TWI351984B - Hydrogenation catalyst composition and method for - Google Patents

Description

1351984 TECHNICAL FIELD The present invention relates to a method for hydrogenating a conjugated diene polymer, a method for hydrogenating a conjugated diene polymer using a special catalyst composition, and a special catalyst composition used. . [Prior Art] Industrially, a conjugated diene monomer is usually used for monomerization or copolymerization to obtain a polymer having an unsaturated alkenyl double bond in a polymer molecular chain. It is advantageous to use this polymer for vulcanization. However, due to the presence of an amount of unsaturated double bonds, the weather resistance, heat resistance, and emulsification resistance are not good. In particular, a polymer which is used in the physical crosslinking of a thermoplastic rubber which is a monomer of a light-diluted and dilute aromatic hydrocarbon (viny) aromatlc 11 > ^1 > 〇 (^1) 〇 11) It is more obvious, and it is more disadvantageous if it is used for styrene resin, a modifier of a dilute hydrocarbon resin, and a transparent impact-resistant material. In contrast, in the field of outdoor materials, due to its poor weather resistance, heat resistance, oxidation resistance and other properties, the strong limit is the polymerization of a mixture of dilute and vinyl aromatic hydrocarbons. Improvements in defects such as weather resistance, heat resistance, oxidation resistance, and the like of the copolymer can be improved by a hydrogenation method, large: elimination of an unsaturated double bond, and many catalysts are known for hydrogenating a compound containing an unsaturated double bond. Catalysts are divided into two broad categories: (1) Heterogeneous catalysts, usually deposited on a support, such as carbon, rock, alumina, carbonic acid, etc., and the metal is typically a compound of H Pt. (2) A homogeneous catalyst, for example, (4) Qiqiele er) catalyst consists of a combination of an organic salt of Ni, c〇, Fe, Ci, etc. with a reducing agent such as an organic compound (b) Ru , Rh, Ti, La single-composition organometallization 1351984 alloy. Heterogeneous catalysts are widely used in the industry, but their activity is low compared to homogeneous catalysts. Therefore, in order to be able to be hydrogenated, a large amount of catalyst must be used and must be carried out at a relatively high 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 moderate pressure and temperature conditions. Using a supported heterogeneous catalyst, the polymer to be hydrogenated is first dissolved in a suitable solvent and then contacted with hydrogen in the presence of a heterogeneous catalyst. The viscosity of the polymer is quite high, due to the space barrier of the polymer and the high adsorption of the polymer (it is easy to remain on the surface of the catalyst once hydrogenated, it is easy to interfere with the activation center close to the non-hydrogenated polymer, so the reactants and catalyst The contact is quite difficult. At the same time, the activity of such catalysts in the polymerization of poly(9) hydrogenation is often abruptly and violently, and must be accompanied by high temperature and high pressure. The hydrogenation reaction heat is very high. Hydrogenation at high temperature causes the reaction temperature to rise sharply to polymerize. The material is easily broken down or forms a gel. Therefore, in such an operating condition, when a copolymer containing a total of two ethylene-based aromatic cigarettes is polymerized as a monomer, the conjugated diene unit in the selectively hydrogenated copolymer = unsaturated double bond It is extremely difficult. The reason is that under the high temperature and high pressure, the benzene ring core in the vinyl aromatic tobacco unit is often aminated. It is difficult to separate the catalyst from the hydrogenated polymer solution due to the polymer. It is strongly adsorbed on the heterogeneous catalyst, and it is impossible to completely remove it. ^ In the method using the Ziegler Catalytic Catalytic System, the reaction is essentially in the sentence "Quality occurs" so that the hydrogenation of the copolymer can be carried out under a moderate pressure: a strip: Further, by selectively selecting the conditions for hydrogenation, the double bond of the coplanar dimer unit can be selectively hydrogenated without hydrogenating the ethyl aromatic i 1351984 aromatic ring. However, the amount of catalyst used is higher (requiring higher field and elongation, the catalyst is completely removed from the obtained product, & instability during production and energy consumption during catalyst removal. Traditionally, The method of hydrogenating a total of diene polymers using a homogeneous catalyst is described as follows:

Φ For example, U.S. Patent No. 4_42! The selective hydrogenation reaction of an unsaturated double bond of a co-consumed polymer is disclosed, including the use of a bis(cyclopentadienyl) chin (+4) compound, a stellate compound (Li0R). Chlorination is carried out with a hydrogenation catalyst of an organometallic compound (such as a compound of Ming, Zi, and Magnesium). & Chlorinated Catalysts are highly active. Therefore, the hydrogenation catalyst in the above can achieve an effective hydrogenation effect without the need of deashing step and under mild conditions. U.S. Patent 5,270,274 discloses a hydrogenation catalyst composition comprising a (cyclopentadienyl)titanium (+4) compound, a polar compound comprising a carbon group and an epoxy group, and an organolithium compound for preferential hydrogenation. The unsaturated double bond of the diene polymer, the weathered polymer has excellent physical properties and weather resistance. U.S. Patent 5,244,980 discloses a co-diene polymer which will be active. After termination with hydrogen, an organic alkali metal (particularly organolithium metal) is added and a Tebbe catalyst is added. It is said to have a good hydrogenation effect. The catalyst combination disclosed in U.S. Patent No. 5,886,108, having an active conjugated diene polymer, at least one bis(cyclopentadienyl)titanium (+) added to a hydroxyloxy, carboxy, or ester group. 4) The compound and the compound formed by long-term reaction of trimethylaluminum (Tebbe) catalyst, it is said that this compound participates in the hydrogenation reaction, and has good hydrogenation efficiency. The catalyst combination disclosed in U.S. Patent No. 5,859,995 has an active conjugated fine polymer, and at least bis-oxylated bis(cyclopentadienyl) is present at 1351984 under the conditions of addition of a lithosfaction fossil or a halogenated group. Titanium compounds, which are said to have quite good hydrogenation efficiency under this catalyst combination. U.S. Patent 5,948,869 discloses the selective hydrogenation of a conjugated dilute polymer unsaturated double bond wherein the catalyst combination is at least a di(cyclopentadienyl)titanium (+4) compound, at least a zinc or magnesium alkane. The substrate, and the addition of a plurality of solvents having an ester group and an aromatic group, are accelerators, and it is said that this catalyst combination is quite helpful for improving hydrogenation efficiency.

The catalyst combination of European Patent Application No. 0 434 469 A2 is a kind of a biscyclopentadienyl titanium compound and one of aluminum or magnesium and an alkali metal in the presence of an alkali metal alkoxide and an ether, a ketone and other types of polar compounds. A composition of an organometallic compound having the ability to hydrogenate a conjugated diene polymer and copolymers thereof.

European Patent Application No. 0 544 430 A describes the use of a catalyst composition comprising: (a) a bis(cyclopentadienyl) transition metal compound; (b) at least one polar compound which is a carbonyl group. a compound or an epoxy group-containing compound such as a monobasic or dibasic acid, an internal compound, an intrinsic amine compound, or an epoxy compound; (c) an organolithium compound; and (d) a reduced organometallic A compound such as a compound, a zinc compound and a money compound is specifically exemplified by triethylaluminum. This combination of catalysts is quite helpful for the improvement of hydrogenation efficiency. A selective hydrogenation reaction of a total of diene polymer unsaturated double bonds is disclosed in U.S. Patent No. 6,313,230 and the Chinese Patent No. 00107660.4, the catalyst combination of which is at least a di(cyclopentadienyl)titanium (+4) compound, and Compounds containing Si-H functional groups are known to be quite helpful in improving the efficiency of deuteration. As noted above, although many catalyst compositions have been used to hydrogenate a total of 8 135 1984 light dilute polymers, the present invention has developed a new hydrogenation process which has a stable and easy to store catalyst composition, using this low metering The catalyst composition can successfully hydrogenate the polymer containing a total of two dilute units' and the catalyst is combined at a higher reaction temperature, still has a relatively high catalytic activity, and is not due to excessive reaction temperature The catalyst is deactivated, which is very suitable for commercial production. [Invention content]

It is an object of the present invention to provide a method for hydrogenating a conjugated diene polymer and a oximation catalyst composition which can successfully hydrogenate a conjugated diene polymer and display it using only a small amount of a hydrogenation catalyst composition. It is quite active. Since the concentration of the catalyst used is very low, there is no need to remove the catalyst from the hydrogenated polymer, which greatly increases the economic efficiency. Further, the hydrogenation reaction of the present invention is very rapid and has good reproducibility of results at a wide range of temperatures and pressures.

In order to achieve the above object, the present invention provides a catalyst composition which is stable and easy to store, and a method of hydrogenating a conjugated diene polymer by the same. The hydrogenation catalyst composition of the present invention comprises the following hydrogenation catalyst (a) a titanium compound as shown in formula (I): (Cp*) 2Ti

Formula (1) wherein R, R2 are the same or different substituents ' and are hydrogen, a halogen atom, (: broad (: 8 alkyl and alkoxy, C6~Ci2 cycloalkyl, phenyl, phenyloxy) 1351984 C7~ci. Arylalkoxy and aralkyl, carboxyl, -CH2p(phenyl)2, _CHJRC丨~c5 alkyl)3 or ·ρ(phenyl)2,

Cp* represents cyclopentadienyl, fluorenyl, fluorenyl or a derivative thereof; (b) compound represented by formula (II) or formula (ΙΠ) 0 II II P-(OR)nM3.n formula (II) Wherein R is CcCu alkyl P-(OR)nM3.n Formula (III), C; 3~C丨2 ring-based, aryl or alkyl aryl' Μ is C丨~C12 alkyl, c-wide a C12 alkoxy group, an aryl group, an alkylaryl group, a phenoxy group or a hydroxyl group, n = 1 to 3; and (c) an alkyl aluminum compound R4 as shown in the formula (IV)

R6 Formula (IV) wherein R, R and r6 may be the same or different substituents, and are C-C Cu alkyl or c6-c12 aryl, hydrogen or halogen atoms. According to a preferred embodiment of the present invention, the molar ratio of the hydrogenation catalyst (b) and the hydrogenation catalyst (a) is 〇1 to 5〇, and the molar ratio of the hydrogenation catalyst (4) and the hydrogenation catalyst (4) is 〇. 1 to 5 〇. The hydrogenation catalyst composition of the present invention is a stable and easy to store catalyst. Things. In particular, the hydrogenation catalyst (9)' whose composition is as shown in the formula (η) or the formula (in) can be combined (the impurity-media is used to enhance the overall hydrogenation effect*, and the other catalysts are stabilized). When the composition is added to the compound of the second compound, it can be stored and used for a long period of time. The activity of the catalyst still has good stability and reproducibility. It is quite economical. The method of the dimer polymer comprises: a :=! agent or a part-containing, an amine-based polar compound-.2, which is first formulated in the catalyst composition of the present invention. Reacting with hydrogen in the presence of hydrogen to selectively hydrogenate the unsaturated double bond of the co-diene unit in the co-diene polymer. According to the present invention, the conjugated diene polymerization used in the method of hydrogenating a co-diuretic polymer The conjugated diene is a homopolymer or a copolymer of a monomer, and the hydrogenation reaction is carried out in the range of the reaction temperature layer d and the gas pressure of 1 kg/cm 2 to 90 kg/cni 2 . The hydrogenation catalyst (a) is used in an amount of 0.0001 to 50 mmole with respect to the conjugated diene polymer.

In order to make the structure, the operation method and the features of the present invention more obvious, the preferred embodiment is described in detail with reference to the accompanying drawings. A composition comprising hydrogenation catalysts (a) to (c) 'wherein the argon catalyst (a) comprises a titanium compound represented by the formula (1): (Cp*) 2 Ti^ R2 Formula (I) wherein R!, Rz The substituents may be the same or different, and may be selected from the group consisting of hydrogen, halogen atom, CfCg, and oxy, C6~C1Z ring, phenyl, phenoxy, C7~C10 square base. Aromatic (arylalkoxy) and arylalkyl, carboxy, 〜CH2P (phenyl) 2, ~CH2Si (C丨~C5 alkyl) 3 or ~P (benzene 11 1351984 d base) 2,

Cp* represents a pentadienyl group, a fluorenyl group, a fluorenyl group or a derivative thereof. According to the invention 'Cp* can be, for example, C5R7r8r9r1〇r11 (cyclopentadienyl or a derivative thereof), wherein R7, R8, r9, R1Q, R11 may be the same or different substituents' and may be selected from money And (iv) an atom, a pyridyl group, an aromatic hydrocarbon group, or a carboxyl group (Carb〇Xyl), -CH2P(phenyl) 2, -CH2Si(Cl~C5 alkyl)3 or Ρ(phenyl)2〇 is suitable for use in the present invention. The hydrogenation catalyst (4) is a compound represented by the formula (1), and in the case of a bis(N. pentylene thiol, fluorenyl, fluorenyl, and derivatives thereof), such specific examples include bis(cyclopentane) Alkenyl) titanium difluoride [bis(cyclopentadienyl)titanium difluoride], bis(cyclopentadienyl)titanium dichloride, bis[(2,4-diphenylphosphorylcyclopentadienyl)]difluoro Titanium, bis[(2,4·dimethylphosphonated cyclopentadienyl)]titanium difluoride, bis[(2,4-diphenylphosphorylcyclopentadienyl)]titanium dichloride Dimethoxylated bis(cyclopentayl)titanium dichloride 'bis[(2,4-dimethylated cyclopentadienyl)]titanium dichloride, bis(cyclopentadienyl) Titanium dibromide, bis[(2,4·diphenylphosphorylation) Cyclopentadienyl)] titanium dibromide, bis[(2,4-dimethylphosphorylcyclopentadienyl)]titanium dibromide, bis(ethylated cyclopentadienyl) dichloride Titanium, bis(n-propylated cyclopentadienyl) di-titanium, bis(n-butylcyclopentadienyl)titanium dichloride, bis(2-ethylhexylated cyclopentadienyl) Dimethylsilylene-bis(T? 5-2,4-cycl〇pentadien -1-ylidene) > (ethylene)-bis (77 5-2,4-cyclopentadien -1-ylidene). The hydrogenation catalyst (4) according to the present invention is a compound represented by the formula (1), wherein in the case of a bis(cyclopentadienyl group and a derivative thereof) titanium hydrocarbyloxy compound, such specific examples include dimethyl groups. Bis(cyclopentadienyl)titanium, dimethanol bis(cyclopentadienyl)titanium dioxime, dimercapto mersin 12 1351984 [(2,4-diphenylphosphorylated cyclopentane) Dienyl)]titanium, dimethanol bis[(2,4-dimethylphosphorylcyclopentadienyl)]titanium, diethoxybis(cyclopentadienyl)titanium-ethoxy bis[( 2,4-Phenylation of cyclopentadienyl)]Titanium, monoethoxybis[(2,4-dimethyldiscyclopentadienyl)]titanium, di-p-oxyl bis[( 2,4-diphenylphosphonated cyclopentadienyl)]titanium, diphenyloxybis[(2,4-dimethylboroncyclopentadienyl)]titanium according to the hydrogenation catalyst of the invention ( a) is a compound represented by the formula (1), wherein in the case of a bis (3⁄4 group, a benzyl group or a derivative thereof) titanium, such a compound

Specific examples include bis(i- fluorenyl)titanium dichloride, bis(1_fluorenyl) titanium hydride

[bis(l-]ndeiiyl)titanium dichloride], bis(dimethoxyindenyl)titanium dichloride, bis(indenyl)dicarbaea, bis(indenyl)titanium difluoride, bis(indenyl) Titanium fluoride, bis(dimethoxyindenyl) titanium difluoride, bis(nod) titanium difluoride, bis(n-)-titanium bromide, bis(indenyl)titanium dibromide, double Dimethoprimyl titanium, double (nodal) two desertification! too. Further, according to the bis (indenyl, sulfhydryl or derivative thereof) titanium hydrocarbyloxy compound, such specific examples include dimethylbis(indenyl)titanium and dimethoxybis(nuki). Titanium, dimethoxy bis(nodotyl) titanium, dimethoxy bis(dimethoxyindenyl), dimethoxy bis(nod) titanium, dimethanol bis(indenyl) titanium, two Methanol-based bis(nodotyl) titanium, dimethanol bis(dimethoxyno), dimethanol diyl) titanium, diphenoxy bis(indenyl) titanium, di-phenyloxy bis(nodule) Titanium, di-phenyloxybis(dimethoxyindenyl)titanium, diphenoxy bis(nodal), the so-called derivative herein refers to a ring on the group 1, or a cyclopentadienyl ring. One or several hydrogens are substituted by a substituent, and the substituent may be, for example, a methyl group, a methoxy group, a p-tert-butylphenyl group, a pentafluorophenyl group, a trifluorophenyl group or a difluorophenyl group. Or a group such as 3,5-(t-butyl M-methoxyphenyl). An example of a preferred hydrogenation catalyst (4) is bis(cyclopentadienyl) di-titanized titanium. 13 1351984 Hydrogenation of the invention Catalyst (b) is included as in formula (11) A compound of Formula (ΠΙ) shown in the: square

II P-(〇R)nM3.n P-(〇R)nM3.n Formula (Π) Formula (III) wherein R is C丨~C〗 2 alkyl, C-C12 cycloalkyl, aryl or alkane Aromatic group, lanthanide is C丨~Cu alkyl, (: 丨~(:12 alkoxy, aryl, alkylaryl, oxy or hydroxy)

,n=l~3 〇

According to the invention, the hydrogenation catalyst (b) is a compound of the formula (II), and R is C丨~C丨2 alkyl, C丨~C丨2 cycloalkyl, aryl or alkylaryl . For example, R is (: broad (: 丨 2 alkyl, c 3 ～ C 12 cycloalkyl, aryl or alkyl aryl. When n = 3) Specific examples of such include Trimethyl phosphate, scale Triethyl acid ester, tripropyl acid ester, tris(isopropyl) discate, tributyl phosphate, tri(isobutyl) phosphate, tri(tert-butyl) phosphate, tris (third Butyl) ester, tri(cyclopropyl) phosphate, di(cyclohexyl)phosphoric acid, triphenyl phosphate, di(n-methyl) acid, di(phenethyl) Vinegar, tris(phenylpropyl) vinegar, tris(phenylisopropyl) acetate, tris(phenylidene butyl) phosphate, tris(phenylbutyl)phosphate, tris(phenylisobutyl) phosphate Ester ester, tris(phenyl tert-butyl) phosphate. For example, R is a C-C12 alkyl group, and Μ is (: wide (: 12 alkyl, alkoxy, aryl, alkyl aryl, phenoxy) Base or hydroxyl group, when η = 2, specific examples of such a type include Dimethyl methyl phosphonate, diethyl decyl phosphate, dimethyl propyl phosphate, butyl phosphate , dimethyl thiophosphate, diethyl ethyl phosphate, diethyl propyl phosphate, diethyl butyl silicate, dipropyl methyl phthalate, ethyl phosphate 14 1351984 dipropylene vinegar, propyl « Dipropylene vinegar, butyl acid dipropylene vinegar, methyl acid dibutyl sulphate, ethyl acid dibutyl vinegar, propyl acid dibutyl sulphate, τ carboxylic acid butyl ketone, methoxy group Diethylation, A. sulphate, sulphate, sulphate, sulphate, sulphate, sulphate, ethoxylate, propyloxy ethoxylate Butyl ester, propyl propyl propyl phosphate, propane oxy phosphate diacetate, dibutyl propane oxy phosphate, dimethyl butoxide dimethyl phosphate, butaneoxy phosphate, butanoxy phosphate Dipropyl phenyl phosphonate, dibasic acid-B

Ester, dipropyl phenyl phosphate, dibutyl phenyl phosphate, dinonyl phenyl phthalate, diethyl phenyl phthalate, dipropyl benzyl phosphate, dibutyl phenyl phthalate, phenyl Didecyl phosphate, phenethyl phosphate, diethyl phenethyl phosphate, dibutyl phenethyl phosphate, phenylpropyl phosphate, phenylpropyl phosphate, phenylpropyl phosphate Dipropyl ester, diphenyl phenyl propyl phosphate, dinonyl phenylbutyl phosphate, diethyl phenylbutyl phosphate, dipropyl phenylbutyl phosphate, dibutyl phenylbutyl phosphate, phenoxy phosphate Ester, diethyl oxyphosphate, dipropyl phenoxy phosphate, dibutyl phenoxy phosphate, dinonyl phosphate, diethyl phosphate, dipropyl phosphate, dibutyl phosphate. For example, R is a C3~C12 cycloalkyl group, and Μ is (: 12 (alkyl, alkoxy, aryl, alkylaryl 'phenoxy or hydroxy), then η = 2, specific to such Examples include di(cyclopropyl)methyl phosphate, di(cyclopropyl)ethyl phosphate, di(cyclopropyl) propyl phosphate, di(cyclopropyl)butyl phosphate, decyl phosphate (cyclohexyl) ester, di(cyclohexyl)ethyl phosphate, di(cyclohexyl) propyl phosphate, di(cyclohexyl)butyl phosphate, di(cyclopropyl)methane phosphate, decane Di(cyclohexyl) oxyphosphate, bis(cyclopropyl) ethaneoxyphosphate, di(cyclohexyl) ethoxyoxyphosphate, propaneoxyphosphoric acid di(cyclopropyl) 15 1351984

Ester, propaneoxyphosphoric acid di(cyclohexyl) ester, butoxykoxyphosphoric acid di(cyclopropyl) albendine oxy-acidic acid (cyclohexyl) s, phenyl acid di(cyclopropyl) Self-purpose, di(cyclohexyl) phenyl phosphate, di(cyclopropyl) benzyl phosphate, di(cyclohexyl) benzyl phosphate, di(cyclopropyl) phenethyl phosphate, phenylethyl Di(cyclohexyl) phosphate, bis(cyclopropyl) phenylpropyl phosphate, phenylpropyl phosphate mono(cyclohexyl) ester, bis(cyclopropyl) phenylbutyl phthalate, phenylbutyl carboxylic acid Di(cyclohexyl) ester, bis(cyclopropyl) phenoxy phosphate, di(cyclohexyl) phenoxy phosphate, di(cyclopropyl) phosphate, di(cyclohexyl) phosphate. For example, R is an aryl group or an alkyl aryl group, and hydrazine is an alkyl group, an alkoxy group, an aryl group, an alkyl aryl group, a phenoxy group or a hydroxy group. When n=2, specific examples of such a group include methyl phosphate. Diphenyl ester, diphenyl ethyl phosphate, diphenyl propyl phosphate, di- butyl butyl phosphate, bis(phenylhydrazinyl) decyl phosphate, di(p-xyl) ethyl silicate, propyl Di(phenylmethyl) phosphate, di(p-methyl) butyl phosphate, di(p-ethyl) methyl phosphate, di(phenylethyl)ethyl phosphate, di(phenylethyl) propyl phosphate Ester, bis(phenethyl)butyl phosphate, bis(phenylpropyl) decyl phosphate, di(phenylpropyl)ethyl phosphate, di(p-propyl) propyl phosphate, butyl phosphate Bis(phenylpropyl) ester, di(phenylbutyl)methyl phosphate, di(phenylbutyl)ethyl phosphate, di(phenylbutyl)propyl phosphate, di(phenylbutyl)butyl phosphate Ester, m-dioxydiphenyl phosphate, methaneoxyphosphoric acid di(p-methyl) ester, methaneoxyphosphoric acid di(p-ethyl) ester, methaneoxyphosphoric acid di(phenylpropyl) vinegar, Di(p-butyl) decyloxy phosphate, di- ethoxy oxyphosphate, bis(benzyl) ethoxy oxyphosphate, bis(phenylethyl) ethoxy oxyphosphate, ethane Di(phenylpropyl) oxyphosphate, bis(phenylbutyl) acetoacetate, diphenyl phenolate, propionate bis(phenylhydrazine) vinegar, propane Di(phenylethyl) oxyphosphate, di(phenyl) propionate phosphate, 16 1351984

Propyloxy di(p-butyl) ester, butanoxy diphenyl phosphate 'butoxy bis(phenyl)), butanoxy bis(phenylethyl) butoxide Di(phenyl) phosphinate, bis(phenylbutyl) butoxide, diphenyl phenyl phosphate, bis(benzyl) phenyl phosphate, bis(phenylethyl) phenyl phosphate Ester, bis(phenylpropyl) phenyl phosphate, di(phenylbutyl) phenyl phosphate, diphenyl benzyl phosphate, di(phenylmethyl) methyl phosphate, benzyl phosphate Phenylethyl) ester, bis(phenylpropyl) phenylmercaptophosphate, bis(phenylbutyl) phenylphosphonate, diphenyl phenylethyl phosphate, bis(phenylhydrazinyl) phenethyl phosphate, Di(phenylethyl) phenethyl phosphate, bis(phenylpropyl) phenethyl phosphate, di(phenylbutyl) phenethyl phosphate, diphenyl phenylpropyl phosphate, phenylpropyl phosphate Benzoyl) ester, bis(phenylethyl) phenylpropyl phosphate, bis(phenylpropyl) phenylpropyl phosphate, di(phenylbutyl) phenylpropyl phosphate, diphenyl phenylbutyl phosphate, Phenidine Di(phenylmethyl) phosphate, bis(phenylethyl) phenylbutyl phosphate, di(phenylpropyl) phenylbutyl phosphate, di(phenylbutyl) phenylbutyl phosphate, phenoxy phosphate (stupyl methyl) ester, phenoxyphosphoric acid di(phenylethyl) ester, phenoxy phosphobis(phenylpropyl) ester, phenoxy phosphobis(phenylbutyl) ester, diphenyl phosphate, phosphoric acid (Benzyl) ester, di(phenylethyl) phosphate, di(phenylpropyl) phosphate, di(phenylbutyl) phosphate. Wherein R is C, C12 alkyl, and hydrazine is also C-C12 alkyl, alkoxy, aryl, alkyl aryl, phenoxy or hydroxy. When n=l, specific examples of this include M-methyl phosphate, diethyl decyl methacrylate, dipropyl methyl phosphate, dibutyl phosphonium phosphate, ethyl dimethyl phosphate, diethyl ethyl phosphate, dipropyl phosphate, two Ethyl butyl phosphate, propyl dimercaptophosphate, propyl diethyl phosphate, propyl dipropyl phosphate, propyl dibutyl phosphate, butyl dimethyl phosphate, butyl diethyl phosphate, dipropyl Butyl phosphate, dibutyl butyl phosphate, dimethaneoxy 17 1351984

Acid ethyl ester, dimethyl oxylate propyl ester, dimethyl oxy butyl phthalate, dimethyl oxy phthalate, diethoxyphosphoric acid propyl vinegar, diethyl ethoxide Butyl acrylate, di-n-propyl-oxy-oxy oxy phthalate, di-propyl oxy-acid acetoacetate, butyl dipropoxy butyl phosphate, dibutoxy phthalic acid bismuth vinegar, dibutyl oxyoxyethyl carbonate , dibutoxy propyl acrylate, di-p-methyl phosphate, diphenyl phosphate, propyl diphenyl phosphate, butyl diphenyl phosphate, methyl diphenyl phthalate, dick Ethyl squarate, propyl diphenyl phthalate, butyl dibenzoate, decyl diphenylethyl phthalate, ethyl diphenylethyl molybdate, propyl diphenylethyl phosphate, Diphenylethyl butyl phosphate, diphenylpropyl phosphamate, diphenylpropyl phosphate, diphenylpropyl propyl phosphate, diphenylpropyl phosphate, diphenylbutyl phosphate, diphenyl Ethyl butyl phosphate, propyl diphenyl butyl phosphate, butyl diphenyl butyl phosphate, methyl diphenoxy phosphate, ethyl diphenoxy phosphate, propyl diphenoxy phosphate, diphenoxy Butyl phosphate, phosphorus Methyl ester, ethyl phosphate, propyl phosphate, butyl phosphate. For example, R is a C3~C丨2 cycloalkyl group, and Μ is (: 12 (alkyl, alkoxy, aryl, alkylaryl, phenoxy or thiol). When η=1, this is Specific examples of the class include (cyclopropyl) dimethyl phosphate, (cyclopropyl) diethyl phosphate, (cyclopropyl) dipropyl phosphate, dicyclophosphoric acid (cyclopropyl) ester, two Methylphosphoric acid (cyclohexyl) ester, diethyl ruthenium (cyclohexyl) ester, dipropyl acid (cyclohexyl) ester, dibutyl phosphate (cyclohexyl) ester, dimethaneoxy phosphate (cyclopropyl) Ester, di-decyloxyphosphoric acid (cyclohexyl) ester, diethoxyoxyphosphoric acid (cyclopropyl) ester, diethyloxyalkyl carbonate (cyclohexyl) ester, dipropoxylated acid acid (cyclopropyl) Ester, dipropanoyloxyphosphoric acid (cyclohexyl) ester, dibutoxyphosphoric acid (cyclopropyl) ester, dibutoxyphosphoric acid (cyclohexyl) ester, dipyridyl phosphate (cyclopropyl) ester , diphenylphosphoric acid (cyclohexyl) ester, diphenylmethyl phosphate (cyclopropyl) ester, diphenyl 18 1351984

(cyclohexyl) phosphate, diphenylethyl phosphate (cyclopropyl) ester, diphenylethyl phosphate (cyclohexyl) ester, diphenylpropyl phosphate (cyclopropyl) ester, dipyridyl phosphate (ring Hexyl)ester, diphenylbutyl acid (cyclopropyl) ester, dipyridyl (cyclohexyl) ester, diphenoxyphosphoric acid (cyclopropyl) ester, diphenoxyphosphoric acid (cyclohexyl) Ester, citric acid (cyclopropyl) ester, acid (cyclohexyl) ester, for example, R is an aryl group or an alkyl aryl group Μ is (^~(^12), alkoxy, aryl, alkane Specific examples of such an aromatic group, a phenoxy group or a hydroxyl group when n = 1, include diphenyl dimethyl phosphate, phenyl diethyl phosphate, phenyl dipropyl phosphate, and phenyl dibutyl phosphate. , dimethyl (phosphomethyl) methacrylate, diethyl (phenyl decyl) phosphate, dipropyl phosphoric acid (benzyl) ester, dibutyl phosphoric acid (benzyl) ester diterpenoid acid (Phenylethyl) ester, diethyl acid (phenethyl) ester, dipropyl phosphoric acid (phenethyl) ester, dibutyl phosphoric acid (phenethyl) ester, dimethyl phosphate (phenylpropyl) ester Diethyl (phenylpropyl) phosphate, dipropyl phosphoric acid (phenylpropyl) ester, dibutyl acid (phenylpropyl) ester, dimethyl acid (phenylbutyl) ester, diethyl phosphate (Phenylbutyl) ester, dipropylphosphoric acid (phenylbutyl) ester, dibutylphosphoric acid (phenylbutyl) ester, dimethaneoxyphosphoryl stearate, dimethaneoxyphosphoric acid (benzyl) ester, two Methaneoxyphosphoric acid (p-ethyl) ester, di-decyloxyphosphoric acid (phenylpropyl) ester, di-f-alkoxyphosphoric acid (phenylbutyl) ester, diethoxylated phenyl phosphate, diethyl ether Base bowl acid (stupyl methyl) ester, diethoxy acid acid (phenethyl) ester, diethyl ethoxy acid (phenylpropyl) ester, diethyl ethoxylated phenyl acid (phenylbutyl) Ester, di-n-propoxyphosphoryl stearate, di-n-propaneoxyphosphoric acid (benzyl) ester, di-n-propoxy phosphatic acid (phenethyl) ester, di-n-propoxy phosphatic acid (phenylpropyl) vinegar, Di-n-propaneoxyphosphoric acid (phenylbutyl) ester, diisopropoxy oxy phosphate benzene, diisopropoxy oxy phosphate (benzyl) ester, diisopropoxy oxy phosphate (phenethyl) ester Propaneoxyphosphoric acid (phenyl) ester, diisopropane 19 1351984

(Phenylbutyl) oxyphosphate, Butyl Di-n-Butyloxyphosphate, Di-n-Butyloxy Phosphate (Phenyl) Ester, Dibutoxyphosphoric Acid (Phenylethyl) Ester, Di-n-butyl Alkoxyphosphoric acid (phenylpropyl) ester, dibutoxyphosphoric acid (phenylbutyl) ester, phenyl diphenyl phosphate, diphenylphosphoryl (benzoyl) ester, diphenyl phosphoric acid (phenethyl) Ester, diphenylphosphoric acid (phenylpropyl) ester, diphenylphosphoric acid (phenylbutyl) ester, diphenylmethyl phosphate phenyl ester, diphenylmethyl phosphate (benzyl) ester, diphenylmethyl phosphate (Phenylethyl) ester, diphenylmethylphosphoric acid (phenylpropyl) ester, diphenylmethylphosphoric acid (phenylbutyl) ester, dipyridylethyl phosphate, diphenylethylphosphoric acid (benzoyl) ester , diphenylethylphosphoric acid (phenethyl) ester, diphenylethylphosphoric acid (phenylpropyl) ester, diphenylethylphosphoric acid (phenylbutyl) ester, diphenylpropyl phosphate phenyl ester, diphenylpropyl phosphate (phenyl decyl) ester, diphenylpropyl phosphate (phenethyl) ester 'diphenylpropyl phosphate (phenylpropyl) ester, diphenylpropyl phosphate (phenylbutyl) ester, diphenyl butyl phosphate ,two Butyl phosphate (benzyl) ester, diphenylbutyl phosphate (phenethyl) ester, diphenylbutyl phosphate (phenylpropyl) ester, diphenylbutyl phosphate (phenylbutyl) ester, diphenoxy Phenyl phosphate, diphenoxyphosphoric acid (benzoyl) ester, diphenoxyphosphoric acid (phenethyl) ester, diphenoxyphosphoric acid (phenylpropyl) ester, diphenoxyphosphoric acid (phenylbutyl) Ester, phenyl phosphate, (phenylhydrazinyl) phosphate, (phenylethyl) phosphate, (phenylpropyl) phosphate, (phenylbutyl) phosphate. When the hydrogenation catalyst (b) is a compound represented by the formula (III), and R is a C丨~C12 alkyl group, a C3~C12 cycloalkyl group, an aromatic group or a alkyl group. For example, R is an alkyl group, a c3 to C12 cycloalkyl group, an aryl group or an alkylaryl group. When n = 3, specific examples of such a group include Triinethyl phosphite, triethyl phosphite, Tripropyl phosphite, tributyl phosphite, tri(cyclopropyl) phosphite, tri(cyclohexyl) phosphite, triphenyl phosphite, tris(phenylmethyl) phosphite , tris(phenylethyl) phosphite, tris(phenyl) phosphite, tris(phenylbutyl) phosphite. Example 20 1351984

For example, R is a C-Cu alkyl group, and an anthracene is also an alkyl group, an alkoxy group, an aryl group, an alkylaryl group or a phenoxy group. When n=2, specific examples of such a group include a mercapto dimethoxy group. Methyl dimethoxyphosphine, ethyl dimethoxy phosphorus, propyl dimethoxy phosphorus, butyl dimethoxy phosphorus, methyl diethoxy phosphorus, ethyl diethoxy phosphorus, propyl di Oxyphosphorus, butyldiethoxyphosphorus, methyldipropoxyphosphorus, ethyldipropoxyphosphorus, propyldipropoxyphosphorus, butyldipropoxyphosphorus, methyldibutoxy Phosphorus, ethyl dibutoxy phosphorus, propyl dibutoxy phosphorus, butyl dibutoxy phosphorus, ethaneoxy dimethoxy phosphorus, propaneoxy dimethoxy phosphorus, decyloxy two Ethoxyphosphorus, propaneoxydiethoxyphosphorus, butaneoxydiethoxyphosphorus, nonyloxydipropoxyphosphine, ethaneoxydipropoxyphosphorus, butaneoxydipropane Oxyphosphorus, methaneoxydibutoxyphosphorus, ethaneoxydibutoxyphosphorus, propaneoxydibutoxyphosphorus, phenyldimethoxyphosphine, benzyldimethoxyphosphorus, benzene Ethyldimethoxyphosphorus, phenylpropyldimethoxyphosphorus, benzene Dimethoxyphosphine, phenoxydimethoxyphosphorus, phenyldiethoxyphosphorus, benzyldiethoxyphosphorus, phenethyldiethoxyphosphorus, phenylpropyldiethoxyphosphorus , phenylbutyl diethoxy phosphorus, phenoxy diethoxy phosphorus, phenyl dipropoxy phosphorus, benzyl dipropoxy phosphorus, phenethyl dipropoxy phosphorus, phenylpropyl dipropyl Oxyphosphorus, phenylbutyldipropoxyphosphorus, phenoxydipropoxyphosphorus, phenyldibutoxyphosphoric acid, benzyldibutoxyphosphoric acid, phenethyldibutoxyphosphoric acid, styrene-acrylic acid Di-butoxy phosphorus, phenylbutyl dibutoxy phosphorus, phenoxy dibutoxy phosphorus. For example, R is a C3 to C12 cycloalkyl group, and hydrazine is an alkyl group, an alkoxy group, an aryl group, an alkylaryl group or a phenoxy group, and η = 2. Specific examples of such include methyl di(cyclopropoxy)phosphorus, ethyl bis(cyclopropoxy)phosphine, propylbis(cyclopropoxy)phosphorus, butylbis(cyclopropoxy)phosphorus, Mercaptobis(cyclobutoxy)phosphorus, ethylbis(cyclobutoxy)phosphorus, propylbis(cyclobutoxy)phosphorus, butylbis(cyclobutoxy)phosphorus, methaneoxydi(cyclo) Propoxy)phosphine, ethaneoxybis(cyclopropoxy)phosphine, propaneoxybis(cyclopropoxy)phosphorus, butaneoxy 21 kb〆1 1351984

Bis(cyclopropoxy)phosphine, methaneoxybis(cyclobutoxy)phosphorus, ethaneoxybis(cyclobutoxy)phosphorus, propaneoxybis(cyclobutoxy)phosphorus, butaneoxy Bis(cyclobutoxy)phosphorus, phenylbis(cyclopropoxy)phosphorus, benzoylbis(cyclopropoxy)phosphorus, phenethylbis(cyclopropoxy)phosphorus, phenylpropyldi(cyclo) Propoxy)phosphorus, phenylbutylbis(cyclopropoxy)phosphorus, phenoxy bis(cyclopropoxy)phosphine, phenylbis(cyclobutoxy)phosphorus, benzyldi(cyclobutoxy) Phosphorus, phenethylbis(cyclobutoxy)phosphorus, phenylpropylbis(cyclobutoxy)phosphorus, phenylbutylbis(cyclobutoxy)phosphorus, phenoxybis(cyclobutoxy)phosphorus . For example, R is an aryl group or an alkyl aryl group, hydrazine is an alkyl 'alkoxy group, an aryl group, an alkyl aryl group or a phenoxy group. When η=2, specific examples of such a group include decyl bis(benzene) Oxy)phosphorus, ethylbis(phenoxy)phosphorus, propylbis(phenoxy)phosphorus, butylbis(phenoxy)phosphorus, methyldi(indolyloxy)phosphorus, ethyldi(() Phenyloxy)phosphorus, propylbis(phenoxy)phosphorus, butylbis(benzyloxy)phosphorus, methylbis(phenethyloxy)phosphorus, ethylbis(phenylethoxy)phosphorus , propyl bis(phenylethoxy)phosphorus, butylbis(phenylethoxy)phosphorus, methylbis(phenylpropoxy)phosphorus, ethylbis(phenylpropoxy)phosphorus, propylbis(benzene) Propoxy)phosphine, butylbis(phenylpropoxy)phosphorus, methylbis(phenylbutoxy)phosphorus, ethylbis(phenylbutoxy)phosphorus, propylbis(thanobutoxy)phosphorus, Butyl bis(phenylbutoxy)phosphorus, decyloxybis(phenoxy)phosphorus, ethaneoxybis(phenoxy)phosphorus, propaneoxybis(phenoxy)phosphorus, butaneoxy Bis(phenoxy)phosphorus, nonyloxybis(stupyloxy)phosphorus, ethaneoxydiyl Alkyloxy)phosphorus, propaneoxybis(benzyloxy)phosphorus, butaneoxybis(benzylidene)phosphine, decyloxybis(phenylethoxy)phosphorus, ethaneoxydi (Phenylethoxy)phosphorus, propaneoxybis(phenethyloxy)phosphorus, butaneoxybis(phenylethoxy)phosphorus, methaneoxybis(phenylpropoxy)phosphorus, ethaneoxydi (Phenylpropoxy)phosphine, propanedecylbis(phenylpropoxy)phosphorus, butaneoxybis(phenylpropoxy)phosphine, methaneoxybis(phenylbutoxy)phosphorus, ethaneoxydi (Phenyloxy)phosphorus, propaneoxybis(phenylbutoxy)phosphorus, butaneoxybis(phenylbutoxy)phosphorus, phenylbis(phenoxy)phosphorus, benzyldi(phenoxy) Phosphate, phenethyl bis(phenoxy)phosphorus, 22 1351984 phenylpropyl bis(phenoxy)phosphorus, phenyl bis(phenoxy)phosphorus, phenylbis(benzoquinoneoxy), Benzyl bis(benzyloxy) benzene, phenethyl bis(benzyloxy) wall, phenylpropyl bis(benzyloxy)phosphorus 'p-butyl butyl (stupyloxy) phosphorus, stupid oxygen Bis(phenylmethoxy)phosphorus, phenylbis(stupyloxy)phosphorus, benzoinyldiyl Stupid ethoxy) phosphorus 'phenethyl bis(phenethyloxy)phosphorus, propyl propyl (stupyloxy) phosphonium butyl bis(phenylethoxy)phosphorus, phenoxy bis(phenylethoxy) Phosphate, phenylbis(phenylpropoxy)phosphorus, benzyldi(p-propoxy)phosphorus, phenethylbis(stupoxy)phosphorus, phenylpropylbis(phenylpropoxy)phosphorus , phenyl bis(phenylpropoxy)phosphorus, phenoxy bis(phenylpropoxy)phosphine, phenylbis(phenylbutoxy)phosphorus, benzyldi(phenylbutoxy)phosphorus, phenylethyl Bis(phenylbutoxy)phosphorus, phenylpropylbis(phenylbutoxy)phosphorus, phenylbutylbis(phenylbutoxy)phosphorus, phenoxybis(phenylbutoxy)phosphorus. And R is (^~(:12 alkyl, Μ is also 2 alkyl, alkoxy, aryl, alkylaryl or phenoxy), when n=l, specific examples of such include dimethyl Methoxy scale, diethyl methoxy phosphorus, dipropyl methoxy phosphorus, dibutyl methoxy phosphorus, dimethyl ethoxy phosphorus, diethyl ethoxy phosphorus, dipropyl ethoxy phosphorus , dibutyl ethoxyphosphorus, dimethyl propoxy phosphorus, diethyl propoxy phosphorus, dipropyl propoxy phosphorus, dibutyl propoxy phosphorus, dimethyl butoxy phosphorus, two Ethylbutoxyphosphorus, dipropylbutoxyphosphorus, dibutylbutoxyphosphorus, diethoxyoxymethoxyphosphorus, dipropoxymethoxyphosphorus, dibutoxymethoxymethoxy Phosphorus, dimethyloxy ethoxy ethoxylate, dipropoxy ethoxy phosphine, dibutoxy ethoxy phosphine, dimethoxy oxy propoxy phosphorus, diethoxy oxy propoxy phosphorus, two Butadiene oxypropoxyphosphine, methaneoxybutoxyphosphorus, diethoxyoxybutoxyphosphorus, dipropoxyoxybutoxyphosphorus, diphenylmethoxyphosphorus, diphenylmethyl Oxyphosphorus, diphenylethylmethoxyphosphorus, diphenylpropylmethoxyphosphorus Diphenylbutyl methoxy phosphorus, diphenoxy methoxy phosphorus, diphenyl ethoxy phosphorus, di-p-methyl ethoxy phosphorus, diphenyl ethyl ethoxy phosphorus, diphenyl propyl ethoxylate , Diphenylbutylethoxyphosphorus, Diphenoxyethoxyphosphorus, Diphenylpropoxy 2 1351984 Phosphorus, Alumcyl Propoxy, Diphenylethylpropoxy, Diphenyl Propyloxyphosphorus, diphenylbutylpropoxyphosphorus, di-phenyloxypropoxyphosphine, diphenylbutoxyphosphorus, diphenylphosphonium butoxide, di-p-ethylbutoxyphosphorus, Di-propyl propyl butoxy phosphorus, diphenylbutyl butoxy phosphorus, diphenoxybutoxy phosphorus. For example, R is an I~C丨2 cycloalkyl group, and Μ is C丨~C丨2 alkyl , alkoxy, aryl, alkylaryl or phenoxy, when n = 1, specific examples of such include dinonyl (cyclopropoxy) phosphorus, diethyl (cyclopropoxy) phosphorus , dipropyl (cyclopropoxy) phosphorus, dibutyl (cyclopropoxy) phosphorus, dimethyl (cyclobutyloxy) phosphorus, ethyl (3⁄4 butoxy) scale, monopropyl (cyclobutane) Oxy), dibutyl(cyclobutoxy)phosphorus, dimethaneoxy (cyclopropoxy) Phosphorus, diethoxyoxy (cyclopropoxy) phosphorus, dipropoxy (cyclopropoxy) phosphorus, butoxy (cyclopropoxy) phosphorus, dimethaneoxy (cyclobutoxy) phosphorus , diethoxyoxy(cyclobutoxy)phosphorus, dipropoxyoxy(cyclobutoxy)phosphorus, dibutoxyoxy(cyclobutoxy)phosphorus, diphenyl(cyclopropoxy)phosphorus, Diphenylmethyl (cyclopropoxy) phosphorus, diphenylethyl (cyclopropoxy) phosphorus, diphenylpropyl (cyclopropoxy) phosphorus, diphenylbutyl (cyclopropoxy) phosphorus, diphenyl Oxy (cyclopropoxy)phosphine, diphenyl(cyclobutoxy)phosphorus, diphenylmethyl(cyclobutoxy)phosphorus, diphenylethyl(cyclobutoxy)phosphorus, diphenylpropyl ( Cyclobutoxy)phosphine, diphenylbutyl(cyclobutoxy)phosphorus, diphenoxy(cyclobutoxy)phosphorus. For example, R is an aryl group or an alkylaryl group, and 1 is a c-haha a base, an alkoxy group, an aromatic aryl group or a phenoxy group. When π = 1, specific examples of such a group include dimethyl (phenoxy), diethyl (phenoxy), and Propyl (phenoxy) phosphorus dibutyl (phenoxy) phosphorus, dimethyl (benzene Oxy)phosphine, diethyl(benzyloxy)phosphorus, dipropyl(benzyloxy)phosphorus, dibutyl(benzyloxy)phosphorus, methyl(phenylethoxy)disc,two Ethyl (phenethyloxy) scale, dipropyl (phenethyl lactyl, dibutyl (phenylethoxy) phosphorus, dimethyl (phenylpropoxy) phosphorus, di-b (phenylpropoxy) phosphorus , dipropyl (phenylpropoxy) phosphorus, dibutyl (phenylpropoxy) phosphorus 'dimethyl (thinoxy) disc, diethyl (phenylbutoxy) disc 'dipropyl 24 1351984 base (Phenyloxy)phosphorus, dibutyl(phenylbutoxy)phosphorus, dimethaneoxy(phenoxy)phosphorus, diethoxyoxy(phenoxy)phosphorus, dipropoxyl (phenoxy) Phosphorus, monobutoxy (aldooxy) phosphorus, dihanyloxy (benzyloxy) phosphorus, diethoxyoxy (phenyl foxy) phosphorus, dipropoxy (benzene? Oxy)phosphine, dibutoxyoxy(benzyloxy)phosphorus, di-f-alkoxy(phenethyloxy)phosphorus, diethoxyoxy(phenethyloxy)phosphorus, propaneoxydi(benzene) Ethoxy)phosphorus, dibutoxyoxy(phenethyloxy)phosphorus, dimethaneoxy(p-propoxy)phosphine, diethoxyoxy(p-propoxy)phosphine, monopropoxy (benzene) Propoxy)phosphorus, dibutoxyoxy(phenylpropoxy)phosphine, dimethaneoxy (thanobutoxy)phosphine, diethoxyoxy(phenylbutoxy)phosphorus, dipropoxyoxyl (benzene) Butoxy)phosphorus, dibutoxyoxy(phenylbutoxy)phosphorus, diphenyl(phenoxy)phosphorus, diphenylmethyl(phenoxy)phosphorus, diphenylethyl(phenoxy)phosphorus , bis-propyl (phenoxy) phosphorus, diphenylbutyl (phenoxy) phosphorus, diphenyl (benzyloxy) phosphorus, monobenzyl (benzyloxy) phosphorus, diphenylethyl (Benzyloxy)phosphorus, phenylpropyl(benzyloxy)phosphorus, diphenylbutyl(benzyloxy)phosphorus, diphenoxy(benzyloxy)scale, triphenyl (stupidyloxy) Base, diphenylmethyl (stupyloxy) phosphorus, diphenylethyl (phenethyloxy) phosphorus, Diphenylpropyl (phenethyloxy) phosphorus, diphenylbutyl (stupylethoxy) phosphorus, diphenoxy (phenethyloxy) scale, diphenyl (phenylpropoxy) phosphorus, two parasexoid (phenylpropoxy)phosphorus, di-p-ethyl (p-propoxy)phosphine, phenylpropyl(phenylpropoxy)phosphine, diphenylbutyl(phenylpropoxy)phosphorus, diphenoxy (benzene) Propoxy)phosphorus, diphenyl(thanobutoxy)phosphorus, diphenylmethyl(stupoxy) disc, = stupid ethyl (phenylbutoxy), diphenyl (phenylbutoxy) A dish, a diphenylbutyl (thanobutoxy)phosphine, a diphenoxy (phenylbutoxy)phosphorus. The hydrogenation catalyst (4) of the present invention is a compound comprising the formula (IV): 25 1351984

Wherein R4, R5, and R6 may be the same or different substituents, and are an alkyl group of Cl~c or a C: 6-C, 2 aryl group, a hydrogen atom or a halogen atom.

According to the hydrogenation catalyst composition of the present invention, specific examples of the hydrogenation catalyst (C) include: trimethyl IS, triethylamine, tri-n-propyl, triisopropyl aluminum, dibutyl IS, II (second butyl), tris(isobutyl) Shaosan (n-pentyl), three (isopentyl), three (n-hexyl), three (isohexyl, three (1) -Methylpentyl)aluminum, tris(2,5-dimethyloctyl)aluminum, tris(2,6-dimethyloctyl)aluminum, tris(2-ethylhexyl)aluminum, triphenylaluminum, Diethylaluminum chloride: Ethyl dichloride, tripropyl chloride in Lu, dibutyl chloride in Lu, diisobutylaluminum chloride, di-butylated aluminum, etc. Preferred choice It is triethyl aluminum, triisopropyl aluminum, tributyl aluminum or tri(isobutyl) aluminum, vaporized diethyl aluminum. The hydrogenation process of the invention will be dissolved in a passive organic solvent or partially

The bluntness of the sulphate and amine polar compounds (iv) the co-different polymer of the solvent reacts with hydrogen in the presence of the hydrogenation composition of the present invention to selectively hydrogenate a total of two dilute polymers The unsaturated double bond of the unit. 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 towel to be hydrogenated in a manner such that the nitrogen gas and the polymer are sufficiently contacted. The hydrogenation reaction can be carried out in a batch or continuous manner. The order of addition of the hydrogenation catalysts (a), (b) ' and (c) is not limited. For example, the catalyst (b) may be first added to the polymer solution, and a mixed solution of the human catalyst (4) and (4) 26 1351984 may be added. Alternatively, the catalyst (8) may be first added to the polymer solution, and then the solution of the catalyst (4) and the solution of the catalyst (4) may be separately added. When all the contacts are added to the polymer and stored in a passive atmosphere for a long period of time, the catalyst is still quite active. Therefore, the touch-communication composition of the present invention is quite suitable for industrial quantities. Production needs. According to the present invention, the passive organic solvent used to dissolve the hydrogenation catalyst and the co-diene polymer may be a linear or branched hydrocarbon such as decane, hexanol, gamma, cinnabar, and others. Analogs; or may be alicyclic hydrocarbons such as chlorhexidine, cycloheptane and fluorenylcycloheptane. The Ring House and the Orthodox House are suitable examples. As the blunt organic solvent, aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene can also be used. The environment for preparing the catalysts (a), (b), and (4) should be carried out under conditions of blunt gas and low water content. The blunt atmosphere means pure gases of cerium, atmosphere and nitrogen, and these gases do not participate in the hydrogenation reaction. Air and oxygen or excessively high: Injury, will oxidize or decompose hydrogenation catalyst, causing the catalyst to lose activity. However, if it involves a process in which the catalyst must be pre-mixed, the temperature is preferably 〇~, and the catalyst will be inactivated when the muscle is too far. If the temperature is too low, the catalyst itself will not lose its activity, but the activity is too low. Not hydrogenated. According to the present invention, a total of dilute polymer used for hydrogenation can be produced according to the prior art, such as anionic polymerization, cationic polymerization radical polymerization, 'polymerization polymerization', solution polymerization, emulsion polymerization . In the polymerization, it is preferred to use an organolithium compound as a contact-promoting polymer having a carbon clock ion at the end of the molecular bond, and thus, after the addition of the precursor, polymerization can be further carried out to grow the molecular chain. Specific examples of the organic clock compound include n-propyl clock, isopropyl clock, n-butyl group, isobutyl pentyl group, n-pentyl group, phenyl chain, phenyl group, and the like. The carbon gas compound of Shuangli is, for example, Μ•双里_正丁烧双锂-戍, 27 1351984 1,2-double bell-double stupid, biphenyl butyl, n or 1,4-double (1-Lithium-3methylpentyl) stupid. The amount of the organolithium compound is determined by the molecular weight of the desired polymer. The term "co-light dilute polymer" as used in the present invention means a homopolymer or copolymer polymerized with a conjugated diene as a monomer, and the terminal of the molecular chain has an active group or a non-active group. The active group refers to the free radical carbon of the dish, and the anion group of the metal ion and the cationic group of the carbon. The copolymer of the light dilute is capable of arranging or embedding the two or more kinds of the dilute monomer. a segment, a graft, a polymer, or a milk row, block, graft copolymer which may be at least one of a conjugated diene monomer and at least one of the above-mentioned #Ethyl aromatic tobacco monomers. The total amount of the dimer monomer in the present invention may be a conjugated diene of + 4 i Η carbon atoms. Specific examples include u butadiene, isoprene, 2,3_1: yl-u-butyl Rare 'u_pental dilute, 2_methyl}, 3_戍二妇, 13_hex-ene '4,5-diethyloctadiene' 3-butyl-octenediene and its mixture Diene 'isoprene and a mixture of dibutyl and isoindol are preferred conjugated diene monomers. Suitable for hydrogenated styrene/butadiene in the present invention. The best styrene 'ethylene-butylene-styrene (SEBS) block copolymer, styrene chloride / /, pentene is best loaded with styrene - ethylene - propylene - Styrene (SEPS) ^ segment copolymerization ^ hydrogenated styrene / (butadiene / isoprene mixture) copolymer = better is styrene-ethylene _ ethylene _ propylene - styrene (sEEps) Segment Copolymer: The polymer containing the divalent unit of the pre-hydrogenation of the present invention preferably has a molecular range of from 1,000 to 1 Å. The conjugated diene/vinyl aromatic copolymer of the present invention can be obtained by hydrogenating P to obtain a high-value thermoplastic elastomer. Specific examples of B 28 1351984 dilute aromatic tobacco monomers suitable for use in the present invention include styrene, tert-butyl styrene, δ-methyl styrene 'o-methyl styrene' p-methyl styrene , bis-diphenyl stupid 1, 1,1-diphenylethylene, ethylene naphthalene, anthracene, fluorene-bismethyl-p-ethylamine styrene, anthracene, fluorene-diethyl-p-ethyl The amine is stupid ethylene. A preferred example is styrene. Specific examples of the conjugated diene/vinyl aromatic copolymer are (?) butadiene/styrene copolymer and (2) isoprene/styrene copolymer (3) butadiene/isoprene / styrene copolymer.

Further, a tertiary amine compound or a ruthenium compound may be added to the system of the conjugated diene polymer to increase the vinyl structure of the conjugated diene. Suitable compounds include the general tertiary amine compounds, tetrahydrofuran or diethyl ether, and the like. In the present invention, the metering ratio of the hydrogenation catalyst (a) is sufficient to add 0.0001 to 5 〇 mmole to a total of 1 〇〇g of a dilute polymer, and more than 5 〇mm〇ie is used for ' Benefits, and the addition of too high a meter will require a procedure to remove the catalyst. The optimum amount of the hydrogenation catalyst (a) is 0.002 to 1 mmol per 1 g of the conjugated polymer.

In the present invention, the mole ratio of the catalyst (b) and the catalyst (a) preferably falls within the range of 〇 j 50. If the mole ratio is less than 0.1, the hydrogenation catalyst can not effectively increase the hydrogenation activity, causing the final hydrogenation process to stagnate without failing to achieve the desired goal. On the other hand, if the mole ratio is more than 50, it is necessary to have a step of removing the catalyst, and it is easy to cause an unnecessary secondary reaction, which hinders the progress of the hydrogenation reaction. The optimum mole ratio of the catalyst (b) and the catalyst (a) is between 2 and 15. In the present invention, the mole ratio of the catalyst (c) and the catalyst (a) preferably falls within the range of 〇1 to 50. Better between. If the molar ratio is lower than 〇丨, there is no ability to activate the catalyst (a), and the relative hydrogenation efficiency is rather poor. If the ratio exceeds 50, unnecessary secondary reactants are generated, which in turn causes a sharp drop in the efficiency of hydrogen 29 135 1984 and there is still a need to remove the catalyst. The reaction temperature of the hydrogenation reaction of the present invention can be carried out at a temperature ranging from 〇 ° C to 2 〇〇〇 c. The reaction temperature is lower than 〇. (: If the reaction rate will become low and inefficient, and the amount of catalyst (a) must be increased, the method is not economical. If it is higher than 20 (the temperature of TC is carried out, it will cause the catalyst to lose = The phenomenon, thus reducing the activity of the catalyst, and the entire system is prone to side reactions, causing the polymer to decompose or form a gel. The preferred hydrogenation temperature is between 4 ° ° and 150 ° C.

The preferred hydrogenation pressure of hydrogen is between IKg/cm2 and 90Kg/cm2. If the hydrogenation pressure is less than 1Kg/cm2, the reaction rate will not become obvious. If the hydrogen pressure exceeds 90Kg/cm2, the hydrogenation will increase in temperature and the hydrogenation reaction will be terminated quickly. The better hydrogenation pressure is preferably 2 to 35Kg/cm2. . Under the above hydrogenation conditions, the amount of the catalyst can be decreased as the hydrogen pressure is increased. In order to achieve a reduction in the amount of the catalyst, a higher hydrogenation pressure can be selected. According to the present invention, the hydrogenation time is between several seconds and 4 hours, and the appropriate range is adjusted depending on the ratio of the catalyst mixture to be added, the pressure of hydrogen, the temperature of hydrogenation, and the like. According to the present invention, the double bond of the conjugated diene polymer can be hydrogenated to any degree as needed by adjusting the amount of the catalyst composition, the hydrogen pressure, and the hydrogenation temperature. By hydrogenating the conjugated diene/vinyl aromatic hydrocarbon copolymer by the catalyst composition of the present invention, the degree of hydrogenation of the double bond in the conjugated diene unit can be stably more than 50%, and even up to above The degree of hydrogenation of the aromatic hydrocarbon benzene ring double bond in the dilute aromatic hydrocarbon unit is below 1%, and may even be as follows. Thus, the catalyst composition used in the present invention has very good catalyst selectivity. The hydrogenation conversion rate is known in the wire dilute unit portion = external spectral analysis, and the hydrogenation rate of the aromatic hydrocarbon core can be determined by UV 30 1351984. For the analysis method similar to this, the polymer solution obtained by hydrogenating the hydrogenation catalyst of the present invention can be referred to as a poor solvent such as a polar solvent to make the polymer coagulant a polymer. Methanol or _. Or ΐ The weathered solution may be poured into hot water and allowed to evaporate the solvent of the polymer disk, or the reaction solution may be directly heated to evaporate the solvent to separate the polymer. According to the present invention, only a very small amount of the hydrogenation catalyst composition is required to successfully hydrogenate the conjugated diene polymer with a satisfactory hydrogenation effect. Most of the catalyst is separated or decomposed from the polymer during the separation process of the polymer, and does not need to be smashed. Raw, soil + special steps for its "washing or money catalyst system"

A special feature of the catalyst composition of the present invention is a hydrogenation catalyst (8), and the presence of a human I = medium can stabilize the effect of other activities after the other contacts are difficult to enhance the other catalysts. Therefore, the catalyst combination of the present invention is used. The addition of the compound to the diene polymer can be carried out for a period of up to 30 minutes or more under the conditions of the pure gas gas, and the reproducibility is very unique, the catalyst composition of the present invention. At a higher reaction temperature, the contact::: The activity of the catalyst in the south of the phase is not due to the high reaction temperature and the activity of the catalyst is inactive, which is quite suitable for commercial mass production. The invention is not limited by the scope of the appended claims, but the scope of the invention is intended to be limited by the scope of the appended claims. Example 1]: Preparation of SBS copolymer in a casing heater with a stirrer, filled with a contact ring 31 1351984 hexane, 7.4 mm 〇le n-butyl lithium (n-butyl 丨 比 比With 252 mm〇le of tetrahydrofuran, and adding 96 g of styrene to it, the polymerization was carried out at 451: After the reaction system was reacted, 4 g of 1,3-butane was added to carry out the reaction. Further, 96 g of stupid ethylene was further added to continue polymerization into a triblock copolymer of SBS (styrene-butadiene-styrene) having a solid content of 9.7% and a molecular weight of 230,000. [Example 2] The polymer solution of the prepared SBS triblock copolymer is transferred to a financial hydrogenation tank, and maintained under a nitrogen atmosphere, and O.llmmole triethyl phosphate is prepared at room temperature at 1 〇m. In a cyclohexane of hydrazine, a cyclohexane solution of 0.1 lmm 〇le triethyl phosphate and 0.16 mmole n-butyllithium, and bis(cyclopentadienyl) 〇〇55 mm〇le were previously mixed in a glove. Titanium dichloride and 0.33 mmole of triisobutylaluminum were added to the SBS polymer prepared above in 2 mL of cyclohexane. The hydrogen gas was blown thereinto to a pressure of 25 kg/cm2 and hydrogenation was carried out at 80 ° C. Figure 1 shows the infrared spectrum of the SBS polymer before and after hydrogenation. # This spectrum shows that the SBS triblock copolymer Before the hydrogenation, the functional groups of the trans double bond were found at the wavelengths of 968 cm·1 and 995 cm-1, and the 1,2-vinyl double bond was found at the wavelength of 9l2cml. After hydrogenation for 2 hours, the above wavelengths were observed. The peak of the disappearance disappeared markedly, and the hydrogenation rate (hydrogenation rate of the unsaturated double bond of the 1,3-butadiene unit) measured at this time was 97%. The data of the hydrogenation reaction were summarized in Table 1. [Example 3] The polymer solution i〇〇〇g of the SBS triblock copolymer prepared in Example 1 was transferred to a pressure-resistant hydrogenation tank, and maintained under a nitrogen atmosphere, and 0.11 mmole of acid-filled triacetate was prepared at room temperature 32 1351984. Vinegar in 〇暮 〇暮 笔 环 环 , 〇 〇 mmol mmol 55 mmole bis (cyclopentadienyl) titanium dichloride in 1 〇 $ 升 升 环 环 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 10 ml of mouthwash a pen liter of hexane solution, respectively added to the SBS polymer prepared above In the middle, in the ^ ^, /, τ people into the hydrogen, the pressure reached 25Kg / cm2, hydrogenation at 80 ° C. 〇, ▲ 邛 after 2 hours of hydrogenation rate can reach 95%. Hydrogenation The data is summarized in Table 1. [Example 4] In the same manner as in Example 3, 〇umm〇ie dish acid triacetate was mixed at room temperature in 1 〇ml of cyclohexane', and premixed in a glove box. 〇, 〇55mm〇le bis(cyclopentadienyl) di-titanium oxide in 1 〇 ml of cyclohexane^ float, and 0.33 mm 〇le of triisobutylaluminum in 1 〇 ml of cyclohexane The SBS polymer solution prepared above was separately added, and chlorine was blown thereinto to a pressure of 25 kg/cm2, and hydrogenation was carried out at 80 t. The rate of deuteration after 2 hours can reach 95%. The data of the hydrogenation reaction are summarized in Table 1. [Example 5] The same procedure as in Example 3 was carried out except that triethyl sulphate was changed to 165.165 mm〇le of methyl dimethyl phosphate in 1 〇ml of cyclohexane, and additionally mixed in a glove box. 0.055 mmole of bis(cyclopentadienyl) di-titanium oxide in 1 mL of cyclohexane suspension, and O33 mmole of triisobutylaluminum in 1 mL of cyclohexane' were separately added to the SBS polymerization prepared above. In the solution, hydrogen gas was blown thereinto to hydrogenate at a pressure of 25 kg/cm 2 ' at 8 rc. The hydrogenation rate after 2 hours reached 97%. The data of the hydrogenation reaction are summarized in Table 1. 33 f ψ» 4 · ν. 1351984 [Example 6] The same procedure as in Example 3 was carried out except that triethyl phosphate was changed to 〇. 2 mmole of decyldiethoxyphosphorin in 1 〇m丨 of cyclohexane, in addition to The glove box was pre-mixed with 0.055mm 〇ie bis(cyclopentadienyl) titanium dioxide in 1 liter of cycloheximide suspension, and 0.33mm 〇le of triisobutyl in 1 liter of cyclohexane. , respectively, added to the SBS polymer solution prepared above, in which hydrogen gas is blown to a pressure of 25 Kg/cm 2 at 8 〇 < t The effect of hydrogenation rate up to 95% after 2.5 hours. The data of the hydrogenation reaction are summarized in the table [Example 7] The same method as in Example 3, but the triethyl phosphate was changed to the phosphoric acid of 〇.2mm〇le Benzyl) ester in 1 〇ml of cyclohexane, additionally mixed with 0.055 mmole of bis(cyclopentadienyl) titanium dihydride in 1 cc of cyclohexane suspension in a glove box, & 0 33 mmole #三isobutyl is added to the SBS polymer solution prepared above in 1 mL of cyclohexane', and hydrogen is blown into it to make the pressure reach 25 Kg/cm2 at 8 (rc for hydrogenation reverse reaction, 2 After the hour, the hydrogenation rate can reach 97%. The data of the hydrogenation reaction is summarized in the table [Example 8] The polymer solution of the SBS triblock copolymer prepared in Example 1 was taken, and transferred to a pressure-resistant hydrogenation. In the tank, the step of adding the catalyst was carried out under the nitrogen atmosphere, and the same procedure as in Example 2 was carried out, and the SBS polymer prepared above was separately added, and after standing for 48 hours under a nitrogen atmosphere, hydrogen was further blown therein to make the pressure. Up to 25Kg/cm2, hydrogenation at 8 (rc). The hydrogenation rate after 25 hours is available. 95%, the data of the hydrogenation reaction are summarized in Table 1. 34 [Example 9] The same procedure as in Example 3 was carried out except that the hydrogenation temperature was changed to a loot: hydrogenation reaction was carried out. After 1 hour, the hydrogenation rate was as high as possible. The data of the hydrogenation reaction are summarized in Table 1. Comparative Example

Several comparative examples are set forth below for comparison with the examples of the present invention. It is noted that the deuterated catalyst compositions used in the comparative examples do not comprise the hydrogenation catalyst of the present invention. (8), by way of further description of the characteristics and advantages of the hydrogenation catalyst composition of the present invention. [Comparative Example 1]

The same procedure as in Example 3 was carried out, but triethyl orthoacetate was not added. Premixed in a glove box with 〇.〇55mm〇le bis(cyclopentadienyl) di-titanium oxide in ίο ml of cyclohexane suspension, and 〇33mm〇le of triisobutylaluminum in 10 ml Cyclohexane was separately added to the SBS polymer solution prepared above, and hydrogen gas was blown thereinto to a pressure of 25 kg/cm2, and hydrogenation was carried out at 8 (rc). Fig. 2 shows the SBS polymer before and after hydrogenation. Infrared spectrum. This spectrum shows that the functional group of the trans double bond was found at the wavelengths of 968 cm·1 and 995 cm·1 before the hydrogenation of the SBS triblock copolymer. The 1,2-vinyl group was found at a wavelength of 912 cm·1. The double bond was present. After hydrogenation for 2 hours, it was found that the absorption at the wavelengths of 995 cm·1 and 912 cm·1 was reduced, but the absorption at 968 cm·1 was hardly changed. The hydrogenation ratio measured at this time was 23%. The data of the reaction were summarized in Table 1. [Comparative Example 2] 35 1351984 100 g of the polymer solution of the SBS triblock copolymer prepared in Example 1 was transferred to a pressure-resistant hydrogenation tank, and hydrogen gas was introduced and stirred for 30 minutes. As in the method of Example 3, but changing the triethyl phosphate to 0.22 mmole Butyllithium, premixed with 0.055 mmole bis(cyclopentadienyl) titanium dichloride in 10 ml of cyclohexane suspension, and 44.44 mmole of triisobutylaluminum in 10 ml of ring in a glove box. Hexane was added to the SBS polymer solution prepared above, and the hydrogen pressure was 25 Kg/cm2, and hydrogenation was carried out at 80 ° C. After 30 minutes, the hydrogenation rate was measured to reach 15%, and the hydrogenation rate after 2 hours reached 24 %. The data of the hydrogenation reaction are summarized in Table 1.

Table 1 Example No. Residual double bond residue (%) 1,2-vinyl double bond residual amount (%) 1,3-butadiene hydrogenation rate (%) benzene ring hydrogenation rate (%) Example 2 2.6 0.3 97 <1 Example 3 2.1 0.2 95 <1 Example 4 2.3 0.3 95 <1 Example 5 1.8 0.497 <1 Example 6 2.5 0.3 95 <1 Example 7 1.5 0.497 <1 Example 8 2.1 0.4 95 <1 Example 9 1.9 0.3 96 <1 Comparative Example 1 75.5 1.5 23 <1 Comparative Example 2 74.4 1.6 24 <1

As can be seen from Table 1, the hydrogenation catalyst composition of the present invention is used to carry out the deuteration reaction of the total diterpene polymer, and the residual double bond residue of the hydrogenated conjugated diene polymer is less than 5%. , the 1,2-vinyl double bond residual amount is less than 5%, 36 1351984 and the 1,3-butadiene hydrogenation rate is greater than 95%; in contrast, Comparative Examples 1 and 2, due to the hydrogenation used The catalyst composition does not comprise the hydrogenation catalyst (b) of the present invention, so that the residual amount of the trans double bond and the 1,2-ethylene double bond is significantly higher, and the 1,3-butylene The hydrogenation rate of the ene is less than 25%.

In summary, the hydrogenation catalyst composition disclosed in the present invention has superior argonization ability for the co-rolled dilute polymer, so that the catalytic reaction can be completed in a small amount. In addition, the hydrogenation catalyst composition is very stable, and after storage for a long period of time, 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 hydrogenation activity in a wide temperature system, and therefore the method of hydrogenating the co-doprene polymer of the present invention can be carried out under a wide temperature system, and is not caused by Too high a heat of hydrogenation reaction and loss of catalyst activity is therefore quite suitable for operation under continuous operating conditions.

Although the present invention has been disclosed in the above preferred embodiments, it is not intended to limit the present invention, and the present invention can be modified and retouched without departing from the spirit and scope of the present invention. The scope of protection shall be as defined in the scope of the patent application attached hereinafter. 37 <S) 1351984 [Simplified illustration of the drawings] Fig. 1 shows the infrared spectrum of the SBS polymer of Example 2 of the present invention before and after hydrogenation. Fig. 2 is a view showing the infrared spectrum of the SBS polymer of Comparative Example 1 before and after hydrogenation.

Claims (1)

1351984 [Scope of Application] I. Announcement this year / 1 ^ Amendment 100. 9.17 1. A catalyst composition of a nitrided conjugated diene polymer, wherein the total diene polymer is a conjugated diene a homopolymer or copolymer comprising the following hydrogenation catalyst: (a) a titanium compound as shown in formula (I): /1 (Cp*)2Ti^R2 (1) 9 wherein R is R2 is the same or different substituent, and is hydrogen, a halogen atom, a c-s-s-alkyl group and an alkoxy group, and C6~^. Cycloalkyl, phenyl, phenoxy, C7~Cio arylalkoxy and aralkyl, carboxy, -CH2P(stupyl)2, _CH2Si(C!~C5 alkyl)3 or -P (stupid 2), Cp* represents a cyclopentadienyl group, a fluorenyl group, a fluorenyl group or a derivative thereof; (b) a compound represented by the formula (II) or the formula (III) 0 II P-(OR)nM3.n P -(〇R)nM3.n Formula (9) Formula (III) wherein R is C&2 alkyl, C3~c, 2 ring alkyl, aryl or alkylaryl ' Μ is alkyl, C widely C丨2 alkoxy, aryl, alkylaryl, oxy or thiol, n = 1 to 3; and (c) as a compound of formula (IV) 39 R4 > 丨-R5 R6 Wherein RR and R may be the same or different substituents, and are a C-Ci2 succinyl group or a C6-Cl2 aryl group, a hydrogen atom or a halogen atom. The catalyst composition according to the first aspect of the invention, wherein the hydrogenation catalyst (a) is a bis (3⁄4 pentylene group and a derivative thereof). 9. The catalyst composition according to claim 2, wherein the nitriding catalyst (4) is bis(cyclopentadiadiyl)titanium difluoride, double (cyclopentadienyl) titanium dichloride 'bis[(2,4-diphenylphosphorylcyclopentadienyl)] Titanium difluoride, bis[(2,4-didecylphosphorylcyclopentadienyl)]titanium difluoride, bis[(2,4-diphenylphosphonated cyclopentadienyl)]dichloride Titanium, dimethoxylated bis(cyclopentadienyl) di-titanized titanium, bis[(2,4-dimethylphosphonium decadienyl)]titanium dichloride, bis(cyclopentane) Alkenyl) dibromide, bis[(2,4-diphenylfluorencyclopentadienyl)]titanium dibromide, bis[(2,4-dimethylphosphonated cyclopentadienyl) 】 titanium dibromide, bis(ethylated cyclopentadienyl) titanium dichloride, bis(n-propylated cyclopentadienyl) titanium dichloride, bis(n-butylated cyclopentadienyl) Di-titanium carbide, bis(2-ethylhexylated cyclopentadienyl) titanium dichloride, dimethyl fluorenyl-biguanide 5 - 2,4-cyclopentadiene-1-ylidene) [冲11161;11718117161^)-1^(775-2,4-cyclopentadien-1-ylidene)], vinyl·bis(β 5_2,4-cyclopentadiene-1-ylidene)[(ethylene)- Bis (7? 5-2,4-cyclopentadien-l- ylidene)] 〇4. The catalyst composition of claim 1, wherein the hydrogenation 40 1351984 catalyst (a) is - (3⁄4 戊Women's base and The catalyst composition of the invention, wherein the catalyzed catalyst (4) is monomethyl bis(cyclopentadienyl). Bis(cyclopentadienyl)titanium, dimethanol bis[(2,4-diphenylphosphorylcyclopentadienyl)]titanium, dimethanol-based bis[cyclo(cyclopentadienyl)titanium] (2,4-dimethyl phosphatized cyclopentadienyl)] titanium, monoethoxybis(cyclopentadienyl)titanium, diethoxybis[(2,4-diphenylphosphorylated ring) Pentadienyl)]titanium, diethoxybis[(2,4-dimethylphosphoniumcyclopentadienyl)]titanium, diphenyloxybis[(2,4-diphenylphosphoryl) Pentadienyl)]titanium, diphenoxy bis[(2,4-dimethylphosphorylcyclopentadienyl)]titanium. 6. Catalyst composition as described in the scope of the patent application ' Wherein the hydrogenation catalyst (a) is a dentate compound of bis(indenyl, fluorenyl or a derivative thereof) titanium. The catalyst composition according to claim 6, wherein the hydrogenation catalyst ( a) is bis(k-fluorenyl)t Itanium dichloride], bis(1 indenyl)titanium dichloride]indenyl)titanium dichloride], bis(dimethoxyindenyl)titanium dichloride, bis(indenyl)difluoro Titanium, bis(node) titanium difluoride, bis(dimethoxyindenyl) titanium difluoride, bis(indenyl)titanium dibromide, bis(nodotic) titanium dibromide, bis(dimethyl Oxyfluorenyl) Titanium, bis(indenyl) titanium dibromide. 8. The catalyst composition according to claim 2, wherein the hydrogenation catalyst (a) is a hydrocarbon (hydrocarbyl) compound of bis(indenyl, fluorenyl or its derivative) titanium. 9. The catalyst composition according to claim 8, wherein the hydrogenation 41 1351984 catalyst (a) is dimethyl bis(indenyl) titanium, dimethoxy bis(indenyl) titanium, two Methoxy bis(indenyl)titanium, dimethoxybis(dioxanthenyl)titanium, dimethoxy bis(nodotyl)titanium, dimethanol bis(indenyl)titanium, dinonanyl double (fluorenyl) titanium, dimethanol bis(dioxin) titanium, dimethanol bis(indenyl) titanium, diphenoxy bis(indenyl) titanium, diphenoxy bis(indenyl) titanium , Diphenoxy bis(dimethoxycarbonyl), diphenoxy bis(indenyl) chin. 10. The catalyst composition according to claim 1, wherein the hydrogenation catalyst (b) is a compound of the formula (II), and R is a Ci~C12 alkyl group, a C3~C12 cycloalkyl group. , an aryl group or an alkyl aryl group, where n = 3. 1 1. The catalyst composition according to claim 10, wherein the hydrogenation catalyst (b) is trimethyl sulphate, triethyl sulphate, tripropyl sulphate, tris(isopropyl) phosphate ) ester, tributyl phosphate, tri(isobutyl) phosphate, tri(tert-butyl) phosphate, tri(tert-butyl) phosphate, tri(cyclopropyl) phosphate, tris(phosphoric acid) Hexyl) ester, tris-ethyl phosphate, tris(benzyl) phosphate, tris(phenylethyl) phosphate, tris(phenylpropyl) phosphate, tris(phenylisopropyl) phosphate, tris(phenyl) phosphate n-Butyl) ester, tris(phenylbutyl)phosphate, tris(phenylisobutyl)phosphate, tris(phenylbutylbutyl)phosphate. 12. The catalyst composition of claim 1, wherein the hydrogenation catalyst (b) is a compound of the formula (II), and R is a C-C12 alkyl group, and the hydrazine is an alkyl group or an alkane. An oxy group, an aryl group, an alkylaryl group, a phenoxy group or a hydroxyl group, in which case n=2. 13. The catalyst composition according to claim 12, wherein the hydrogenation catalyst (b) is dimethyl decyl phosphate, dimethyl ethyl phosphate, dimethyl propyl phosphate, butyl phosphate Dimethyl ester, diethyl methyl phosphate, diethyl ethyl phosphate, diethyl propyl phosphate, diethyl butyl phosphate, dipropyl methyl phosphate, dipropyl ethyl phosphate, propyl phosphate Propyl ester, dipropyl butyl phosphate, diethyl decyloxy phosphate, 42 1351984 decyloxy acid dipropylene, ethylene oxylate acid bismuth, 6 oxy oxy phthalate , propane oxyphosphoric acid dimethyl ester, propane oxyphosphoric acid diethyl ester, stupyl dimethyl phosphate, stupid bisphosphonate, phenyl phosphate dipropylene, stupid methyl phosphate diacetate, alum Diethyl phosphate, dipropyl benzyl phosphate, dimethyl phenethyl phosphate, diethyl phenethyl phosphate, dipropyl ethyl citrate, diisopropyl propyl phosphate, propyl propyl phosphate Ethyl ester, dipropyl propyl dipropyl phosphate, dimethyl phenoxy phosphate, diethyl phenoxy phosphate, dipropyl phenoxy phosphate, dimethyl phosphate, phosphoric acid Diethyl vinegar, dipropyl phosphate, dibutyl phosphate. Φ 14. The catalyst composition as described in claim 1, wherein the hydrogen catalyst (b) is a compound of the formula (II) and R is an aryl group or an alkyl aryl group, Μ It is a Q-Q2 decyl group, an alkoxy group, an aryl group, an alkyl aryl group, a phenoxy group or a thio group. 15. The catalyst composition of claim 14, wherein the hydrogenation catalyst (b) is di-methyl methyl phosphate, diphenyl ethyl phosphate, di(phenylmethyl) methyl phosphate. , bis(benzyl)ethyl phosphate, di(phenylethyl)methyl phosphate, di(phenylethyl)ethyl phosphate, bis(phenylpropyl) acetonate, ethyl scale Acid mono(propyl) vinegar, decyloxy diphenyl phosphate, methane oxyphosphoric acid di(phenylmethyl) vinegar, alpha oxyphosphoric acid bis(phenethyl) ester, ethene alkoxylate Diphenyl ester, ethoxylated bis(benzyl) ester, bis(phenylethyl) ethoxy oxyphosphate, diphenyl phenyl phosphate, bis(benzyl) phenyl phosphate, stupid Di(phenylethyl) vinegar, benzyl bisphosphonate, benzyl bis(benzyl) S, benzyl bis(phenylethyl) s, phenethyl phosphate Ester, bis(benzyl) phenethyl phosphate, di(phenethyl) phenethyl phosphate, di(p-methyl) phenoxy phosphate, di(phenylethyl) phenoxy phosphate, Di-p-propyl phosphate, di(p-methyl)S, bis(phenethyl) hydride, diacid benzene Yl) vinegar. 16. The catalyst composition as described in claim 1 wherein the hydrogenation catalyst 0 is a compound of the formula (ΙΠ), and R is a CcCi2, C3 to C12 cycloalkyl, aromatic The catalyst composition of the invention, wherein the hydrogenation catalyst (b) is trimethyl phosphite, phosphorous acid tris. Ethyl ester 'tripropyl phosphite, tributyl phosphite, tri(cyclopropyl) phosphite, tri(cyclohexyl) phosphite, triphenyl phosphite, tris (benzyl) phosphite, Di(p-ethyl) phosphite, tris(phenylpropyl) phosphite, tris(phenylbutyl) phosphite. 18. The catalyst composition according to claim 2, wherein the hydrogenation catalyst (b) is a compound of the formula (III), and the ruthenium is an alkyl group, and the ruthenium is also a CrCu alkane. Alkyl, alkoxy, aryl, alkylaryl or phenyloxy. 19. The catalyst composition according to claim 18, wherein the hydrogenation catalyst (b) is f-based dimethoxy phosphorus, ethyl dimethoxy phosphorus, propyl dimethoxy phosphorus, A Ethyl ethoxy scale, ethyl diethoxy scale, propyl diethoxy phosphorus, methyl 1-propoxy scale, ethyl dipropoxy dish, propyl dipropoxy scale, ethyl oxy Dimethoxyphosphine, propaneoxydimethoxyphosphorus, methaneoxydiethoxyphosphorus, ethaneoxydiethoxyphosphorus, propaneoxydiethoxyphosphorus, methaneoxydipropoxy Phosphorus, ethoxyoxydipropoxyphosphorus, phenyldimethoxyplatin, benzyldimethoxyscale, stupid ethyldimethoxyphosphorus, phenylpropyldimethoxyphosphorus, oxy Phosphyl dimethoxy phosphorus, phenyl diethoxy phosphorus, benzyl diethoxy phosphorus, phenethyl diethoxy phosphorus, propyl propyl diethoxy phosphorus, phenoxy diethoxy phosphorus Phenyldipropoxyphosphorus, benzyldipropoxyphosphorus, phenethyldipropoxyphosphorus, phenylpropyldipropoxyphosphorus, phenoxydipropoxyphosphorus. 20. The catalyst composition according to claim 1, wherein the hydrogenation catalyst (c) is trimethyl aluminum, triethyl aluminum, tri-n-propyl aluminum, triisopropyl aluminum, and tributyl. Base aluminum, tri(t-butyl)aluminum, tri(isobutyl)aluminum, tris(n-pentyl), tris(isopentyl), tris(n-hexyl), tris(isohexyl)aluminum, Tris(1-methylpentyl)aluminum, tris(2,5-dimethyloctyl)aluminum, tris(2,6-dimethyloctyl)aluminum, tris(2-ethylhexyl)aluminum, triphenyl Base aluminum, diethyl chlorinated, diemulsified ethyl ester, tripropyl chloride, dibutyl 44-alkyl aluminum, vaporized diisobutyl aluminum, butyl aluminum dichloride or a combination thereof. The catalyst composition according to the above-mentioned patent application, wherein the hydrogenation catalyst (C) is triisobutylaluminum or triethylaluminum. The catalyst composition according to claim 1, wherein the conjugated diene polymer is a monomer or a copolymer obtained by anionic polymerization, radical polymerization, coordination polymerization, or cationic polymerization. 23. The catalyst composition according to item j of the patent application, the order of addition of the hydrogenation catalysts (a), (b), and (c), respectively, is added to the conjugated diene polymer simultaneously or in different order. In solution. 24. The catalyst composition of claim 1, wherein the hydrogenation catalyst (&) is used in an amount of from 0.001 to 50 mmole, relative to 1 gram of the conjugated diene polymer. The catalyst composition according to claim 1, wherein the hydrogenation catalyst (a) is used in an amount of from 0.002 to 1 mmole based on 0 gram of the conjugated diene polymer. 26. The catalyst composition of claim 1, wherein the hydrogenation catalyst (b) and the hydrogenation catalyst (a) have a molar ratio of up to 5 Torr. 27. The catalyst composition of claim 1, wherein the hydrogenation catalyst and the hydrogenation catalyst (a) have a molar ratio of from 0.1 to 50. 28. The catalyst composition of claim j, wherein the conjugated dilute polymer has a molecular weight in the range of from 1,000 to 1,000,000. 29. The catalyst composition of claim 1, wherein the hydrogenation catalyst composition is a hydrogenation catalyst applied to a conjugated diene monomeric monomer or a vinyl aromatic hydrocarbon unit and conjugated The diene is a monomer-polymerized copolymer. The catalyst composition according to claim 29, wherein the vinyl aromatic hydrocarbon unit and the conjugated diene unit copolymer are styrene-butadiene 45 copolymerized. a 'styrene-isoindole two-copolymer, styrene-(butyl di-isoprene/isoprene) copolymer. 31. The catalyst composition as described in paragraph 3G of the / please = range, the ethyl sulphate te singular 7 〇 and the total | 16 bis; ^ unit copolymer for the latter stage (bi〇ck), out of order (Random ), progressive block (Taper) arrangement. 32. The catalyst composition described in the third paragraph of the patent in March, the post-nitriding ethylene-butylene copolymer is a styrene butadiene styrene copolymer (SEBS). 33. The catalyst composition as described in the third paragraph of the Guangming Patent Target, the hydrogenated-isoprene copolymer, stupid ethylene-ethylene-propylene-styrene copolymer (SEPS) ). 34. = f Please use the thief of the full-time @3G rhyme, the stupid ethylene-(butadiene/isoprene) copolymer is a stupid ethylene-ethylene-ethylene-propylene-styrene copolymer (Seeps). 35. A method for hydrogenating a total of a diene polymer, and wherein the co-diuretic unit polymer is a homopolymer or copolymer of a conjugated diene, dissolved in a blunt organic core agent The olefin polymer is reacted with hydrogen in the presence of a catalyst composition as described in the scope of claim 1 to selectively hydrogenate the unsaturated double bond of the common diene unit in the conjugated diene polymer. The method of claim 35, wherein the hydrogenation is at a reaction temperature of from 0 ° C to 200 ° C. (Between: and the hydrogen pressure is in the range of j to 9 〇 kg/cm 2 . 37. The method described in claim 35 of the patent application 'can reduce the conjugated diene unit and the hydrogenation rate of the double bond At least 50% or more. 3 8. The method according to claim 35, wherein the nitridation ratio of the unsaturated double bond of the conjugated diene unit can be at least 90% or more. 46 1351984 39. The method of claim 35, wherein the hydrogenation rate of the benzene ring double bond of the vinyl aromatic hydrocarbon unit is less than 10%. 40. The method of claim 35, wherein the hydrogenation rate of the benzene ring double bond of the vinyl aromatic hydrocarbon unit is less than 3%. 47