditions, the amount of catalyst used can be gradually decreased with the increase of hydrogen pressure. In order to achieve the effect of reducing the amount of catalyst, it is better to choose a higher hydrogenation pressure.

According to the present invention, the hydrogenation time ranges from a few seconds to 40 hours, and the suitable range needs to be adjusted according to the ratio of the catalyst combination, hydrogen pressure, hydrogenation temperature and other conditions.

According to the present invention, the double bond of the conjugated diene polymer can be hydrogenated to any degree by adjusting the amount of catalyst composition, hydrogen pressure and hydrogenation temperature as required. By using the catalyst composition of the present invention to hydrogenate the conjugated diene/vinyl aromatic hydrocarbon copolymer, the degree of hydrogenation of the double bond in the conjugated diene unit can stably reach more than 50%, and even reach more than 90%. However, the degree of hydrogenation of the aromatic hydrocarbon benzene ring double bond in the vinyl aromatic hydrocarbon unit is less than 10%, or even less than 3%. It can be seen that the catalyst composition used in the present invention has very good catalyst selectivity. The hydrogenation conversion rate of the conjugated diene unit can be analyzed by infrared spectroscopy, while the hydrogenation rate of the aromatic hydrocarbon core can be analyzed by ultraviolet spectroscopy. For similar analysis methods, please refer to US Patent No. 4,501,857.

A polar solvent can be added to the polymer solution obtained after hydrogenation by the hydrogenation catalyst of the present invention to coagulate the polymer. The polar solvent is a poor solvent for the hydrogenated polymer, such as methanol or acetone. Alternatively, the polymer may be isolated by pouring the hydrogenated solution into hot water and stirring to evaporate the polymer together with the solvent, or directly heating the reaction solution to evaporate the solvent.

According to the present invention, the conjugated diene polymer can be successfully hydrogenated with only a very small amount of hydrogenation catalyst composition, and the hydrogenation effect is quite satisfactory. Moreover, most of the catalyst is separated from the polymer or decomposed during the polymer separation process, and does not require other special steps for cleaning or removing the catalyst system.

A major feature of the catalyst composition of the present invention is that the hydrogenation catalyst (b) is a fully substituted silane compound with a Si-R or Si-OR structure, which does not contain hydrogen atoms, so it is not easy to cause hydrolysis or react with more polar functional groups It can maintain a certain storage stability at room temperature, and is very suitable as a catalyst additive for hydrogenation reactions in industrial processes. With the presence of other catalysts, it can achieve the effect of stabilizing other catalysts and improving the activity of other catalysts. Therefore, adding the catalyst composition of the present invention After the conjugated diene polymer is stored, it can be stored under the condition of inert gas for a period of time and still have considerable activity. This time can generally reach more than 30 minutes, and the reproducibility is very good. Another feature is that the catalyst composition of the present invention still has a relatively high catalytic activity at a relatively high reaction temperature, and does not cause the catalyst to lose activity due to an excessively high reaction temperature, which is quite suitable for commercial mass production needs.

The method, features and advantages of the present invention are further illustrated by several examples below, but they are not intended to limit the scope of the present invention. The scope of the present invention should be determined by the scope of the appended patent application.

[Preparation of embodiment 1-SBS copolymer]

In a 10L sleeve heater with a stirrer, fill 5400 grams of cyclohexane, 7.4 mmol of n-butyl lithium (n-butyl lithium) and 252 mmol of tetrahydrofuran, and add 96 grams of styrene therein, at 45 The polymerization reaction was carried out at ℃. Add 400 grams of 1,3-butadiene after the polymerization reaction in the reaction system for reaction, add 96 grams of styrene after the reaction to continue polymerization, place it in a nitrogen-sealed tank, and repeat the same polymerization steps as above, Also placed in the same nitrogen-tight tank, after mixing, a triblock copolymer solution of SBS (styrene-butadiene-styrene) with a solid content of 9.7% and a weight average molecular weight of 230,000 can be obtained .

[Example 2]

Get the polymer solution 1000g of the SBS triblock copolymer prepared in Example 1, move to the pressure-resistant hydrogenation tank, keep under the environment of nitrogen, allocate 0.11mmol bis(trimethoxysilyl) hexane at room temperature [bis(trimethoxysilyl)hexane] in 10ml of cyclohexane, additionally in the glove box pre-mixed 0.11mmol bis(trimethoxysilyl)hexane cyclohexane solution and 0.16mmol n-butyllithium, and 0.055mmol Two (cyclopentadienyl) titanium dichloride and 0.66 mmol of triisobutylaluminum in 20 ml of cyclohexane were added to the SBS polymer prepared above, and hydrogen gas was blown therein to make the pressure reach 25Kg /cm ² , hydrogenation was carried out at 100°C.

Figure 1 shows the infrared spectra of SBS polymers before and after hydrogenation. This spectrum shows that before the SBS triblock copolymer is hydrogenated, the functional group of the trans double bond is found at the wavelength of 968cm ^-1 and 995cm ^-1 , and the 1,2-vinyl double bond is found at the wavelength of 912cm ^-1 . After 1 hour of hydrogenation, the hydrogenation rate measured reached 87.5%. After 5 hours, it could be found that the wave peaks at the above-mentioned wavelengths disappeared significantly. Bond hydrogenation rate) was 95.2%. The data of the hydrogenation reaction are summarized in Table 1.

[Example 3]

Get the polymer solution 1000g of the SBS triblock copolymer prepared in Example 1, move to the pressure-resistant hydrogenation tank, keep under the environment of nitrogen, allocate 0.11mmol bis(trimethoxysilyl) hexane at room temperature In 10 ml of cyclohexane, 0.055 mmol of bis(cyclopentadienyl)dimethoxytitanium in 10 ml of cyclohexane and 0.66 mmol of triethylaluminum in 10 ml of cyclohexane, respectively Add the above-prepared SBS polymer solution, blow hydrogen into it, make the pressure reach 25Kg/cm ² , and carry out hydrogenation at 100°C. After 1 hour, the measured hydrogenation rate reached 87.5%, and after 2 hours, the hydrogenation rate could reach 98%. The data of the hydrogenation reaction are summarized in Table 1.

【Example 4】

In the same manner as in Example 3, prepare 0.11 mmol of bis (diethoxymethylsilyl) ethane [bis (diethoxymethylsilyl) ethane] in 10 ml of cyclohexane at room temperature, and pre-mix 0.055 Mmol bis(cyclopentadienyl)diphenyltitanium in 10 ml of cyclohexane, and 0.66 mmol of diisobutylaluminum hydride in 10 ml of cyclohexane were added to the SBS polymer solution prepared above , blowing hydrogen into it to make the pressure reach 25Kg/cm ² , and carry out hydrogenation at 100°C. After 1 hour, the measured hydrogenation rate reached 94.3%, and after 2 hours, the hydrogenation rate could reach 98.5%. The data of the hydrogenation reaction are summarized in Table 1.

【Example 5】

Same method as embodiment 3, but two (trimethoxysilyl) hexane is changed into two (trimethoxysilyl propyl) amine [bis (trimethoxysilylpropyl)amine] of 0.11mmol in the cyclohexane of 10ml , In addition, pre-mixed 0.055mmol of bis(cyclopentadienyl)titanium dichloride in 10 ml of cyclohexane and 0.66 mmol of triisobutylaluminum in 10 ml of cyclohexane in the glove box, respectively added Hydrogen gas was blown into the SBS polymer solution prepared above to make the pressure reach 25Kg/cm ² , and the hydrogenation was carried out at 100°C. After 1 hour, the measured hydrogenation rate reached 93.5%, and after 2 hours, the hydrogenation rate could reach 96.5%. The data of the hydrogenation reaction are summarized in Table 1.

[Example 6]

In the same manner as in Example 3, prepare 0.11 mmol of bis(trimethoxysilyl) hexane in 10 ml of cyclohexane at room temperature, and pre-mix 0.055 mmol of bis(cyclopentadienyl) di Titanium chloride in 10 milliliters of cyclohexane, and 0.33 mmol of triethylaluminum in 10 milliliters of cyclohexane, were respectively added in the SBS polymer solution prepared above, and hydrogen gas was blown therein to make the pressure reach 25Kg/ cm ² , hydrogenation was carried out at 120°C. After 1 hour, the measured hydrogenation rate reached 84.9%, and after 5 hours, the hydrogenation rate could reach 91.1%. The data of the hydrogenation reaction are summarized in Table 1.

comparative example

Several comparative examples are listed below for comparison with the examples of the present invention. It should be noted that the hydrogenation catalyst compositions used in these comparative examples do not include the hydrogenation catalyst (b) described in the present invention. , so as to further illustrate the characteristics and advantages of the hydrogenation catalyst composition of the present invention.

[Comparative Example 1]

The same method as in Example 3, but no bis(trimethoxysilyl)hexane was added. Pre-mix 0.055mmol of bis(cyclopentadienyl)titanium dichloride in 10ml of cyclohexane and 0.33mmol of triisobutylaluminum in 10ml of cyclohexane in the glove box, add the above preparation Hydrogen gas was blown into the SBS polymer solution to make the pressure reach 25Kg/cm ² , and the hydrogenation was carried out at 100°C.

Figure 2 shows the infrared spectra of SBS polymers before and after hydrogenation. This spectrum shows that before the SBS triblock copolymer is hydrogenated, the functional group of the trans double bond is found at the wavelength of 968cm ^-1 and 995cm ^-1 , and the 1,2-vinyl double bond is found at the wavelength of 912cm ^-1 . After 1 hour of hydrogenation, it can be found that the absorption at wavelengths 995cm ^-1 and 912cm ^-1 decreases, but the absorption at 968cm ^-1 hardly changes. The hydrogenation rate measured at this time was 23%. The data of the hydrogenation reaction are summarized in Table 1.

[Comparative Example 2]

Get the polymer solution 1000g of the SBS triblock copolymer prepared in Example 1, move to the pressure-resistant hydrogenation tank, introduce hydrogen and stir for 30 minutes in advance, as the method of Example 3, but bis(trimethoxysilyl ) hexane was changed to 0.22mmol n-butyllithium, pre-mixed 0.055mmol bis(cyclopentadienyl)titanium dichloride in 10ml cyclohexane, and 0.44mmol triisobutylaluminum in the glove box Add 10 ml of cyclohexane to the above-prepared SBS polymer solution respectively, make the hydrogen pressure reach 25Kg/cm ² , and carry out hydrogenation at 100°C. After 30 minutes, the measured hydrogenation rate reached 15%, and after 1 hour, the hydrogenation rate could reach 24%. The data of the hydrogenation reaction are summarized in Table 1.

Table 1

Example number Residual amount of trans double bond (%) 1,2-vinyl double bond residue (%) 1,3-butadiene hydrogenation rate (%) Benzene ring hydrogenation rate (%) Example 2 3.5 0.3 95.2 <5 Example 3 1.5 0.2 98 <5 Example 4 1.1 0.2 98.5 <5 Example 5 2.4 0.3 96.5 <5 Example 6 7.2 0.7 91.1 <5 Comparative Example 1 75.5 1.5 twenty three <5 Comparative Example 2 74.4 1.6 twenty four <5

It can be known from Table 1 that the hydrogenation reaction of the conjugated diene polymer is carried out using the hydrogenation catalyst composition of the present invention, and the residual amount of trans double bonds of the hydrogenated conjugated diene polymer is lower than 9%, while 1,2-vinyl double bond residue is less than 5%, and 1,3-butadiene hydrogenation rate is greater than 89%; On the other hand, comparative examples 1 and 2, because the hydrogenation catalyst composition that it uses does not have Contains the hydrogenation catalyst (b) described in the present invention, so the residual amount of its trans double bond and 1,2-vinyl double bond is significantly higher, and its hydrogenation rate to 1,3-butadiene is lower than 25% or less.

To sum up, the hydrogenation catalyst composition disclosed in the present invention has excellent hydrogenation ability for conjugated diene polymers, so only a small amount can be used to complete the catalytic reaction. In addition, since the hydrogenation catalyst (b) silane compound has a fully substituted Si-R or Si-OR structure, it is not easy to react with oxygen, and the presence of other catalysts can make the hydrogenation catalyst composition very stable, and achieve the effect of improving the activity of other catalysts After a long period of storage, the activity of the catalyst still has good stability and reproducibility, which is quite economical. Furthermore, the catalyst composition of the present invention still has a high degree of hydrogenation activity in a wide range of temperature systems. In the examples, the catalyst reaction temperature is up to 100°C, and the preferred hydrogenation reaction temperature described in the specification is 40°C to 150°C Therefore, the method for hydrogenating conjugated diene polymers described in the present invention can be carried out in a wide range of temperature systems, and does not lose the activity of the catalyst due to excessive heat of hydrogenation reaction, so it is quite suitable for operating conditions in continuous production down operation.

Although the present invention has been disclosed above with preferred embodiments, it is not intended to limit the present invention. Anyone skilled in this art can make changes and modifications without departing from the spirit and scope of the present invention. Therefore, the present invention The scope of protection should be defined by the appended claims.

Claims (33)

1. the catalyst composition of a hydrogenated conjugated diene polymer, this conjugated diolefin polymer is for being the homopolymers of monomer with the conjugated diene or being the copolymer of monomer with conjugated diene and vinylaromatic hydrocarbon that this hydrogenation catalyst composition comprises following hydrogenation catalyst:

(a) titanium compound;

(b) compound shown in formula (II):

Formula (II)

R wherein ⁵Be C ₁～C ₁₂Alkyl, thiazolinyl, amido, ether, ketone group or ester group, R ³And R ⁶Be C ₁～C ₁₂Alkyl or alkenyl, R ⁴And R ⁷Be C ₁～C ₁₂Alkyl, thiazolinyl, amido, ether, ketone group or ester group, 1≤n≤3,1≤m≤3;

And

(c) alkyl aluminum compound.

2. catalyst composition as claimed in claim 1 is characterized in that, wherein said hydrogenation catalyst (a) titanium compound is (Cp*) ₂TiR ₁R ₂, R wherein ¹, R ²Be identical or different substituting group, and be hydrogen, halogen atom, C ₁～C ₈Alkyl, C ₁～C ₈Alkoxyl, C ₆～C ₁₂Cycloalkyl, phenyl, phenoxy group, C ₇～C ₁₀Alkoxy aryl, C ₇～C ₁₀Aralkyl, carboxyl ,-CH ₂P (phenyl) ₂,-CH ₂Si (C ₁～C ₅Alkyl) ₃Or-P (phenyl) ₂Cp* represents cyclopentadienyl group, fluorenyl, indenyl or their derivative; Described derivative is that on the ring of fluorenyl, indenyl or cyclopentadienyl group one or several hydrogen are replaced by a substituting group.

3. catalyst composition as claimed in claim is characterized in that, wherein said hydrogenation catalyst (c) alkyl aluminum compound is R ₈R ₉R ₁₀Al, wherein R ⁸, R ⁹And R ¹⁰Be identical or different substituting group, and be C ₁～C ₁₂Alkyl, C ₆～C ₁₂Aromatic radical, hydrogen atom or halogen atom.

4. catalyst composition as claimed in claim 2 is characterized in that, wherein said hydrogenation catalyst (a) is the halide of two (cyclopentadienyl group and derivative thereof) titaniums.

5. catalyst composition as claimed in claim 4, it is characterized in that, wherein said hydrogenation catalyst (a) is two (cyclopentadienyl group) bifluoride titaniums, two (cyclopentadienyl group) titanium chloride, two ((2,4-diphenylphosphine cyclopentadienyl group)) bifluoride titanium, two ((2,4-dimethyl phosphine cyclopentadienyl group)) bifluoride titanium, two ((2,4-diphenylphosphine cyclopentadienyl group)) titanium chloride, two (methoxyl group cyclopentadienyl group) titanium chloride, two ((2,4-dimethyl phosphine cyclopentadienyl group)) titanium chloride, two (cyclopentadienyl group) dibrominated titanium, two ((2,4-diphenylphosphine cyclopentadienyl group)) dibrominated titanium, two ((2,4-dimethyl phosphine cyclopentadienyl group)) dibrominated titanium, two (ethylization cyclopentadienyl group) titanium chloride, two (n-pro-pyl cyclopentadienyl group) titanium chloride, two (normal-butyl cyclopentadienyl group) titanium chloride or two (2-ethylhexyl cyclopentadienyl group) titanium chloride.

6. catalyst composition as claimed in claim 2 is characterized in that, wherein said hydrogenation catalyst (a) is the alkoxyl or the alkyl organic compound of two (cyclopentadienyl group and derivative thereof) titaniums.

7. catalyst composition as claimed in claim 6, it is characterized in that, wherein said hydrogenation catalyst (a) is two (cyclopentadienyl group) titaniums of dimethyl, two (cyclopentadienyl group) titaniums of dimethoxy, dimethoxy two ((2,4-diphenylphosphine cyclopentadienyl group)) titanium, dimethoxy two ((2,4-dimethyl phosphine cyclopentadienyl group)) titanium, two (cyclopentadienyl group) titaniums of diethoxy, diethoxy two ((2,4-diphenylphosphine cyclopentadienyl group)) titanium, diethoxy two ((2,4-dimethyl phosphine cyclopentadienyl group)) titanium, two phenoxy groups two ((2,4-diphenylphosphine cyclopentadienyl group)) two ((2,4-dimethyl phosphine cyclopentadienyl group)) titaniums of titanium or two phenoxy groups.

8. catalyst composition as claimed in claim 2 is characterized in that, wherein said hydrogenation catalyst (a) is the halide of two (fluorenyl, indenyl or derivatives thereof) titaniums.

9. catalyst composition as claimed in claim 8, it is characterized in that wherein said hydrogenation catalyst (a) is two (1-fluorenyl) titanium chloride, two (1-indenyl) titanium chloride, two (dimethoxy fluorenyl) titanium chloride, two (fluorenyl) bifluoride titanium, two (indenyl) bifluoride titanium, two (dimethoxy fluorenyl) bifluoride titanium, two (fluorenyl) dibrominated titanium, two (indenyl) dibrominated titanium, two (indenyl) titanium chloride, two (dimethoxy fluorenyl) titanium or two (indenyl) dibrominated titanium.

10. catalyst composition as claimed in claim 2 is characterized in that, wherein said hydrogenation catalyst (a) is the alkoxyl or the alkyl organic compound of two (fluorenyl, indenyl or derivatives thereof) titaniums.

11. catalyst composition as claimed in claim 10, it is characterized in that wherein said hydrogenation catalyst (a) is two (fluorenyl) titaniums of dimethyl, two (fluorenyl) titaniums of dimethoxy, two (indenyl) titaniums of dimethoxy, two (dimethoxy fluorenyl) titaniums of dimethoxy, two (fluorenyl) titaniums of two phenoxy groups, two (indenyl) titaniums of two phenoxy groups, two (dimethoxy fluorenyl) titaniums of two phenoxy groups or two (indenyl) titaniums of two phenoxy groups.

12. catalyst composition as claimed in claim 1 is characterized in that, the R in the wherein said hydrogenation catalyst (b) ³And R ⁶Be C ₁～C ₈Alkyl, R ⁴, R ⁷And R ⁵All be selected from C ₁～C ₈Alkyl, amido, ether or ketone group.

13. catalyst composition as claimed in claim 1 is characterized in that, the R in the wherein said hydrogenation catalyst (b) ³And R ⁶Be C ₁～C ₄Alkyl, R ⁴And R ⁷Be C ₁～C ₆Alkyl, R ⁵Be C ₁～C ₈Alkyl.

14. catalyst composition as claimed in claim 1 is characterized in that, the R in the wherein said hydrogenation catalyst (b) ³And R ⁶Be C ₁～C ₄Alkyl, R ⁴And R ⁷Be C ₁～C ₆Alkyl, R ⁵Be R ¹¹R ¹²R ¹³N, R ¹¹, R ¹², R ¹³Be C ₁～C ₆Alkyl or wherein one be hydrogen atom.

15. catalyst composition as claimed in claim 1 is characterized in that, the R in the wherein said hydrogenation catalyst (b) ³And R ⁶Be C ₁～C ₄Alkyl, R ⁴And R ⁷Be C ₁～C ₆Alkyl, R ⁵Be R ¹⁴-O-R ¹⁵, R ¹⁴And R ¹⁵Be C ₁～C ₆Alkyl.

16. catalyst composition as claimed in claim 1, the R in the wherein said hydrogenation catalyst (b) ³And R ⁶Be C ₁～C ₄Alkyl, R ⁴And R ⁷Be C ₁～C ₆Alkyl, R ⁵For

, R ¹⁶And R ¹⁷Be C ₁～C ₆Alkyl.

17. catalyst composition according to claim 1 is characterized in that, the R in the wherein said hydrogenation catalyst (b) ³And R ⁶Be C ₁～C ₄Alkyl, R ⁴And R ⁷Be C ₁～C ₆Alkyl, R ⁵Be C ₁～C ₆Alkyl or R ¹¹-NH-R ¹², R ¹¹And R ¹²Be C ₁～C ₄Alkyl.

18. catalyst composition as claimed in claim 3, it is characterized in that, wherein said hydrogenation catalyst (c) alkyl aluminum compound is a trimethyl aluminium, triethyl aluminum, tri-n-n-propyl aluminum, triisopropylaluminiuand, tri-butyl aluminum, three (sec-butyl) aluminium, three (isobutyl group) aluminium, three (n-pentyl) aluminium, three (isopentyl) aluminium, three (n-hexyl) aluminium, three (isohesyl) aluminium, three (1-methyl amyl) aluminium, three (2,5-dimethyl octyl group) aluminium, three (2,6-dimethyl octyl group) aluminium, three (2-ethylhexyl) aluminium, triphenyl aluminum, diethylaluminum chloride, ethylaluminium dichloride, the chlorination tri-propyl aluminum, chlorination dibutyl aluminium, di-isobutyl aluminum chloride, the combination of dichloride butyl aluminium or above-mentioned organo-aluminum compound.

19. catalyst composition as claimed in claim 1 is characterized in that, wherein said hydrogenation catalyst (c) is triisobutyl aluminium or triethyl aluminum.

20. catalyst composition as claimed in claim 1 is characterized in that, described conjugated diolefin polymer is homopolymers or the copolymer by anionic polymerisation, radical polymerization, coordination polymerization or cationic polymerization gained.

21. catalyst composition as claimed in claim 1 is characterized in that, wherein with respect to the described conjugated diolefin polymer of 100 grams, the use amount of hydrogenation catalyst (a) is 0.001～50mmol.

22. catalyst composition as claimed in claim 1 is characterized in that, the mol ratio of wherein said hydrogenation catalyst (b) and hydrogenation catalyst (a) is 0.1 to 50.

23. catalyst composition as claimed in claim 1 is characterized in that, the mol ratio of wherein said hydrogenation catalyst (c) and hydrogenation catalyst (a) is 0.1 to 50.

24. catalyst composition as claimed in claim 1 is characterized in that, the molecular weight ranges of described conjugated diolefin polymer is 1000～1,000,000.

25. catalyst composition is characterized in that according to claim 1, the conjugated diene unit content of wherein said conjugated diolefin polymer is 5% to 85%.

26. method of making hydrogenated conjugated diene polymer, this conjugated diolefin polymer is for being the homopolymers of monomer with the conjugated diene or being the copolymer of monomer with conjugated diene and vinylaromatic hydrocarbon, this conjugated diolefin polymer is dissolved in the inert organic solvents, in the presence of hydrogenation catalyst composition, react with hydrogen, unsaturated double-bond with conjugated diene unit in this conjugated diolefin polymer of selective hydration, wherein, described hydrogenation catalyst composition comprises following hydrogenation catalyst:

(a) titanium compound;

(b) compound shown in formula (II):

Formula (II)

R wherein ⁵Be C ₁～C ₁₂Alkyl, thiazolinyl, amido, ether, ketone group or ester group, R ³And R ⁶Be C ₁～C ₁₂Alkyl or alkenyl, R ⁴And R ⁷Be C ₁～C ₁₂Alkyl, thiazolinyl, amido, ether, ketone group or ester group, 1≤n≤3,1≤m≤3;

And

(c) alkyl aluminum compound.

27. method as claimed in claim 26 is characterized in that, hydrogenation catalyst (a) and (b) and addition sequence (c) are that while or different sequencing add respectively in the conjugated diolefin polymer solution.

28. method as claimed in claim 26 is characterized in that, wherein hydrogenation is 0 ℃ to 200 ℃ in temperature, and Hydrogen Vapor Pressure is 1 to 90kg/cm ²Carry out in the scope.

29. method as claimed in claim 26 is characterized in that, the hydrogenation ratio that makes the unsaturated double bond of conjugated diene unit is more than 50%.

30. method as claimed in claim 26 is characterized in that, the hydrogenation ratio that makes the unsaturated double bond of conjugated diene unit is more than 90%.

31. method as claimed in claim 26 is characterized in that, makes the hydrogenation ratio of the two keys of phenyl ring of vinylaromatic hydrocarbon unit be lower than 10%.

32. method as claimed in claim 26 is characterized in that, makes the hydrogenation ratio of the two keys of phenyl ring of vinylaromatic hydrocarbon unit be lower than 5%.

33. method as claimed in claim 26 is characterized in that, wherein said conjugated diene and vinylaromatic hydrocarbon are that the copolymer of monomer is block or random arrangement.

34. method as claimed in claim 26 is characterized in that, wherein said conjugated diene and vinylaromatic hydrocarbon are that the copolymer of monomer is a SB, styrene-isoprene copolymer or styrene-(butadiene/isoprene) copolymer.

35. method as claimed in claim 34 is characterized in that, the hydrogenated products of wherein said SB is the styrene-ethylene-butylene-styrene copolymer.

36. method as claimed in claim 34 is characterized in that, the hydrogenated products of wherein said styrene-isoprene copolymer is styrene-ethylene-propylene-styrene copolymer.

37. method as claimed in claim 34 is characterized in that, the hydrogenated products of wherein said styrene-(butadiene/isoprene) copolymer is styrene-ethylene-ethylene-propylene-styrol copolymer.

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