CN100354319C - Hydrogenation catalyst composition and method for hydrogenating conjugate diene polymer - Google Patents

Hydrogenation catalyst composition and method for hydrogenating conjugate diene polymer Download PDF

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CN100354319C
CN100354319C CNB200410096736XA CN200410096736A CN100354319C CN 100354319 C CN100354319 C CN 100354319C CN B200410096736X A CNB200410096736X A CN B200410096736XA CN 200410096736 A CN200410096736 A CN 200410096736A CN 100354319 C CN100354319 C CN 100354319C
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silicon
hydrogenation catalyst
alkoxyl group
oxygen base
aluminium
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CN1781955A (en
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林福
蔡敬诚
蔡智光
刘顺安
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Taiwan Synthetic Rubber Corp
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Abstract

The present invention provides a hydrogenation catalyst composition and a method for hydrogenating conjugated diene polymers. The method comprises the following step: conjugated diene polymers dissolved in a passive organic solvent react with hydrogen gas under the existence of the hydrogenation catalyst composition for selectively hydrogenating the unsaturation double bonds of conjugated diene units in the conjugated diene polymers. The hydrogenation catalyst composition of the present invention comprises a dicyclopentadiene group titanium compound (a), a compound (b) shown as the general formula (II) and the general formula (III) and a trialkyl aluminum compound (c). Compared with the traditional techniques, the method related by the present invention for hydrogenating conjugated diene polymers only needs to use a small quantity of hydrogenation catalyst compositions and has no need removal.

Description

The method of hydrogenation catalyst composition and hydrogenated conjugated diene polymer
Technical field
The present invention relates to a kind of method of hydrogenated conjugated diene polymer, particularly the method for using the special catalyst composition to come hydrogenated conjugated diene polymer.
Background technology
Industrially carry out polymerization or copolymerization to obtain to contain in the polymer molecular chain polymkeric substance of the two keys of unsaturated thiazolinyl with conjugated diolefine (conjugated diene) monomer usually.It is very favourable that this polymkeric substance is used in sulfuration, yet just because of the existence of a large amount of unsaturated double bonds is arranged, can cause the not good of performances such as its weathering resistance, thermotolerance, scale resistance.Particularly use with conjugated diolefine and vinylaromatic hydrocarbon (vinyl aromatichydrocarbon) and carry out the polymkeric substance that blocked polymeric thermoplastic rubber physical crosslinking exists as monomer, its situation is more obvious, and unfavorable especially as if the modification agent and the transparent impact-resistant material that are used in styrene resin, olefin resin.And relative its be in the Application Areas of exterior material, more because performances such as its weathering resistance, thermotolerance, scale resistance not good, and is subjected to a lot of restrictions.
With conjugated diolefine and vinylaromatic hydrocarbon is the available hydrogenant method of improvement of defectives such as monomeric block or the multipolymer weathering resistance of arranging by preface, thermotolerance, scale resistance, significantly eliminate unsaturated double bond and be improved, known have a lot of catalyzer to be used for the compound that hydrogenation contains unsaturated double-bond, catalyzer can be divided into two big classes:
(1) heterogeneous catalyst must be deposited on the carrier usually according to circumstances, and carrier is carbon, silica, alumina, lime carbonate etc. for example, and metal is generally the compound that Ni, Pd, Pt form.
(2) homogeneous catalyst, for example (a) Ziegler (Ziegler) catalyzer is by organic salt and a kind of reductive agent of Ni, Co, Fe, Cr etc., and for example the association of organo-aluminium compound forms the single composition organometallic compound of (b) Ru, Rh, Ti, La.
Heterogeneous catalyst extensively applies to industry member, but and homogeneous catalyst compare, its activity is lower, thus in order to want hydrogenization to some extent, must a large amount of catalyzer of use, and must under higher temperature and pressure, carry out.Relative, homogeneous catalyst is usually than the tool activity, and a spot of catalyzer is promptly enough, and its hydrogenation can carry out under than modest pressure and temperature condition.
Use the method for the heterogeneous catalyst on the carrier, at first dissolve in the suitable solvent, in the presence of heterogeneous catalyst, contact then with hydrogen with desiring to give the hydrogenant polymkeric substance.The viscosity of polymkeric substance is quite high, since the spatial obstacle of polymkeric substance and the absorption of the height of polymkeric substance, (in case give hydrogenation, it is easy to stay catalyst surface), disturb the approaching of non-hydropolymer active center easily, so contacting of reactant and catalyzer is quite difficult.And this type of catalyzer active normal rapid decline suddenly when polymkeric substance hydrogenation simultaneously, the mode that must be accompanied by High Temperature High Pressure is carried out, and hydrogenant reaction heat is very high, and hydrogenation meeting at high temperature makes the rapid rising of temperature of reaction, makes polymkeric substance be easy to decompose or form gel.So be in this kind operational condition, when desiring the multipolymer of hydrogenating conjugate diene and vinylaromatic hydrocarbon, optionally the unsaturated double bond of the conjugated diolefine in the hydrogenated copolymer is very difficult.Reason is under this High Temperature High Pressure, and regular meeting is hydrogenated the phenyl ring core in the vinylaromatic hydrocarbon unit.Situation of another difficulty operation is, catalyzer separated with polymers soln after the hydrogenation be quite to be difficult for, because polymkeric substance is adsorbed on the heterogeneous catalyst by brute force, can not remove fully.
And in the method for using the Z-type catalyst catalysis system, reaction comes down to take place on uniform dielectric, so the hydrogenation of multipolymer can be carried out under the pressure of appropriateness and temperature condition.And, by abundant selection hydrogenant condition, can selective hydration the two keys of block of poly-(conjugated diolefine) and aromatic nucleus that can poly-(vinyl aromatic hydrocarbon) block of hydrogenation.
Traditionally, the method for using homogeneous catalyst to come hydrogenated conjugated diene polymer is described below:
For example United States Patent (USP) case 4980421 is delivered the selective hydrogenation of the unsaturated double-bond of conjugated diolefin polymer, be utilize comprise two (cyclopentadienyl) titanium (+4) compound, alcoxyl lithiumation thing, and the hydrogenation catalyst of organometallic compound (as the compound of aluminium, zinc, magnesium) carry out hydrogenation.Therefore this hydrogenation catalyst tool high activity, a spot of hydrogenation catalyst can reach effective hydrogenation effect, and must the deliming step, can carry out under the condition of gentleness again.
Deliver a kind of hydrogenation catalyst composition in the United States Patent (USP) 5270274, it comprises two (cyclopentadienyl) titanium (+4) compound, comprises the polar compound of carbon back and epoxy group(ing), reaches organolithium compound, the preferential unsaturated double-bond of hydrogenated conjugated diene polymer, the polymkeric substance after the hydrogenation has outstanding rerum natura and weathering resistance.
Deliver in the United States Patent (USP) 5244980 and will have active conjugated diolefin polymer, after the hydrogen termination, add organic alkali metal (particularly organolithium metal), and add Typee (Tebbe) catalyzer.It is said good hydrogenation effect.
The catalyst combination that relates in the United States Patent (USP) 5886108; To have active conjugated diolefin polymer, under the condition that adds hydroxyl, carbonyl or ester group, at least a two (cyclopentadienyl) titanium (+4) compound and trimethyl aluminium react compound Typee (Tebbe) catalyzer of formation for a long time, it is said to participate in hydrogenation, have good hydrogenation efficiency with this compound.
The catalyst combination of delivering in the United States Patent (USP) 5985995, has active conjugated diolefin polymer, under the condition that adds alkyl halide silicon or alkyl tin halide, at least there are two (cyclopentadienyl) titanium compounds of benzyloxy, it is said under this catalyst combination, have quite good hydrogenation efficiency.
Deliver the selective hydrogenation of conjugated diolefin polymer unsaturated double-bond in the United States Patent (USP) 5948869, its catalyst combination is at least two (cyclopentadienyl) titanium (+a 4) compound, be at least the alkyl thing of zinc or magnesium, reaching the some solvents with ester group and aromatic base of adding is promotor, it is said that this catalyst combination is quite helpful for promoting hydrogenation efficiency.
The catalyst combination of European patent application 0434469A2 is under the existence about the polar compound that is contained in alkali-metal alkoxide and ether, ketone and other type, the composition of a kind of bicyclic pentadiene titanium compound and aluminium or magnesium and alkali-metal a kind of organometallic compound, this catalyst system has the ability of hydrogenated conjugated diene polymer and multipolymer thereof.
Narration in European patent application 0544304A number is used to comprise following catalyst composition: (a) two (cyclopentadienyl) transistion metal compound; (b) at least a polar compound, it is the compound that contains the compound of carbonyl or contain epoxy group(ing), for example ester of monoprotic acid or diprotic acid, lactone compound, lactam compound or epoxy compounds; (c) organolithium compound; And (d) reductive organometallic compound, for example aluminum compound, zn cpds and magnesium compound, object lesson such as triethyl aluminum.This catalyst combination has suitable help for the lifting of hydrogenation efficiency.
Deliver the selective hydrogenation of conjugated diolefin polymer unsaturated double-bond in the United States Patent (USP) 6313230, its catalyst combination is at least two (cyclopentadienyl) titanium (+a 4) compound, and comprise and have hydrogenous silicon compound, tool is known this catalyst combination has suitable help for promoting hydrogenation efficiency.
As mentioned above, though existing many kinds of catalyst compositions can be used for hydrogenated conjugated diene polymer, yet therefore the required consumption higher (needing higher catalyst concn) of traditional catalyst composition is difficult for removing fully from the reaction product of gained.
Therefore, develop catalyst composition and come hydrogenated conjugated diene polymer,, become a target that urgency is to be studied to avoid complicated and expensive purification step with high hydrogenation efficiency and low usage quantity.
Summary of the invention
The objective of the invention is: a kind of method of hydrogenated conjugated diene polymer is provided, only needs to use a spot of hydrogenation catalyst composition, hydrogenated conjugated diene polymer successfully, and demonstrate suitable activity.Because employed catalyst concn is very low, therefore do not need from hydropolymer, to remove catalyzer, promoted economic benefit greatly.And hydrogenation of the present invention is very fast, has good reproducibility as a result under temperature and the pressure widely.
For reaching above-mentioned purpose, the invention provides a kind of stable and catalyst composition of being easy to store and utilize the method for the hydrogenated conjugated diene polymer that it carries out.
The present invention relates to a kind of method of hydrogenated conjugated diene polymer, and this conjugated diolefin polymer is the homopolymer or the multipolymer of conjugated diolefine, this method comprises that this conjugated diolefin polymer that will be dissolved in the passivity organic solvent reacts with hydrogen in the presence of a hydrogenation catalyst composition, with the unsaturated double-bond of conjugated diene unit in this conjugated diolefin polymer of selective hydration, and this hydrogenation is between 0 ℃ to 200 ℃ of the temperature of reaction, hydrogen pressure is 0.1kg/cm 2To 100kg/cm 2Scope in carry out, wherein, this hydrogenation catalyst composition comprises following hydrogenation catalyst:
(a) titanium compound shown in general formula (I):
Figure C20041009673600151
General formula (I)
R wherein 1, R 2Be identical or different substituting group, and be hydrogen, halogen atom, C 1～C 8Alkyl and alkoxyl group, C 6～C 12Cycloalkyl, phenyl, phenoxy group, C 7～C 10Alkoxy aryl and aralkyl, carboxyl ,-CH 2P (phenyl) 2,-CH 2Si (C 1～C 5Alkyl) 3Or-P (phenyl) 2, Cp *Represent cyclopentadienyl, indenyl, fluorenyl or derivatives thereof;
(b) compound shown in general formula (II) or general formula (III):
Figure C20041009673600161
General formula (II) general formula (III)
L wherein 1Be IV A family element, L 2Be III A family element, R 3Be C 1～C 12Alkyl or C 1～C 12Cycloalkyl, X 1, X 2, X 3Be identical or different substituting group, and be C 1～C 12Alkyl, C 1～C 12Alkoxyl group, C 1～C 12Cycloalkyloxy, phenyl or phenoxy group; And
(c) trialkyl aluminium compound shown in general formula (IV)
Figure C20041009673600162
General formula (IV)
R wherein 4, R 5, R 6Can be identical or different substituting group, and be C 1～C 12Alkyl or C 6～C 12Aromatic base,
Wherein, the mol ratio of this hydrogenation catalyst (b) and hydrogenation catalyst (a) is 0.1 to 50, and the mol ratio of hydrogenation catalyst (c) and hydrogenation catalyst (a) is 0.1 to 50, and with respect to these conjugated diolefin polymers of 100 grams, the usage quantity of this hydrogenation catalyst (a) is 0.0001 to 50mmol.
Method described in the method for hydrogenation catalyst composition of the present invention and hydrogenated conjugated diene polymer, wherein this hydrogenation catalyst (a) can be molybdenyl dichloride (cyclopentadienyl) titanium, molybdenyl dichloride (1-fluorenyl) titanium, molybdenyl dichloride (1-indenyl) titanium, two (1-fluorenyl) titaniums of dibrominated, two (1-indenyl) titaniums of dibrominated, two (cyclopentadienyl) titaniums of dimethyl, two (cyclopentadienyl) titaniums of diethyl, two (cyclopentadienyl) titaniums of dimethanol, two (indenyl) titaniums of dimethanol, two (fluorenyl) titaniums of dimethanol, two (cyclopentadienyl) titaniums of diethoxy, two (cyclopentadienyl) titaniums of dibutoxy, two (cyclopentadienyl) titaniums of two phenoxy groups, two (cyclopentadienyl) titaniums of benzyloxy, two (cyclopentadienyl) titaniums of diphenol oxygen base, two (cyclopentadienyl) titanium or derivatives thereofs of dicarboxyl.
Method described in the method for hydrogenation catalyst composition of the present invention and hydrogenated conjugated diene polymer, wherein this hydrogenation catalyst (a) is molybdenyl dichloride (cyclopentadienyl) titanium.
The method of stating in the method for hydrogenation catalyst composition of the present invention and hydrogenated conjugated diene polymer, wherein this hydrogenation catalyst (b) is the compound shown in the general formula (II), and X 1, X 2And X 3Among at least one is C 1～C 12Alkoxyl group or C 1～C 12Cycloalkyloxy.
Method described in the method for hydrogenation catalyst composition of the present invention and hydrogenated conjugated diene polymer, wherein this hydrogenation catalyst (b) is the compound shown in the general formula (II), and X 1, X 2And X 3Among the two is C 1～C 12Alkoxyl group or C 1～C 12Cycloalkyloxy, and another person is phenyl or alkyl.
Method described in the method for hydrogenation catalyst composition of the present invention and hydrogenated conjugated diene polymer, wherein this hydrogenation catalyst (b) is three (n-propane oxygen base) phenyl silicon, three (different third alkoxyl group) phenyl silicon, three (normal butane oxygen base) phenyl silicon, three (isobutyl alkoxyl group) phenyl silicon, three (Skellysolve A oxygen base) phenyl silicon, three (isoamyl alkoxyl group) phenyl silicon, three (n-propane oxygen base) methyl silicon, three (different third alkoxyl group) ethyl silicon, three (second alkoxyl group) ylmethyl tin, three (second alkoxyl group) methyl tin, three (n-propane oxygen base) ylmethyl tin, three (different third alkoxyl group) methyl tin, three (normal butane oxygen base) methyl tin, three (isobutyl alkoxyl group) methyl tin or its mixing.
Method described in the method for hydrogenation catalyst composition of the present invention and hydrogenated conjugated diene polymer, wherein this hydrogenation catalyst (b) is the compound shown in the general formula (II), and X 1, X 2And X 3Among one be C 1～C 12Alkoxyl group or C 1～C 12Cycloalkyloxy, and the two is a phenyl in addition.
Method described in the method for hydrogenation catalyst composition of the present invention and hydrogenated conjugated diene polymer wherein is two (n-propane oxygen base) two (phenyl) silicon, two (normal butane oxygen base) two (phenyl) silicon, two (isoamyl alkoxyl group) two (phenyl) silicon, two (n-propane oxygen base) two (phenyl) tin or its mixing in this hydrogenation catalyst (II).
Method described in the method for hydrogenation catalyst composition of the present invention and hydrogenated conjugated diene polymer, wherein this hydrogenation catalyst (b) is the compound shown in the general formula (II), and X 1, X 2And X 3Be identical or different C 1～C 12Alkoxyl group or C 1～C 12Cycloalkyloxy.
Method described in the method for hydrogenation catalyst composition of the present invention and hydrogenated conjugated diene polymer, wherein this hydrogenation catalyst (b) is four (C 1～C 12Alkoxyl group) silicon or four (C 1～C 12Alkoxyl group) tin.
Method described in the method for hydrogenation catalyst composition of the present invention and hydrogenated conjugated diene polymer, wherein this hydrogenation catalyst (b) is four (hexane oxygen base) silicon, four (n-propane oxygen base) silicon, four (different third alkoxyl group) silicon, four (normal butane oxygen base) silicon, four (Zhong Ding alkoxyl group) silicon, four (isobutyl alkoxyl group) silicon, four (Skellysolve A oxygen base) silicon, four (isoamyl alkoxyl group) silicon, four (1-methylbutane oxygen base) silicon, four (2-methylbutane oxygen base) silicon, four (1,2-dimethyl propylene alcoxyl base) silicon, four (neopentane oxygen base) silicon, four (normal hexane oxygen base) silicon, four (dissident's alkoxyl group) silicon, four (1,1-dimethyl butyrate alcoxyl base) silicon, four (2,2-dimethyl butyrate alcoxyl base) silicon, four (3,3-dimethyl butyrate alcoxyl base) silicon, four (n-undecane oxygen base) silicon, four (n-dodecane oxygen base) silicon, four (hexane oxygen base) tin, four (n-propane oxygen base) tin, four (different third alkoxyl group) tin, four (normal butane oxygen base) tin, four (Zhong Ding alkoxyl group) tin, four (isobutyl alkoxyl group) tin, four (Skellysolve A oxygen base) tin or its combination.
Method described in the method for hydrogenation catalyst composition of the present invention and hydrogenated conjugated diene polymer is the compound shown in the general formula (III) at this hydrogenation catalyst (b) wherein, and X 1And X 2At least one is C 1～C 12Alkoxyl group or C 1～C 12Cycloalkyloxy.
Method described in the method for hydrogenation catalyst composition of the present invention and hydrogenated conjugated diene polymer, wherein this hydrogenation catalyst (b) is the compound shown in the general formula (III), and X 1And X 2Be identical or different C 1～C 12Alkoxyl group or C 1～C 12Cycloalkyloxy.
Method described in the method for hydrogenation catalyst composition of the present invention and hydrogenated conjugated diene polymer, wherein this hydrogenation catalyst (b) is three (C 1～C 12Alkoxyl group) aluminium or three (C 1～C 12Alkoxyl group) gallium.
Method described in the method for hydrogenation catalyst composition of the present invention and hydrogenated conjugated diene polymer, wherein this hydrogenation catalyst (b) is three (hexane oxygen base) aluminium, three (n-propane oxygen base) aluminium, three (different third alkoxyl group) aluminium, three (normal butane oxygen base) aluminium, three (Zhong Ding alkoxyl group) aluminium, three (isobutyl alkoxyl group) aluminium, three (hexane oxygen base) gallium, three (n-propane oxygen base) gallium, three (different third alkoxyl group) gallium, three (normal butane oxygen base) gallium, three (Zhong Ding alkoxyl group) gallium or its combinations.
Method described in the method for hydrogenation catalyst composition of the present invention and hydrogenated conjugated diene polymer, wherein this hydrogenation catalyst (c) is trimethyl aluminium, triethyl aluminum, tri-n-n-propyl aluminum, triisopropylaluminiuand, tri-butyl aluminum, three (sec-butyl) aluminium, three (isobutyl-) aluminium, three (n-pentyl) aluminium, three (isopentyl) aluminium, three (n-hexyl) aluminium, three (isohexyl) aluminium, three (1-methyl amyl) aluminium, three (2,5-dimethyl octyl group) aluminium, three (2,6-dimethyl octyl group) aluminium, triphenyl aluminum or its combination.
Method described in the method for hydrogenation catalyst composition of the present invention and hydrogenated conjugated diene polymer, wherein this hydrogenation catalyst (c) is a triisobutyl aluminium.
Method described in the method for hydrogenation catalyst composition of the present invention and hydrogenated conjugated diene polymer comprises, to be dissolved in the passivity organic solvent, this conjugated diolefin polymer is reacted, with the unsaturated double-bond of conjugated diene unit in the selective hydrogenation of conjugated diolefine polymer in the presence of the hydrogenation catalyst composition that the present invention relates to hydrogen.
Method described in the method for hydrogenation catalyst composition of the present invention and hydrogenated conjugated diene polymer, wherein with respect to this conjugated diolefin polymer of 100 grams, the usage quantity of hydrogenation catalyst (a) is between 0.005 to 0.2mmol.
Method described in the method for hydrogenation catalyst composition of the present invention and hydrogenated conjugated diene polymer, wherein the mol ratio of this hydrogenation catalyst (b) and hydrogenation catalyst (a) is 2 to 15.
Method described in the method for hydrogenation catalyst composition of the present invention and hydrogenated conjugated diene polymer, wherein the mol ratio of this hydrogenation catalyst (c) and hydrogenation catalyst (a) is 2 to 15.
Method described in the method for hydrogenation catalyst composition of the present invention and hydrogenated conjugated diene polymer, wherein the number molecular-weight average of this conjugated diolefin polymer is between 1000 to 1000000.
Method described in the method for hydrogenation catalyst composition of the present invention and hydrogenated conjugated diene polymer, wherein this conjugated diolefin polymer is a conjugated diene/vinyl aromatic hydrocarbons multipolymer.
Method described in the method for hydrogenation catalyst composition of the present invention and hydrogenated conjugated diene polymer, wherein this hydrogenation be between 40 ℃ to 140 ℃ of temperature of reaction, hydrogen pressure is 1 to 50kg/cm 2Carry out in the scope.
Method in the method for hydrogenation catalyst composition of the present invention and hydrogenated conjugated diene polymer, wherein the hydrogenation ratio of the unsaturated double bond of this conjugated diene unit is for more than at least 50%.
Method described in the method for hydrogenation catalyst composition of the present invention and hydrogenated conjugated diene polymer, wherein the hydrogenation ratio of the unsaturated double bond of this conjugated diene unit is for more than at least 90%.
Method described in the method for hydrogenation catalyst composition of the present invention and hydrogenated conjugated diene polymer, wherein the hydrogenation ratio of the two keys of the unitary phenyl ring of this vinylaromatic hydrocarbon is lower than 10%.
Method described in the method for hydrogenation catalyst composition of the present invention and hydrogenated conjugated diene polymer, wherein the hydrogenation ratio of the two keys of the unitary phenyl ring of this vinylaromatic hydrocarbon is lower than 3%.
According to a preferred embodiment of the present invention, the method for this hydrogenated conjugated diene polymer, employed conjugated diolefin polymer is the homopolymer or the multipolymer of conjugated diolefine, and this hydrogenation is between 0 ℃ to 200 ℃ of the temperature of reaction, hydrogen pressure is 0.1kg/cm 2To 100kg/cm 2Scope in carry out.In addition, with respect to these conjugated diolefin polymers of 100 grams, the usage quantity of hydrogenation catalyst (a) is 0.0001 to 50mmol.
Hydrogenation catalyst composition described in the method for hydrogenation catalyst composition of the present invention and hydrogenated conjugated diene polymer, comprising following hydrogenation catalyst:
(a) titanium compound shown in general formula (I):
Figure C20041009673600211
General formula (I)
R wherein 1, R 2Be identical or different substituting group, and be hydrogen, halogen atom, C 1～C 8Alkyl and alkoxyl group, C 6～C 12Cycloalkyl, phenyl, phenoxy group, C 7～C 10Alkoxy aryl and aralkyl, carboxyl ,-CH 2P (phenyl) 2,-CH 2Si (C 1～C 5Alkyl) 3Or-P (phenyl) 2,
Cp *Represent cyclopentadienyl, indenyl, fluorenyl or derivatives thereof;
(b) compound shown in general formula (II) or general formula (III):
Figure C20041009673600212
General formula (II) general formula (III)
L wherein 1Be IV A family element, L 2Be III A family element, R 3Be C 1～C 12Alkyl or C 1～C 12Cycloalkyl, X 1, X 2, X 3Be identical or different substituting group, and be C 1～C 12Alkyl, C 1～C 12Alkoxyl group, C 1～C 12Cycloalkyloxy, phenyl or phenoxy group; And
(c) trialkyl aluminium compound shown in general formula (IV)
Figure C20041009673600221
General formula (IV)
R wherein 4, R 5, R 6Can be identical or different substituting group, and be C 1～C 12Alkyl or C 6～C 12Aromatic base, wherein the mol ratio of this hydrogenation catalyst (b) and hydrogenation catalyst (a) is 0.1 to 50, and the mol ratio of hydrogenation catalyst (c) and hydrogenation catalyst (a) is 0.1 to 50.
Hydrogenation catalyst composition described in the method for hydrogenation catalyst composition of the present invention and hydrogenated conjugated diene polymer, also comprise a conjugation diene polymer, wherein with respect to these conjugated diolefin polymers of 100 grams, the usage quantity of hydrogenation catalyst (a) is 0.0001 to 50mmol.
Hydrogenation catalyst composition described in the method for hydrogenation catalyst composition of the present invention and hydrogenated conjugated diene polymer, wherein this hydrogenation catalyst (a) is molybdenyl dichloride (cyclopentadienyl) titanium, molybdenyl dichloride (1-fluorenyl) titanium, molybdenyl dichloride (1-indenyl) titanium, two (1-fluorenyl) titaniums of dibrominated, two (1-indenyl) titaniums of dibrominated, two (cyclopentadienyl) titaniums of dimethyl, two (cyclopentadienyl) titaniums of diethyl, two (cyclopentadienyl) titaniums of dimethanol, two (indenyl) titaniums of dimethanol, two (fluorenyl) titaniums of dimethanol, two (cyclopentadienyl) titaniums of diethoxy, two (cyclopentadienyl) titaniums of dibutoxy, two (cyclopentadienyl) titaniums of two phenoxy groups, two (cyclopentadienyl) titaniums of benzyloxy, two (cyclopentadienyl) titaniums of diphenol oxygen base, two (cyclopentadienyl) titanium or derivatives thereofs of dicarboxyl.
Hydrogenation catalyst composition described in the method for hydrogenation catalyst composition of the present invention and hydrogenated conjugated diene polymer, wherein this hydrogenation catalyst (a) is molybdenyl dichloride (cyclopentadienyl) titanium.
Hydrogenation catalyst composition described in the method for hydrogenation catalyst composition of the present invention and hydrogenated conjugated diene polymer, wherein this hydrogenation catalyst (b) is the compound shown in the general formula (II), and X 1, X 2And X 3Among at least one is C 1～C 12Alkoxyl group or C 1～C 12Cycloalkyloxy.
Hydrogenation catalyst composition described in the method for hydrogenation catalyst composition of the present invention and hydrogenated conjugated diene polymer, wherein this hydrogenation catalyst (b) is the compound shown in the general formula (II), and X 1, X 2And X 3Among the two is C 1～C 12Alkoxyl group or C 1～C 12Cycloalkyloxy, and another person is phenyl or alkyl.
Hydrogenation catalyst composition described in the method for hydrogenation catalyst composition of the present invention and hydrogenated conjugated diene polymer, wherein this hydrogenation catalyst (b) is three (n-propane oxygen base) phenyl silicon, three (different third alkoxyl group) phenyl silicon, three (normal butane oxygen base) phenyl silicon, three (isobutyl alkoxyl group) phenyl silicon, three (Skellysolve A oxygen base) phenyl silicon, three (isoamyl alkoxyl group) phenyl silicon, three (n-propane oxygen base) methyl silicon, three (different third alkoxyl group) ethyl silicon, three (second alkoxyl group) ylmethyl tin, three (second alkoxyl group) methyl tin, three (n-propane oxygen base) ylmethyl tin, three (different third alkoxyl group) methyl tin, three (normal butane oxygen base) methyl tin, three (isobutyl alkoxyl group) methyl tin or its combinations.
Hydrogenation catalyst composition described in the method for hydrogenation catalyst composition of the present invention and hydrogenated conjugated diene polymer, wherein this hydrogenation catalyst (b) is the compound shown in the general formula (II), and X 1, X 2And X 3Among one be C 1～C 12Alkoxyl group or C 1～C 12Cycloalkyloxy, and the two is a phenyl in addition.
Hydrogenation catalyst composition described in the method for hydrogenation catalyst composition of the present invention and hydrogenated conjugated diene polymer, wherein this hydrogenation catalyst (b) is two (n-propane oxygen base) two (phenyl) silicon, two (normal butane oxygen base) two (phenyl) silicon, two (isoamyl alkoxyl group) two (phenyl) silicon, two (n-propane oxygen base) two (phenyl) tin or its combination.
Hydrogenation catalyst composition described in the method for hydrogenation catalyst composition of the present invention and hydrogenated conjugated diene polymer, wherein this hydrogenation catalyst (b) is the compound shown in the general formula (II), and X 1, X 2And X 3Be identical or different C 1～C 12Alkoxyl group or C 1～C 12Cycloalkyloxy.
Hydrogenation catalyst composition described in the method for hydrogenation catalyst composition of the present invention and hydrogenated conjugated diene polymer, wherein this hydrogenation catalyst (b) is four (C 1～C 12Alkoxyl group) silicon, four (C 1～C 12Alkoxyl group) tin or its combination.
Hydrogenation catalyst composition described in the method for hydrogenation catalyst composition of the present invention and hydrogenated conjugated diene polymer, wherein this hydrogenation catalyst (b) is four (hexane oxygen base) silicon, four (n-propane oxygen base) silicon, four (different third alkoxyl group) silicon, four (normal butane oxygen base) silicon, four (Zhong Ding alkoxyl group) silicon, four (isobutyl alkoxyl group) silicon, four (Skellysolve A oxygen base) silicon, four (isoamyl alkoxyl group) silicon, four (1-methylbutane oxygen base) silicon, four (2-methylbutane oxygen base) silicon, four (1,2-dimethyl propylene alcoxyl base) silicon, four (neopentane oxygen base) silicon, four (normal hexane oxygen base) silicon, four (dissident's alkoxyl group) silicon, four (1,1-dimethyl butyrate alcoxyl base) silicon, four (2,2-dimethyl butyrate alcoxyl base) silicon, four (3,3-dimethyl butyrate alcoxyl base) silicon, four (n-undecane oxygen base) silicon, four (n-dodecane oxygen base) silicon, four (hexane oxygen base) tin, four (n-propane oxygen base) tin, four (different third alkoxyl group) tin, four (normal butane oxygen base) tin, four (Zhong Ding alkoxyl group) tin, four (isobutyl alkoxyl group) tin, four (Skellysolve A oxygen base) tin or its combination.
Hydrogenation catalyst composition described in the method for hydrogenation catalyst composition of the present invention and hydrogenated conjugated diene polymer is the compound shown in the general formula (III) at this hydrogenation catalyst (b) wherein, and X 1And X 2At least one is C 1～C 12Alkoxyl group or C 1～C 12Cycloalkyloxy.
Hydrogenation catalyst composition described in the method for hydrogenation catalyst composition of the present invention and hydrogenated conjugated diene polymer, wherein this hydrogenation catalyst (b) is the compound shown in the general formula (III), and X 1And X 2Be identical or different C 1～C 12Alkoxyl group or C 1～C 12Cycloalkyloxy.
Hydrogenation catalyst composition described in the method for hydrogenation catalyst composition of the present invention and hydrogenated conjugated diene polymer, wherein this hydrogenation catalyst (b) is three (C 1～C 12Alkoxyl group) aluminium or three (C 1～C 12Alkoxyl group) gallium.
Hydrogenation catalyst composition described in the method for hydrogenation catalyst composition of the present invention and hydrogenated conjugated diene polymer, wherein this hydrogenation catalyst (b) is three (hexane oxygen base) aluminium, three (n-propane oxygen base) aluminium, three (different third alkoxyl group) aluminium, three (normal butane oxygen base) aluminium, three (Zhong Ding alkoxyl group) aluminium, three (isobutyl alkoxyl group) aluminium, three (hexane oxygen base) gallium, three (n-propane oxygen base) gallium, three (different third alkoxyl group) gallium, three (normal butane oxygen base) gallium, three (Zhong Ding alkoxyl group) gallium or its combinations.
Hydrogenation catalyst composition described in the method for hydrogenation catalyst composition of the present invention and hydrogenated conjugated diene polymer is a kind of stable catalyst composition that is easy to store.The hydrogenation catalyst (b) of its composition (b) shown in general formula (II) or general formula (III) particularly, the composition that can cooperate other catalyzer, to promote whole hydrogenation efficiency, stablize other activity of such catalysts, therefore when catalyst composition of the present invention adds in the conjugated diolefin polymer, can store a segment length time, activity of such catalysts still has satisfactory stability and circulation ratio, and is quite economical.
Hydrogenation catalyst composition described in the method for hydrogenation catalyst composition of the present invention and hydrogenated conjugated diene polymer, wherein this hydrogenation catalyst (c) is trimethyl aluminium, triethyl aluminum, tri-n-n-propyl aluminum, triisopropylaluminiuand, tri-butyl aluminum, three (sec-butyl) aluminium, three (isobutyl-) aluminium, three (n-pentyl) aluminium, three (isopentyl) aluminium, three (n-hexyl) aluminium, three (isohexyl) aluminium, three (1-methyl amyl) aluminium, three (2,5-dimethyl octyl group) aluminium, three (2,6-dimethyl octyl group) aluminium or triphenyl aluminum.
Hydrogenation catalyst composition described in the method for hydrogenation catalyst composition of the present invention and hydrogenated conjugated diene polymer, wherein this hydrogenation catalyst (c) is a triisobutyl aluminium.
According to a preferred embodiment of the present invention, the mol ratio of this hydrogenation catalyst (b) and hydrogenation catalyst (a) is 0.1 to 50, and the mol ratio of hydrogenation catalyst (c) and hydrogenation catalyst (a) is 0.1 to 50.
Hydrogenation catalyst composition described in the method for hydrogenation catalyst composition of the present invention and hydrogenated conjugated diene polymer, wherein the mol ratio of this hydrogenation catalyst (b) and hydrogenation catalyst (a) is 2 to 15.
Hydrogenation catalyst composition described in the method for hydrogenation catalyst composition of the present invention and hydrogenated conjugated diene polymer, wherein the mol ratio of this hydrogenation catalyst (c) and hydrogenation catalyst (a) is 2 to 15.
According to the present invention, only need the hydrogenation catalyst composition of minute quantity, successfully hydrogenated conjugated diene polymer can be arranged, quite gratifying hydrogenation effect is arranged.And most catalyzer just separates or decomposes with polymkeric substance in the sepn process of polymkeric substance, does not need the specific step of other cleaning or removal catalyst system.
One big characteristic of catalyst composition of the present invention is hydrogenation catalyst (b), cooperates the existence of other catalyzer can reach the effect of stablizing other catalyzer and promoting other catalyst activity.Another characteristic is that catalyst composition of the present invention is in still having hydrogenation activity highly in the temperature system widely.In addition, catalyst composition of the present invention can be high temperature resistant, lose activity of such catalysts because of too high hydrogenation heat, therefore quite is adapted at operating under the operational condition of continous way production.
Description of drawings
Fig. 1 shows the infrared spectrum of SBS polymkeric substance before and after hydrogenation of the embodiment of the invention 2.
Fig. 2 shows the infrared spectrum of SBS polymkeric substance before and after hydrogenation of comparing embodiment 1.
Embodiment
For structure of the present invention, working method and feature can be become apparent, preferred embodiment cited below particularly, and cooperate appended graphic, be described in detail below: the hydrogenation catalyst composition that the present invention relates to, wherein comprise hydrogenation catalyst (a)～(c), wherein hydrogenation catalyst (a) comprises the titanium compound shown in the general formula (I):
Figure C20041009673600271
General formula (I)
R wherein 1, R 2Can be identical or different substituting group, can be selected from hydrogen, halogen atom, C 1～C 8Alkyl and alkoxyl group, C 6～C 12Cycloalkyl, phenyl, phenoxy group (phenoxy), C 7～C 10Alkoxy aryl (arylalkoxy) and aralkyl (arylalkyl), carboxyl (carboxy) ,-CH 2P (phenyl) 2,-CH 2Si (C 1～C 5Alkyl) 3Or-P (phenyl) 2, Cp *Represent cyclopentadienyl, indenyl, fluorenyl or above-mentioned derivative.
According to a preferred embodiment of the present invention, Cp *Can be C 5R 5, R wherein 5Can be identical or different substituting groups, and R 5The optional hydrogen of doing for oneself, halogen atom, alkyl, alkyl aryl radical or aryl radical.
Be applicable to that hydrogenation catalyst of the present invention (a) can be molybdenyl dichloride (cyclopentadienyl) titanium [bis (cyclopentadienyl) titanium dichloride], molybdenyl dichloride (1-fluorenyl) titanium [bis (1-fluorenyl) titanium dichloride], molybdenyl dichloride (1-indenyl) titanium [bis (1-indenyl) titaniumdichloride], two (1-fluorenyl) titaniums of dibrominated, two (1-indenyl) titaniums of dibrominated, two (cyclopentadienyl) titaniums of dimethyl, two (cyclopentadienyl) titaniums of diethyl, two (cyclopentadienyl) titaniums [bis (cyclopenta dienyl) titanium dimethoxy] of dimethanol, two (indenyl) titaniums of dimethanol, two (fluorenyl) titaniums of dimethanol, two (cyclopentadienyl) titaniums of diethoxy, two (cyclopentadienyl) titaniums of dibutoxy, two (cyclopentadienyl) titaniums [bis (cyclopentadienyl) titanium diphenoxy] of two phenoxy groups, two (cyclopentadienyl) titaniums of benzyloxy, two (cyclopentadienyl) titaniums of diphenol oxygen base, two (cyclopentadienyl) titanium [bis (cyclopentadienyl) titanium dicarboxy] or derivatives thereofs of dicarboxyl.
The so-called derived thing is meant that on the ring of indenyl, fluorenyl or cyclopentadienyl one or several hydrogen are replaced by a substituting group herein, this substituting group can example be methyl, methoxyl group, to butyl phenyl, pentafluorophenyl group, trifluorophenyl, difluorophenyl or 3,5-(tertiary butyl)-groups such as 4-p-methoxy-phenyl.The example of preferable hydrogenation catalyst (a) is molybdenyl dichloride (cyclopentadienyl) titanium.
Hydrogenation catalyst of the present invention (b) is for comprising the compound shown in general formula (II) or general formula (III):
Figure C20041009673600281
General formula (II) general formula (III)
Wherein
L 1Be IV A family element,
L 2Be III A family element,
R 3Be C 1～C 12Alkyl or C 1～C 12Cycloalkyl,
X 1, X 2, X 3Be identical or different substituting group, and be C 1～C 12Alkyl, C 1～C 12Alkoxyl group, C 1～C 12Cycloalkyloxy, phenyl or phenoxy group.
According to a preferred embodiment of the present invention, this hydrogenation catalyst (b) is the compound shown in the general formula (II), and X 1, X 2And X 3Among at least one is C 1～C 12Alkoxyl group or C 1～C 12Cycloalkyloxy.For example, X 1And X 2Be C 1～C 12Alkoxyl group or C 1～C 12Cycloalkyloxy, and X 3Be phenyl or alkyl.This type of object lesson comprises: three (second alkoxyl group) ylmethyl silicon, three (second alkoxyl group) methyl silicon, three (n-propane oxygen base) ylmethyl silicon, three (different third alkoxyl group) methyl silicon, three (normal butane oxygen base) methyl silicon, three (isobutyl alkoxyl group) methyl silicon, three (Skellysolve A oxygen base) ethyl silicon, three (isoamyl alkoxyl group) ethyl silicon, three (n-propane oxygen base) phenyl silicon, three (different third alkoxyl group) phenyl silicon, three (normal butane oxygen base) phenyl silicon, three (isobutyl alkoxyl group) phenyl silicon, three (Skellysolve A oxygen base) phenyl silicon, three (isoamyl alkoxyl group) phenyl silicon, three (second alkoxyl group) ylmethyl tin, three (second alkoxyl group) methyl tin, three (n-propane oxygen base) ylmethyl tin, three (different third alkoxyl group) methyl tin, three (normal butane oxygen base) methyl tin, or three (isobutyl alkoxyl group) methyl tin.
In addition, according to another preferred embodiment of the present invention, this hydrogenation catalyst (b) is the compound shown in the general formula (II), and X 1, X 2And X 3Among one be C 1～C 12Alkoxyl group or C 1～C 12Cycloalkyloxy, and the two is a phenyl in addition.This type of object lesson comprises two (n-propane oxygen base) two (phenyl) silicon, two (normal butane oxygen base) two (phenyl) silicon, two (isoamyl alkoxyl groups), two (phenyl) silicon or two (n-propane oxygen base) two (phenyl) tin.
Moreover this hydrogenation catalyst (b) also can be the compound shown in the general formula (II), and X 1, X 2And X 3Be identical or different C 1～C 12Alkoxyl group or C 1～C 12Cycloalkyloxy for example is four (C 1～C 12Alkoxyl group) silicon or four (C 1～C 12Alkoxyl group) tin, this type of object lesson comprises four (hexane oxygen base) silicon, four (n-propane oxygen base) silicon, four (different third alkoxyl group) silicon, four (normal butane oxygen base) silicon, four (Zhong Ding alkoxyl group) silicon, four (isobutyl alkoxyl group) silicon, four (Skellysolve A oxygen base) silicon, four (isoamyl alkoxyl group) silicon, four (1-methylbutane oxygen base) silicon, four (2-methylbutane oxygen base) silicon, four (1,2-dimethyl propylene alcoxyl base) silicon, four (neopentane oxygen base) silicon, four (normal hexane oxygen base) silicon, four (dissident's alkoxyl group) silicon, four (1,1-dimethyl butyrate alcoxyl base) silicon, four (2,2-dimethyl butyrate alcoxyl base) silicon, four (3,3-dimethyl butyrate alcoxyl base) silicon, four (n-undecane oxygen base) silicon, four (n-dodecane oxygen base) silicon, four (hexane oxygen base) tin, four (n-propane oxygen base) tin, four (different third alkoxyl group) tin, four (normal butane oxygen base) tin, four (Zhong Ding alkoxyl group) tin, four (isobutyl alkoxyl group) tin, or four (Skellysolve A oxygen base) tin.
According to another preferred embodiment of the present invention, this hydrogenation catalyst (b) can be the compound shown in the general formula (III), and X 1And X 2At least one is C 1～C 12Alkoxyl group or C 1～C 12Cycloalkyloxy.In addition, this hydrogenation catalyst (b) also can be the compound shown in the general formula (III), and X 1And X 2Be identical or different C 1～C 12Alkoxyl group or C 1～C 12Cycloalkyloxy for example is three (C 1～C 12Alkoxyl group) aluminium or three (C 1～C 12Alkoxyl group) gallium, this type of object lesson comprise three (hexane oxygen base) aluminium, three (n-propane oxygen base) aluminium, three (different third alkoxyl group) aluminium, three (normal butane oxygen base) aluminium, three (Zhong Ding alkoxyl group) aluminium, three (isobutyl alkoxyl group) aluminium, three (hexane oxygen base) gallium, three (n-propane oxygen base) gallium, three (different third alkoxyl group) gallium, three (normal butane oxygen base) gallium or three (Zhong Ding alkoxyl group) galliums.
When hydrogenation catalyst (b) was compound shown in the general formula (II), except above-mentioned silicon compound, the object lesson of this hydrogenation catalyst (b) also comprised 1-methyl pentyloxy silicon, 2-methyl pentyloxy silicon, 3-methyl pentyloxy silicon, 1,2-dimethyl butoxy silicon, 1,3-dimethyl butoxy silicon, 1-ethyl butoxy silicon, 2-ethyl butoxy silicon, cyclohexyloxy silicon, positive heptan oxygen base silicon, different heptan oxygen base silicon, 4-methyl hexyloxy silicon, 3-methyl hexyloxy silicon, 2-methyl hexyloxy silicon, 1-methyl hexyloxy silicon, 1,1-dimethyl pentyloxy silicon, 2,2-dimethyl pentyloxy silicon, 3,3-dimethyl pentyloxy silicon, 4,4-dimethyl pentyloxy silicon, 1,2-dimethyl pentyloxy silicon, 1,3-dimethyl pentyloxy silicon, 1,4-dimethyl pentyloxy silicon, 1-ethyl pentyloxy silicon, 1-propyl group pentyloxy silicon, 2-ethyl pentyloxy silicon, 3-ethyl pentyloxy silicon, 1,1-ethyl-methyl butoxy silicon, 1,1-diethyl propoxy-silicon, 2,3-dimethyl pentyloxy silicon, 2,4-dimethyl pentyloxy silicon, 3,4-dimethyl pentyloxy silicon, 1-ethyl-3 methyl butoxy silicon, 4-methyl cyclohexane oxygen base silicon, 3-methyl butoxy silicon, 4-methyl epoxy group(ing) silicon, 3-methyl cyclohexane oxygen base silicon, ring oxygen base silicon in heptan, 1,1,2-trimethylammonium fourth propoxy-silicon, 1,1,3-trimethylammonium butoxy silicon, 2,2,1-trimethylammonium butoxy silicon, 2,2,3-trimethylammonium butoxy silicon, 3,3,1-trimethylammonium butoxy silicon, 3,3,2-trimethylammonium butoxy silicon, 1,1,2,2-tetramethyl-propoxy-silicon, n-octyloxy silicon, 1-methyl oxygen in heptan base silicon, 2-methyl oxygen in heptan base silicon, 3-methyl oxygen in heptan base silicon, 4-methyl oxygen in heptan base silicon, 5-methyl oxygen in heptan base silicon, different octyloxy silicon, 1-ethyl hexyl oxy silicon, 2-ethyl hexyl oxy silicon, 3-ethyl hexyl oxy silicon, 4-ethyl hexyl oxy silicon, 1,1-dimethyl hexyloxy silicon, 2,2-dimethyl hexyloxy silicon, 3,3-dimethyl hexyloxy silicon, 4,4-dimethyl hexyloxy silicon, 5,5-dimethyl hexyloxy silicon, 1,2-dimethyl hexyloxy silicon, 1,3-dimethyl hexyloxy silicon, 1,4-dimethyl hexyloxy silicon, 1,5-dimethyl hexyloxy silicon, 2,3-dimethyl hexyloxy silicon, 2,4-dimethyl hexyloxy silicon, 3,4-dimethyl hexyloxy silicon, 2,5-dimethyl hexyloxy silicon, 3,5-dimethyl hexyloxy silicon, 1,1-methylethyl pentyloxy silicon, 1-ethyl-2-methyl pentyloxy silicon, 1-ethyl-3-methyl pentyloxy silicon, 1-ethyl-4-methyl pentyloxy silicon, 2-ethyl-1-methyl pentyloxy silicon, 2-ethyl-1-methyl pentyloxy silicon, 2,2-ethyl-methyl pentyloxy silicon, 3,3-ethyl-methyl pentyloxy silicon, 2-ethyl-3-methyl pentyloxy silicon, 2-ethyl-4-methyl pentyloxy silicon, 3-ethyl-4-methyl pentyloxy silicon, 3-ethyl-2-methyl pentyloxy silicon, 1,1-diethyl butoxy silicon, 2,2-diethyl butoxy silicon, 1,2-diethyl butyl oxygen base silicon, 1,1-methyl-propyl butoxy silicon, 2-methyl isophthalic acid-propyl group butoxy silicon, 3-methyl isophthalic acid-propyl group butoxy silicon, 4-ethyl cyclohexyloxy silicon, 3-ethyl cyclohexyloxy silicon, 3,4-dimethyl cyclohexyloxy silicon, 1,1,2-trimethylpentyloxy silicon, 1,1,3-trimethylpentyloxy silicon, 1,1,4-trimethylpentyloxy silicon, 2,2,1-trimethylpentyloxy silicon, 2,2,3-trimethylpentyloxy silicon, 2,2,4-trimethylpentyloxy silicon, 3,3,1-trimethylpentyloxy silicon, 3,3,2-trimethylpentyloxy silicon, 3,3,4-trimethylpentyloxy silicon, 1,2,3-trimethylpentyloxy silicon, 1,2,4-trimethylpentyloxy silicon, 1,3,4-trimethylpentyloxy silicon, 1,2,3-trimethylpentyloxy silicon, 1,2,4-trimethylpentyloxy silicon, 1,3,4-trimethylpentyloxy silicon, 1,1,2,2-tetramethyl-butoxy silicon, 1,1,3,3-tetramethyl-butoxy silicon, 1,1,2,3-tetramethyl-butoxy silicon, 2,2,1,3-tetramethyl-butoxy silicon, 1-ethyl-1,2-dimethyl butoxy silicon, 1-ethyl-2,3-diformazan butoxy silicon, positive ninth of the ten Heavenly Stems oxygen base silicon, different ninth of the ten Heavenly Stems oxygen base silicon, 1-first octyloxy silicon, 2 methyl octyloxy silicon, 3 methyl octyloxy silicon, 4-methyl octyloxy silicon, 5-methyl octyloxy silicon, 6-methyl octyloxy silicon, 1-ethyl oxygen in heptan base silicon, 2-ethyl oxygen in heptan base silicon, 3-ethyl oxygen in heptan base silicon, 4-ethyl oxygen in heptan base silicon, 5-ethyl oxygen in heptan base silicon, 1,1-dimethyl-g oxygen base silicon, 2,2-dimethyl-g oxygen base silicon, 3,3-dimethyl-g oxygen base silicon, 4,4-dimethyl-g oxygen base silicon, 5,5-dimethyl-g oxygen base silicon, 6,6-dimethyl hexyl oxygen base silicon, 1,2-dimethyl-g oxygen base silicon, 1,3-dimethyl-g oxygen base silicon, 1,4-dimethyl-g oxygen base silicon, 1,5-dimethyl-g oxygen base silicon, 1,6-dimethyl-g oxygen base silicon, 2,3-dimethyl-g oxygen base silicon, 2,4-dimethyl-g oxygen base silicon, 2,5-dimethyl-g oxygen base silicon, 2,6-dimethyl-g oxygen base silicon, 3,4-dimethyl-g oxygen base silicon, 3,5-dimethyl-g oxygen base silicon, 3,6-dimethyl-g oxygen base silicon, 4,5-dimethyl-g oxygen base silicon, 4,6-dimethyl-g oxygen base silicon, 5,6-dimethyl-g oxygen base silicon, 1,1,2-trimethylammonium hexyloxy silicon, 1,1,3-trimethylammonium hexyloxy silicon, 1,1,4-trimethylammonium hexyl oxygen base silicon, 1,1,5-trimethylammonium hexyloxy silicon, 2,2,1-trimethylammonium hexyloxy silicon, 2,2,3-trimethylammonium hexyloxy silicon, 2,2,4-trimethylammonium hexyloxy silicon, 2,2,5-trimethylammonium hexyloxy silicon, 3,3,1-trimethylammonium hexyloxy silicon, 4,4,1-trimethylammonium hexyloxy silicon, 4,4,2-trimethylammonium hexyloxy silicon, 4,4,3-trimethylammonium hexyloxy silicon, 4,4,5-trimethylammonium hexyloxy silicon, 2,3,4-trimethylammonium hexyloxy silicon, 3,4,5-trimethylammonium hexyloxy silicon, 1,3,4-trimethylammonium hexyloxy silicon, 1,4,5-trimethylammonium hexyloxy silicon, 2,4,5-trimethylammonium hexyloxy silicon, 1,2,5-trimethylammonium hexyloxy silicon, 1,2,4-trimethylammonium hexyloxy silicon, positive certain herbaceous plants with big flowers oxygen base silicon, different certain herbaceous plants with big flowers oxygen base silicon, 1-methyl oxygen in ninth of the ten Heavenly Stems base silicon, 2-methyl oxygen in ninth of the ten Heavenly Stems base silicon, 3-methyl oxygen in ninth of the ten Heavenly Stems base silicon, 4-methyl oxygen in ninth of the ten Heavenly Stems base silicon, 5-methyl oxygen in ninth of the ten Heavenly Stems base silicon, 6-methyl oxygen in ninth of the ten Heavenly Stems base silicon, 7-methyl oxygen in ninth of the ten Heavenly Stems base silicon, 1-ethyl octyloxy silicon, 2-ethyl first octyloxy silicon, 3-ethyl octyloxy silicon, 4 one ethyl octyloxy silicon, 5-ethyl octyloxy silicon, 6 one ethyl octyloxy silicon, 1,1-dimethyl octyloxy silicon, 2,2-dimethyl octyloxy silicon, 3,3-dimethyl octyloxy silicon, 4,4-dimethyl octyloxy silicon, 5,5-dimethyl octyloxy silicon, 6,6-dimethyl octyloxy silicon, 7,7-dimethyl octyloxy silicon, 1,2-dimethyl octyloxy silicon, 1,3-dimethyl octyloxy silicon, 1,4-dimethyl octyloxy silicon, 1,5-dimethyl octyloxy silicon, 1,6-dimethyl octyloxy silicon, 1,7-dimethyl octyloxy silicon, 2,3-dimethyl octyloxy silicon, 2,4-dimethyl octyloxy silicon, 2,5-dimethyl octyloxy silicon, 2,6-dimethyl octyloxy silicon, 2,7-dimethyl octyloxy silicon, 3,4-dimethyl octyloxy silicon, 3,5-dimethyl octyloxy silicon, 3,6-dimethyl octyloxy silicon, 3,7-dimethyl octyloxy silicon, 4,5-dimethyl octyloxy silicon, 4,6-dimethyl octyloxy silicon, 4,7-dimethyl octyloxy silicon, 5,6-dimethyl octyloxy silicon, 5,7-dimethyl octyloxy silicon, three just own oxygen methyl silicon, three dissident's oxygen ethyl silicon, three o-phenyl-isopropyl silicon, three positive butoxyphenyl silicon, three isobutyl oxygen phenyl silicon, three (1-methyl fourth) oxygen phenyl silicon, three positive penta oxygen methyl silicon, triisopentyl oxygen methyl silicon, three (1-methyl fourth) phenyl silicon, three (2-methyl fourth) oxygen phenyl silicon, three (1, the 2-dimethyl propylene) oxygen phenyl silicon, three new penta oxygen phenyl silicon, three just own oxygen phenyl silicon, three dissident's oxygen phenyl silicon, three (1, the 1-dimethyl butyrate) oxygen phenyl silicon, three (2, the 2-dimethyl butyrate) oxygen phenyl silicon, three (3, the 3-dimethyl butyrate) oxygen phenyl silicon, three (1-ethyl fourth) oxygen phenyl silicon, three (2-ethyl fourth) oxygen phenyl silicon, three hexamethylene oxygen phenyl silicon, three positive heptan oxygen phenyl silicon, three different heptan oxygen phenyl silicon, three (1, the 1-dimethyl-penten) oxygen phenyl silicon, three (2, the 2-dimethyl-penten) oxygen phenyl silicon, three (3, the 3-dimethyl-penten) oxygen phenyl silicon, three (4, the 4-dimethyl-penten) oxygen phenyl silicon, 1-methyl pentyloxy tin, 2-methyl pentyloxy tin, 3-methyl pentyloxy tin, 1,2-dimethyl butoxy tin, 1,3-dimethyl butoxy tin, 1-ethyl butoxy tin, 2-ethyl butoxy tin, cyclohexyloxy tin, positive heptan oxygen base tin, different heptan oxygen base tin, 4-methyl hexyloxy tin, 3-methyl hexyloxy tin, 2-methyl hexyloxy tin, 1-methyl hexyloxy tin, 1,1-dimethyl pentyloxy tin, 2,2-dimethyl pentyloxy tin or its combination.
When this hydrogenation catalyst (b) is compound shown in the general formula (III), the object lesson of this hydrogenation catalyst (b) comprising: positive aluminum ethoxide [Aluminum (III) n-ethoxide], positive propoxy aluminium [Aluminum (III) n-propoxide], n-pentyloxy aluminium, isopentyloxy aluminium, 1-methyl butoxy aluminium, 2-methyl butoxy aluminium, 1,2-dimethyl propoxy-aluminium, neopentyl oxygen aluminium, positive hexyloxy aluminium, different hexyloxy aluminium, 1-methyl pentyloxy aluminium, 2-methyl pentyloxy aluminium, 3-methyl pentyloxy aluminium, 1,1-dimethyl butoxy aluminium, 2,2-dimethyl butoxy aluminium, 3,3-dimethyl butoxy aluminium, 1,2-dimethyl butoxy aluminium, 1,3-dimethyl butoxy aluminium, 1-ethyl butoxy aluminium, 2-ethyl butoxy aluminium, cyclohexyloxy aluminium, aluminum isopropoxide, n-butoxy aluminium, aluminium-sec-butylate, isobutoxy aluminium, n-pentyloxy aluminium, isopentyloxy aluminium, 1-methyl butoxy aluminium, 2-methyl butoxy aluminium, 1,2-dimethyl propoxy-aluminium, neopentyl oxygen aluminium, positive hexyloxy aluminium, different hexyloxy aluminium, 1-methyl pentyloxy aluminium, 2-methyl pentyloxy aluminium, 3-methyl pentyloxy aluminium, 1,1-dimethyl butoxy aluminium, 2,2-dimethyl butoxy aluminium, 3,3-dimethyl butoxy aluminium, 1,2-dimethyl butoxy aluminium, 1,3-dimethyl butoxy aluminium, 1-ethyl butoxy aluminium, 2-ethyl butoxy aluminium, cyclohexyloxy aluminium, positive oxyethyl group gallium (Gallium (III) n-ethoxide), positive propoxy gallium (Gallium (III) n-propoxide), the n-pentyloxy gallium, the isopentyloxy gallium, 1-methyl butoxy gallium, 2-methyl butoxy gallium, 1,2-dimethyl propoxy-gallium, neopentyl oxygen gallium or its mixing.
Hydrogenation catalyst of the present invention (c) is for comprising the compound shown in general formula (IV):
Figure C20041009673600341
General formula (IV)
R wherein 4, R 5, R 6Can be identical or different substituting group, and be C 1～C 12Alkyl or C 6～C 12Aromatic base.
According to the hydrogenation catalyst composition that the present invention relates to, the object lesson of this hydrogenation catalyst (c) comprising: trimethyl aluminium, triethyl aluminum, tri-n-n-propyl aluminum, triisopropylaluminiuand, tri-butyl aluminum, three (sec-butyl) aluminium, three (isobutyl-) aluminium, three (n-pentyl) aluminium, three (isopentyl) aluminium, three (n-hexyl) aluminium, three (isohexyl) aluminium, three (1-methyl amyl) aluminium, three (2,5-dimethyl octyl group) aluminium, three (2,6-dimethyl octyl group) aluminium or triphenyl aluminum etc.Preferable triethyl aluminum, triisopropylaluminiuand, triisopropylaluminiuand, tri-butyl aluminum or three (isobutyl-) aluminium of being chosen as, better person is three (isobutyl-) aluminium.
Method for hydrogenation of the present invention is that the conjugated diolefin polymer that will be dissolved in the passivity organic solvent reacts with hydrogen in the presence of the hydrogenation catalyst composition that the present invention relates to, with the unsaturated double-bond of conjugated diene unit in the selective hydrogenation of conjugated diolefine polymer.The hydrogenation catalyst composition that the present invention relates to promptly comprises the hydrogenation catalyst (a) and (b), reaches (c).For example, gaseous hydrogen can be imported and desire in the hydrogenant conjugated diolefin polymer, then, hydrogen be contacted fully with polymkeric substance in the mode that stirs.Hydrogenation can be criticized the mode of formula or continous way and carry out.
Hydrogenation catalyst (a) and (b), the addition sequence that reaches (c) do not limit.For example, can earlier catalyzer (b) be added in the polymers soln, add catalyzer (a) and mixing solutions (c) again.In addition, also can earlier catalyzer (b) be added in the polymers soln, add the solution of catalyzer (a) and the solution of catalyzer (c) more respectively.And after all catalyzer all are incorporated in the polymkeric substance, be stored in the atmospheric environment of passivity, keep a segment length time, catalyzer still has suitable activity, and therefore catalyst composition of the present invention quite is suitable for the demand of industrial production.
According to the present invention, the passivity organic solvent that is used for dissolving hydrogenation catalyst and conjugated diolefin polymer can be the straight or branched hydrocarbon polymer, for example pentane, hexane, heptane, octane and other analogue; Or can be alicyclic hydrocarbon type, for example hexanaphthene, suberane and methyl suberane etc.The example that hexanaphthene is best suited for.The passivity organic solvent also can use arene, for example as benzene,toluene,xylene and ethylbenzene, but its only limit to the two keys of aromatic series can the person of being hydrogenated under employed hydrogenation conditions.
Preparation catalyzer (a) and (b), the environment that reaches (c) should carry out under passivity atmosphere and low water content condition, the passivity atmosphere means the passivity gas of helium, neon, nitrogen, these gases can not participate in hydrogenation, and air and oxygen or the moisture content of too high levels is arranged, meeting oxidation or decomposition hydrogenation catalyst cause catalyzer to lose activity.And if relate to the process that catalyzer must be pre-mixed, its temperature also only need get final product by normal temperature, and the blended time is not too long, and preferably deployed just the adding in the polymeric solution is in order to avoid produce side reaction.
According to the present invention, carry out the used conjugated diolefin polymer of hydrogenation and can make, anionic polymerization for example, cationic polymerization, radical polymerization, complex body polymerization, solution polymerization process, emulsion polymerization method according to the skill of previously known.During polymerization, preferably use organolithium compound as catalyst initiator, and obtain reactive polymer, it has lithium atom at molecule chain end, thereby can carry out polymerization again and molecular chain is grown up after adding monomer.The object lesson of organolithium compound comprises the n-propyl lithium, sec.-propyl lithium, tertiary butyl lithium, n-pentyl lithium, phenyl lithium, tolyl lithium etc.The hydrocarbon polymer example of two lithiums is as 1, the two lithium-normal butanes, 1 of 4-, the two lithium-pentanes, 1 of 5-, the two lithiums of 2--two diphenylphosphino ethanes, 1, the two lithiums-1,1,4 of 4-, 4-tetraphenyl butane, 1,3-or 1, two (1-lithium-3 methyl amyl) benzene of 4-.The consumption of organolithium compound is determined with the molecular weight that institute's desire obtains polymkeric substance, is generally in 0.05 to the 5wt% scope, and be benchmark with whole monomer consumptions.
The term of employed among the present invention " conjugated diolefin polymer ", looking like is the single polymers or the multipolymer of conjugated diolefine.The multipolymer of conjugated diolefine can be random row, block, the graft copolymer of two or more conjugate diene monomer, perhaps, can be at least a above conjugate diene monomer and at least a above formed random row of vinyl aromatic hydrocarbon monomer, block, graft copolymer.
Being applicable to that conjugate diene monomer of the present invention can be contains 4 conjugated diolefines to 12 carbon atoms.Object lesson comprises 1,3 divinyl, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl isophthalic acid, 3-pentadiene, 1,3-hexadiene, 4,5-diethyl-1,3-octadiene, 3-butyl-1,3-octadiene.
Conjugated diene/vinyl aromatic hydrocarbon copolymer of the present invention can obtain the thermoplastic elastomer of high value behind over hydrogenation.The object lesson that is applicable to vinyl aromatic hydrocarbon monomer of the present invention comprises vinylbenzene, spy-butylstyrene, δ-vinyl toluene, neighbour-vinyl toluene, p-methylstyrene, double-vinyl benzene, 1, the two phenyl ethene of 1-, vinyl naphthalene, N, the two methyl of N--right-ethylamine vinylbenzene, N, the two ethyls of N--right-ethylamine vinylbenzene.Preferable example is a vinylbenzene.The object lesson of conjugated diene/vinyl aromatic hydrocarbon copolymer is butadiene/styrene copolymers and isoprene/styrol copolymer.Preferably select the reason of this type of typical example to be that the multipolymer after the hydrogenation has industrial value.
In addition, can in the system of conjugated diolefin polymer, add a kind of tertiary amine compound or ether compound, to improve the vinyl structure of conjugated diolefine.Compounds suitable for use comprises general tertiary amine compound, tetrahydrofuran (THF) etc.
The dose ratio of hydrogenation catalyst among the present invention (a), conjugated diolefin polymer interpolation 0.0001 to 50mmol with respect to 100g is promptly enough, surpassing the 50mmol consumption carries out, its hydrogenant result can't be better, and do not meet economic benefit yet, and the dosage that adds is too high, and the program that makes the reaction back remove catalyzer is seemed quite complicated.The optimum amount of hydrogenation catalyst (a) is that the conjugated diolefin polymer of every 100g adds 0.002 to 1mmol, and good to 0.2mmol spy with 0.005.
The molar ratio of catalyzer among the present invention (b) and catalyzer (a) preferably falls in 0.1～50 the scope.If its molar ratio was less than 0.1 o'clock, hydrogenation catalyst can't effectively promote hydrogenation activity, causes the stagnation of latter end hydrogenation process and can not reach the ideal target.And if its molar ratio can cause the step that the removal catalyzer must be arranged greater than 50, and is easy to generate unnecessary secondary reaction, hinder the carrying out of hydrogenation on the contrary.The optimum molar ratio of catalyzer (b) and catalyzer (a) is between 2 to 15.
The molar ratio of catalyzer among the present invention (c) and catalyzer (a) preferably falls between 0.1 to 50.If molar ratio is lower than 0.1, the ability of deactivated catalyst (a) can't be arranged, it is suitable not good that its relative hydrogenation efficiency seems.Molar ratio is if surpass 50, the hydrogenation efficiency that can promote at first, but to the process in stage casing, owing to produce unnecessary secondary reaction thing, cause the rapid decline of hydrogenation efficiency on the contrary, and the action of removing catalyzer still must be arranged, cause the complexity that its follow-up program becomes and make us frustrating.The molar ratio of catalyzer (c) and catalyzer (a) the best is between 6 to 20, and is better between 6 to 10.
The temperature of reaction of hydrogenation of the present invention can be carried out in 0 ℃ to 200 ℃ temperature range.Temperature of reaction is if be lower than 0 ℃, and it is low and inefficent that speed of reaction can become, and must promote the consumption of catalyzer (a), and its practice does not also meet economic benefit.If the temperature that is higher than 200 ℃ is carried out, can cause the phenomenon of catalyst deactivation, thereby reduce catalyst activity, and total system is easy to generate side reaction, cause polymer to decompose or form gel, preferable hydrogenation temperature is between 40 ℃ to 140 ℃.
The hydrogen pressure of preferable hydrogenization is 1Kg/cm 2To 90Kg/cm 2Between.If hydrogenation pressure is less than 1Kg/cm 2The time, it is not obvious that speed of reaction can become, if hydrogen pressure surpasses 90Kg/cm 2The time, hydrogenation meeting temperature rises and stops hydrogenation fast.Best hydrogenation pressure with 2 to 35Kg/cm 2Be advisable.Under above-mentioned hydrogenation conditions, catalyst consumption can be successively decreased along with the increase of hydrogen pressure, and in order to reach the effect that reduces catalytic amount, it is good selecting higher hydrogenation pressure as far as possible.
According to the present invention, the hydrogenant time, suitable scope need be looked its ratio that adds catalyst combination between several seconds to 40 hour, the pressure of hydrogen, and conditions such as hydrogenant temperature adjust.
According to the present invention, can optionally adjust under consumption, hydrogen pressure and the hydrogenation temperature of catalyst composition, two keys of conjugated diolefin polymer are hydrogenated to degree arbitrarily.Come hydrogenating conjugate diene/aromatic vinyl hydrocarbon copolymer by catalyst composition of the present invention, the degree of hydrogenation of the two keys in the conjugated diolefine unit can be stable reach more than 95%, even can reach to more than 97%, and in the vinyl aromatic hydrocarbons unit degree of hydrogenation of the two keys of aromatic hydrocarbon phenyl ring below 3%.This shows that catalyst composition used in the present invention has very good catalyst selectivity.The hydrogenation turnover ratio is understood at the available infrared spectrum analysis of conjugated diene unit part, then can be about the hydrogenation ratio of aromatic hydrocarbon core by ultraviolet spectral analysis, similar in this respect analytical procedure, can be with reference to No. 4501857, United States Patent (USP).
Carry out the polymers soln of gained after the hydrogenation by hydrogenation catalyst of the present invention, can add a kind of polar solvent and make polymkeric substance condense out.This polar solvent is the poor solvent of this hydropolymer, for example methyl alcohol or acetone.Perhaps, the solution after the hydrogenation can be poured in the hot water and stir, polymkeric substance is distilled with solvent, or the direct heating reaction soln is with evaporating solvent, and separate this polymkeric substance.
According to the present invention, only need the hydrogenation catalyst composition of minute quantity, successfully hydrogenated conjugated diene polymer can be arranged, quite gratifying hydrogenation effect is arranged.And most catalyzer just separates or decomposes with polymkeric substance in the sepn process of polymkeric substance, does not need the specific step of other cleaning or removal catalyst system.
One big characteristic of catalyst composition of the present invention is hydrogenation catalyst (b), cooperate the existence of other catalyzer can reach the effect of stablizing other catalyzer and promoting other catalyst activity, so after adding catalyst composition of the present invention in the conjugated diolefin polymer, can under the condition of passivity gas, store 4 to 5 days and still have suitable activity, and reproducibility is very good.Another characteristic is that catalyst composition of the present invention is in still having hydrogenation activity highly in the temperature system widely.In addition, catalyst composition of the present invention can be high temperature resistant, lose activity of such catalysts because of too high hydrogenation heat, therefore quite is adapted at operating under the operational condition of continous way production.
Below by several embodiment illustrating further method of the present invention, feature and advantage, but be not to be used for limiting the scope of the invention, scope of the present invention should be as the criterion with appended claim scope.
Embodiment 1
The preparation of SBS co-polymer
Have in the double pipe heater of agitator in 10L, the hexanaphthene of filling 5400 grams, the n-Butyl Lithium (n-butyl lithium) of 7.4mmol and the tetrahydrofuran (THF) of 252mmol, and, under 45 ℃, carry out polyreaction in the vinylbenzene that wherein add 96 grams.In this reactive system, add 400 1,3-butadienes that restrain, and continue to aggregate into a kind of solid content 9.7%, the triblock copolymer compound of the SBS of molecular weight 230,000 (styrene-butadiene-styrene) in the vinylbenzene that wherein add 96 grams.
Embodiment 2
Get the polymers soln 1000g of the SBS triblock copolymer of preparation among the embodiment 1, move in the withstand voltage hydrogenation groove, remain under the environment of nitrogen, in the hexanaphthene of allotment 0.11mmol four (isopropoxy) silicon at 10ml under the room temperature, in glove box, be pre-mixed 0.11mmol four (isopropoxy) silicon and 0.16mmol n-Butyl Lithium in addition in the hexanaphthene of 10ml, reach two (cyclopentadienyl) titanium dichloride of 0.055mmol and 0.33mmol triisobutyl aluminium in 20 milliliters hexanaphthene, add respectively in the SBS polymkeric substance of above-mentioned preparation, in wherein being blown into hydrogen, make partial pressure reach 25Kg/cm 2, under 80 ℃, carry out hydrogenization.
Fig. 1 show before the hydrogenation and hydrogenation after the infrared spectrum of SBS polymkeric substance.This spectrum shows, the SBS triblock copolymer is before hydrogenation not, in wavelength 968cm -1And 995cm -1The place finds the functional group place of trans double bond, in wavelength 912cm -1Find 1,2-vinyl double bond place.After the hydrogenation 1 hour, can find that the crest that above-mentioned wavelength place manifests significantly disappears, the hydrogenation ratio (hydrogenation ratio of the unitary unsaturated double bond of 1,3-butadiene) that measure this moment is 98%.The data preparation of hydrogenation is in table 1.
Embodiment 3
Get the polymers soln 1000g of the SBS triblock copolymer of preparation among the embodiment 1, move in the withstand voltage hydrogenation groove, remain under the environment of nitrogen, in allocating 0.11mmol four (isopropoxy) silicon under the room temperature in 10 milliliters hexanaphthene, two 0.055mmol (cyclopentadienyl) titanium dichloride in 10 milliliters hexanaphthene and the triisobutyl aluminium of 0.33mmol at 10 milliliters cyclohexane solution, add respectively in the SBS polymers soln of above-mentioned preparation, in wherein being blown into hydrogen, make partial pressure reach 25Kg/cm 2, under 80 ℃, carry out hydrogenization.After 30 minutes, record the hydrogenation ratio of hydrogenation ratio arrival after 76%, 1 hour and can arrive 96%.The data preparation of hydrogenation is in table 1.
Embodiment 4
As the identical method of embodiment 3, in the hexanaphthene of allotment 0.11mmol four (isopropoxy) silicon at 10ml under the room temperature, in glove box, be pre-mixed two (cyclopentadienyl) titanium dichloride of 0.055mmol in addition in 10 milliliters hexanaphthene suspended substance, and the triisobutyl aluminium of 0.33mmol is at 10 milliliters hexanaphthene, add respectively in the SBS polymers soln of above-mentioned preparation, in wherein being blown into hydrogen, make partial pressure reach 25Kg/cm 2, under 80 ℃, carry out hydrogenization.After 30 minutes, record the hydrogenation ratio of hydrogenation ratio arrival after 85%, 1 hour and can arrive 98%.The data preparation of hydrogenation is in table 1.
Embodiment 5
As the identical method of embodiment 3, but change four (isopropoxy) silicon four (isobutoxy) silicon of 0.165mmol in the hexanaphthene of 10ml, in glove box, be pre-mixed two (cyclopentadienyl) titanium dichloride of 0.055mmol in addition in 10 milliliters hexanaphthene suspended substance, and the triisobutyl aluminium of 0.33mmol is at 10 milliliters hexanaphthene, add respectively in the SBS polymers soln of above-mentioned preparation, in wherein being blown into hydrogen, make partial pressure reach 25Kg/cm 2, under 80 ℃, carry out hydrogenization.After 30 minutes, record the hydrogenation ratio of hydrogenation ratio arrival after 90%, 1 hour and can arrive 98%.The data preparation of hydrogenation is in table 1.
Embodiment 6
As the same method of embodiment 3, but change four (isopropoxy) silicon four (positive ten dioxy bases) silicon of 0.2mmol in the hexanaphthene of 10ml, in glove box, be pre-mixed two (cyclopentadienyl) titanium dichloride of 0.055mmol in addition in 10 milliliters hexanaphthene suspended substance, and the triisobutyl aluminium of 0.33mmol is at 10 milliliters hexanaphthene, add respectively in the SBS polymers soln of above-mentioned preparation, in wherein being blown into hydrogen, make partial pressure reach 25Kg/cm 2, carry out hydrogenization in 80 ℃.After 30 minutes, hydrogenation ratio can reach 97% after recording hydrogenation ratio and arriving hydrogenation ratio after 65%, 1 hour and can arrive 86%, 1.5 hour.The data preparation of hydrogenation is in table 1.
Embodiment 7
As the same method of embodiment 3, but change four (isopropoxy) silicon three (positive propoxy) phenyl silicon of 0.2mmol in the hexanaphthene of 10ml, in glove box, be pre-mixed two (cyclopentadienyl) titanium dichloride of 0.055mmol in addition in 10 milliliters hexanaphthene suspended substance, and the triisobutyl aluminium of 0.33mmol is at 10 milliliters hexanaphthene, add respectively in the SBS polymers soln of above-mentioned preparation, in wherein being blown into hydrogen, make partial pressure reach 25Kg/cm 2, carry out hydrogenation in 80 ℃.After 30 minutes, hydrogenation ratio can reach 97% after recording hydrogenation ratio and arriving hydrogenation ratio after 65%, 1 hour and can arrive 86%, 1.5 hour.The data preparation of hydrogenation is in table 1.
Embodiment 8
As the same method of embodiment 3, but change four (isopropoxy) silicon two (positive third oxygen) two (phenyl) silicon of 0.275mmol in the hexanaphthene of 10ml, in glove box, be pre-mixed two (cyclopentadienyl) titanium dichloride of 0.055mmol in addition in 10 milliliters hexanaphthene suspended substance, and the triisobutyl aluminium of 0.33mmol is at 10 milliliters hexanaphthene, add respectively in the SBS polymers soln of above-mentioned preparation, in wherein being blown into hydrogen, make partial pressure reach 25Kg/cm 2, carry out hydrogenization in 80 ℃.After 30 minutes, hydrogenation ratio can reach 97% after recording hydrogenation ratio and arriving hydrogenation ratio after 65%, 1 hour and can arrive 76%, 2 hour.The data preparation of hydrogenation is in table 1.
Embodiment 9
As the same method of embodiment 3, but with four (isopropoxy) silicon change into 0.275mmol four (hexane oxygen base) tin in the hexanaphthene of 10ml, in glove box, be pre-mixed two (cyclopentadienyl) titanium dichloride of 0.055mmol in addition in 10 milliliters hexanaphthene suspended substance, and the triisobutyl aluminium of 0.33mmol is at 10 milliliters hexanaphthene, add respectively in the SBS polymers soln of above-mentioned preparation, in wherein being blown into hydrogen, make partial pressure reach 25Kg/cm 2, carry out hydrogenization in 80 ℃.After 30 minutes, hydrogenation ratio can reach 97% after recording hydrogenation ratio and arriving hydrogenation ratio after 65%, 1 hour and can arrive 76%, 2 hour.The data preparation of hydrogenation is in table 1.
Embodiment 10
As the same method of embodiment 3, but change four (isopropoxy) silicon three (isobutoxy) aluminium of 0.25mmol in the hexanaphthene of 10ml, in glove box, be pre-mixed two (cyclopentadienyl) titanium dichloride of 0.055mmol in addition in 10 milliliters hexanaphthene suspended substance, and the triisobutyl aluminium of 0.33mmol is at 10 milliliters hexanaphthene, add respectively in the SBS polymers soln of above-mentioned preparation, in wherein being blown into hydrogen, make partial pressure reach 25Kg/cm 2, in carrying out hydrogenization under with 80 ℃ under this condition.After 30 minutes, hydrogenation ratio can reach 95% after recording hydrogenation ratio and arriving hydrogenation ratio after 65%, 1 hour and arrive 86%, 1.5 hour.The data preparation of hydrogenation is in table 1.
Embodiment 11
As the same method of embodiment 3, but change four (isopropoxy) silicon the positive oxyethyl group gallium of 0.25mmol in the hexanaphthene of 10ml, in glove box, be pre-mixed two (cyclopentadienyl) titanium dichloride of 0.055mmol in addition in 10 milliliters hexanaphthene suspended substance, and the triisobutyl aluminium of 0.33mmol is at 10 milliliters hexanaphthene, add respectively in the SBS polymers soln of above-mentioned preparation, in wherein being blown into hydrogen, make partial pressure reach 25Kg/cm 2, in carrying out hydrogenization under with 80 ℃ under this condition.After 30 minutes, hydrogenation ratio can reach 95% after recording hydrogenation ratio and arriving hydrogenation ratio after 65%, 1 hour and arrive 86%, 1.5 hour.The data preparation of hydrogenation is in table 1.
Comparing embodiment
Below enumerate several comparing embodiments, be used for doing a comparison with embodiments of the invention, it should be noted that, the employed hydrogenation catalyst composition of these comparing embodiments does not comprise hydrogenation catalyst of the present invention (b), is used for further specifying the feature and the advantage of hydrogenation catalyst composition of the present invention.
Comparing embodiment 1
As the identical method of embodiment 3, but do not add four (isopropoxy) silicon.In glove box, be pre-mixed two (cyclopentadienyl) titanium dichloride of 0.055mmol in 10 milliliters hexanaphthene suspended substance, and the triisobutyl aluminium of 0.33mmol is at 10 milliliters hexanaphthene, add respectively in the SBS polymers soln of above-mentioned preparation, in wherein being blown into hydrogen, make partial pressure reach 25Kg/cm 2, under 80 ℃, carry out hydrogenization.
Fig. 2 show before the hydrogenation and hydrogenation after the infrared spectrum of SBS polymkeric substance.This spectrum shows, the SBS triblock copolymer is before hydrogenation not, in wavelength 968cm -1And 995cm -1The place finds the functional group place of trans double bond, in wavelength 912cm -1Find 1,2-vinyl double bond place.After the hydrogenation 1 hour, can find at wavelength 995cm -1And 912cm -1Being absorbed with of place reduces, but 968cm -1The absorption at place does not almost change.The hydrogenation ratio that measure this moment is 23%.The data preparation of hydrogenation is in table 1.
Comparing embodiment 2
Get the polymers soln 1000g of the SBS triblock copolymer of preparation among the embodiment 1, move in the withstand voltage hydrogenation groove, importing hydrogen stirred 30 minutes in advance, method as embodiment 3, but change four (isopropoxy) silicon into the 0.22mmol n-Butyl Lithium, in glove box, be pre-mixed two (cyclopentadienyl) titanium dichloride of 0.055mmol in 10 milliliters hexanaphthene suspended substance, and the triisobutyl aluminium of 0.44mmol is at 10 milliliters hexanaphthene, add respectively in the SBS polymers soln of above-mentioned preparation, make the partial pressure of hydrogen reach 25Kg/cm 2, carry out hydrogenation in 80 ℃.After 30 minutes, record the hydrogenation ratio of hydrogenation ratio arrival after 15%, 1 hour and can arrive 24%.The data preparation of hydrogenation is in table 1.
Table 1
The embodiment numbering Trans double bond residual quantity (%) 1,2-vinyl double bond residual quantity (%) 1,3-butadiene hydrogenation ratio (%) Phenyl ring hydrogenation ratio (%)
Embodiment 2 2.7 0.3 98 ＜1
Embodiment 3 2.6 0.4 96 ＜1
Embodiment 4 1.5 0.5 98 ＜1
Embodiment 5 1.7 0.3 98 ＜1
Embodiment 6 2.7 0.3 97 ＜1
Embodiment 7 2.6 0.4 97 ＜1
Embodiment 8 1.5 0.2 97 ＜1
Embodiment 9 1.7 0.3 97 ＜1
Embodiment 10 4.2 0.8 95 ＜1
Embodiment 11 4.2 0.8 95 ＜1
Comparing embodiment 1 75.5 1.5 23 ＜1
Comparing embodiment 2 74.4 1.6 24 ＜1
As shown in Table 1, utilize hydrogenation catalyst composition of the present invention to carry out the hydrogenation of conjugated diolefin polymer, the trans double bond residual quantity of the conjugated diolefin polymer that is hydrogenated is lower than 5%, and 1,2-vinyl double bond residual quantity is lower than 1%, and the 1,3-butadiene hydrogenation ratio is greater than (embodiment 1～9) below 95%; Review, comparing embodiment 1 and 2 is not because its employed hydrogenation catalyst composition comprises hydrogenation catalyst of the present invention (b), so its trans double bond and 1, the residual quantity of 2-vinyl double bond is obviously higher, and its hydrogenation ratio to 1,3-butadiene is lower than below 25%.
Embodiment 12-17
Hydrogenant catalyzer and dosage reference example 3, but change different hydrogenation temperatures, hydrogen pressure, reaction times, its hydrogenant degree arrangement is as table 2.
Table 2
The embodiment numbering Hydrogenation temperature (℃) Hydrogenation pressure (Kg/cm 2) Reaction times (hour) 1,3-butadiene hydrogenation ratio (%)
Embodiment 12 60 10 1 65
Embodiment 13 60 10 3 94
Embodiment 14 80 10 1 97
Embodiment 15 80 25 0.5 97
Embodiment 16 100 10 0.5 97
Embodiment 17 100 25 0.5 97
In sum, hydrogenation catalyst composition disclosed in this invention has superior hydrogenation ability for conjugated diolefin polymer, therefore only needs can finish catalyzed reaction with less amount.In addition, this hydrogenation catalyst composition is highly stable, and after the time that stores a segment length, activity of such catalysts still has satisfactory stability and reproducibility, and is quite economical.Moreover, catalyst composition of the present invention is in still having hydrogenation activity highly in the temperature system widely, therefore the method for hydrogenated conjugated diene polymer of the present invention can carried out under the temperature system widely, do not lose activity of such catalysts, therefore be well suited under the operational condition that continous way is produced, operating because of too high hydrogenation heat.
Though the present invention discloses as above with preferred embodiment, so it is not in order to restriction the present invention, and any those who are familiar with this art without departing from the spirit and scope of the present invention, change and retouching when doing, so protection scope of the present invention are when being as the criterion with claim.

Claims (47)

1, a kind of method of hydrogenated conjugated diene polymer, and this conjugated diolefin polymer is the homopolymer or the multipolymer of conjugated diolefine, this method comprises that this conjugated diolefin polymer that will be dissolved in the passivity organic solvent reacts with hydrogen in the presence of a hydrogenation catalyst composition, with the unsaturated double-bond of conjugated diene unit in this conjugated diolefin polymer of selective hydration, and this hydrogenation between 0 ℃ to 200 ℃ of temperature of reaction, hydrogen pressure is 0.1kg/cm 2To 100kg/cm 2Scope in carry out, it is characterized in that this hydrogenation catalyst composition comprises following hydrogenation catalyst:
(a) titanium compound shown in general formula (I):
Figure C2004100967360002C1
General formula (I)
R wherein 1, R 2Be identical or different substituting group, and be hydrogen, halogen atom, C 1～C 8Alkyl and alkoxyl group, C 6～C 12Cycloalkyl, phenyl, phenoxy group, C 7～C 10Alkoxy aryl and aralkyl, carboxyl ,-CH 2P (phenyl) 2,-CH 2Si (C 1～C 5Alkyl) 3Or-P (phenyl) 2, Cp *Represent cyclopentadienyl, indenyl, fluorenyl or derivatives thereof;
(b) compound shown in general formula (II) or general formula (III):
Figure C2004100967360002C2
General formula (II) general formula (III)
L wherein 1Be IV A family element, L 2Be III A family element, R 3Be C 1～C 12Alkyl or C 1～C 12Cycloalkyl, X 1, X 2, X 3Be identical or different substituting group, and be C 1～C 12Alkyl, C 1～C 12Alkoxyl group, C 1～C 12Cycloalkyloxy, phenyl or phenoxy group; And
(c) trialkyl aluminium compound shown in general formula (IV)
Figure C2004100967360003C1
General formula (IV)
R wherein 4, R 5, R 6Can be identical or different substituting group, and be C 1～C 12Alkyl or C 6～C 12Aromatic base,
Wherein, the mol ratio of this hydrogenation catalyst (b) and hydrogenation catalyst (a) is 0.1 to 50, and the mol ratio of hydrogenation catalyst (c) and hydrogenation catalyst (a) is 0.1 to 50, and with respect to these conjugated diolefin polymers of 100 grams, the usage quantity of this hydrogenation catalyst (a) is 0.0001 to 50mmol.
2, method according to claim 1 is characterized in that this hydrogenation catalyst (a) is molybdenyl dichloride (cyclopentadienyl) titanium, molybdenyl dichloride (1-fluorenyl) titanium, molybdenyl dichloride (1-indenyl) titanium, two (1-fluorenyl) titaniums of dibrominated, two (1-indenyl) titaniums of dibrominated, two (cyclopentadienyl) titaniums of dimethyl, two (cyclopentadienyl) titaniums of diethyl, two (cyclopentadienyl) titaniums of dimethanol, two (indenyl) titaniums of dimethanol, two (fluorenyl) titaniums of dimethanol, two (cyclopentadienyl) titaniums of diethoxy, two (cyclopentadienyl) titaniums of dibutoxy, two (cyclopentadienyl) titaniums of two phenoxy groups, two (cyclopentadienyl) titaniums of benzyloxy, two (cyclopentadienyl) titaniums of diphenol oxygen base, two (cyclopentadienyl) titanium or derivatives thereofs of dicarboxyl.
3, method according to claim 2 is characterized in that this hydrogenation catalyst (a) is molybdenyl dichloride (cyclopentadienyl) titanium.
4, method according to claim 1 is characterized in that this hydrogenation catalyst (b) is the compound shown in the general formula (II), and X 1, X 2And X 3Among at least one is C 1～C 12Alkoxyl group or C 1～C 12Cycloalkyloxy.
5, method according to claim 1 is characterized in that this hydrogenation catalyst (b) is the compound shown in the general formula (II), and X 1, X 2And X 3Among the two is C 1～C 12Alkoxyl group or C 1～C 12Cycloalkyloxy, and another person is phenyl or alkyl.
6, method according to claim 5 is characterized in that this hydrogenation catalyst (b) is three (n-propane oxygen base) phenyl silicon, three (different third alkoxyl group) phenyl silicon, three (normal butane oxygen base) phenyl silicon, three (isobutyl alkoxyl group) phenyl silicon, three (Skellysolve A oxygen base) phenyl silicon, three (isoamyl alkoxyl group) phenyl silicon, three (n-propane oxygen base) methyl silicon, three (different third alkoxyl group) ethyl silicon, three (second alkoxyl group) ylmethyl tin, three (second alkoxyl group) methyl tin, three (n-propane oxygen base) ylmethyl tin, three (different third alkoxyl group) methyl tin, three (normal butane oxygen base) methyl tin, three (isobutyl alkoxyl group) methyl tin or its mixing.
7, method according to claim 1 is characterized in that this hydrogenation catalyst (b) is the compound shown in the general formula (II), and X 1, X 2And X 3Among one be C 1～C 12Alkoxyl group or C 1～C 12Cycloalkyloxy, and the two is a phenyl in addition.
8, method according to claim 7 is characterized in that in this hydrogenation catalyst (II) being two (n-propane oxygen base) two (phenyl) silicon, two (normal butane oxygen base) two (phenyl) silicon, two (isoamyl alkoxyl group) two (phenyl) silicon, two (n-propane oxygen base) two (phenyl) tin or its mixing.
9, method according to claim 1 is characterized in that this hydrogenation catalyst (b) is the compound shown in the general formula (II), and X 1, X 2And X 3Be identical or different C 1～C 12Alkoxyl group or C 1～C 12Cycloalkyloxy.
10, method according to claim 9 is characterized in that this hydrogenation catalyst (b) is four (C 1～C 12Alkoxyl group) silicon or four (C 1～C 12Alkoxyl group) tin.
11, method according to claim 10, it is characterized in that this hydrogenation catalyst (b) is four (hexane oxygen base) silicon, four (n-propane oxygen base) silicon, four (different third alkoxyl group) silicon, four (normal butane oxygen base) silicon, four (Zhong Ding alkoxyl group) silicon, four (isobutyl alkoxyl group) silicon, four (Skellysolve A oxygen base) silicon, four (isoamyl alkoxyl group) silicon, four (1-methylbutane oxygen base) silicon, four (2-methylbutane oxygen base) silicon, four (1,2-dimethyl propylene alcoxyl base) silicon, four (neopentane oxygen base) silicon, four (normal hexane oxygen base) silicon, four (dissident's alkoxyl group) silicon, four (1,1-dimethyl butyrate alcoxyl base) silicon, four (2,2-dimethyl butyrate alcoxyl base) silicon, four (3,3-dimethyl butyrate alcoxyl base) silicon, four (n-undecane oxygen base) silicon, four (n-dodecane oxygen base) silicon, four (hexane oxygen base) tin, four (n-propane oxygen base) tin, four (different third alkoxyl group) tin, four (normal butane oxygen base) tin, four (Zhong Ding alkoxyl group) tin, four (isobutyl alkoxyl group) tin, four (Skellysolve A oxygen base) tin or its combination.
12, method according to claim 1 is characterized in that being the compound shown in the general formula (III) at this hydrogenation catalyst (b), and X 1And X 2At least one is C 1～C 12Alkoxyl group or C 1～C 12Cycloalkyloxy.
13, method according to claim 1 is characterized in that this hydrogenation catalyst (b) is the compound shown in the general formula (III), and X 1And X 2Be identical or different C 1～C 12Alkoxyl group or C 1～C 12Cycloalkyloxy.
14, method according to claim 13 is characterized in that this hydrogenation catalyst (b) is three (C 1～C 12Alkoxyl group) aluminium or three (C 1～C 12Alkoxyl group) gallium.
15, method according to claim 14 is characterized in that this hydrogenation catalyst (b) is three (hexane oxygen base) aluminium, three (n-propane oxygen base) aluminium, three (different third alkoxyl group) aluminium, three (normal butane oxygen base) aluminium, three (Zhong Ding alkoxyl group) aluminium, three (isobutyl alkoxyl group) aluminium, three (hexane oxygen base) gallium, three (n-propane oxygen base) gallium, three (different third alkoxyl group) gallium, three (normal butane oxygen base) gallium, three (Zhong Ding alkoxyl group) gallium or its combinations.
16, method according to claim 1, it is characterized in that this hydrogenation catalyst (c) is trimethyl aluminium, triethyl aluminum, tri-n-n-propyl aluminum, triisopropylaluminiuand, tri-butyl aluminum, three (sec-butyl) aluminium, three (isobutyl-) aluminium, three (n-pentyl) aluminium, three (isopentyl) aluminium, three (n-hexyl) aluminium, three (isohexyl) aluminium, three (1-methyl amyl) aluminium, three (2,5-dimethyl octyl group) aluminium, three (2,6-dimethyl octyl group) aluminium, triphenyl aluminum or its combination.
17, method according to claim 1 is characterized in that this hydrogenation catalyst (c) is a triisobutyl aluminium.
18, method according to claim 1 is characterized in that the usage quantity of hydrogenation catalyst (a) is between 0.005 to 0.2mmol with respect to this conjugated diolefin polymer of 100 grams.
19, method according to claim 1 is characterized in that the mol ratio of this hydrogenation catalyst (b) and hydrogenation catalyst (a) is 2 to 15.
20, method according to claim 1 is characterized in that the mol ratio of this hydrogenation catalyst (c) and hydrogenation catalyst (a) is 2 to 15.
21, method according to claim 1, the number molecular-weight average that it is characterized in that this conjugated diolefin polymer is between 1000 to 1000000.
22, method according to claim 1 is characterized in that this conjugated diolefin polymer is a conjugated diene/vinyl aromatic hydrocarbons multipolymer.
23, method according to claim 1, it is characterized in that this hydrogenation be between 40 ℃ to 140 ℃ of temperature of reaction, hydrogen pressure is 1 to 50kg/cm 2Carry out in the scope.
24, method according to claim 1, the hydrogenation ratio of unsaturated double bond that it is characterized in that this conjugated diene unit is for more than at least 50%.
25, method according to claim 24, the hydrogenation ratio of unsaturated double bond that it is characterized in that this conjugated diene unit is for more than at least 90%.
26,, it is characterized in that the hydrogenation ratio of the two keys of the unitary phenyl ring of this vinylaromatic hydrocarbon is lower than 10% according to the described method of claim 1.
27, method according to claim 26 is characterized in that the hydrogenation ratio of the two keys of the unitary phenyl ring of this vinylaromatic hydrocarbon is lower than 3%.
28, a kind of hydrogenation catalyst composition, it comprises following hydrogenation catalyst:
(a) titanium compound shown in general formula (I):
Figure C2004100967360006C1
General formula (I)
R wherein 1, R 2Be identical or different substituting group, and be hydrogen, halogen atom, C 1～C 8Alkyl and alkoxyl group, C 6～C 12Cycloalkyl, phenyl, phenoxy group, C 7～C 10Alkoxy aryl and aralkyl, carboxyl ,-CH 2P (phenyl) 2,-CH 2Si (C 1～C 5Alkyl) 3Or-P (phenyl) 2,
Cp *Represent cyclopentadienyl, indenyl, fluorenyl or derivatives thereof;
(b) compound shown in general formula (II) or general formula (III):
General formula (II) general formula (III)
L wherein 1Be IV A family element, L 2Be III A family element, R 3Be C 1～C 12Alkyl or C 1～C 12Cycloalkyl, X 1, X 2, X 3Be identical or different substituting group, and be C 1～C 12Alkyl, C 1～C 12Alkoxyl group, C 1～C 12Cycloalkyloxy, phenyl or phenoxy group; And
(c) trialkyl aluminium compound shown in general formula (IV)
Figure C2004100967360007C2
General formula (IV)
R wherein 4, R 5, R 6Can be identical or different substituting group, and be C 1～C 12Alkyl or C 6～C 12Aromatic base, wherein the mol ratio of this hydrogenation catalyst (b) and hydrogenation catalyst (a) is 0.1 to 50, and the mol ratio of hydrogenation catalyst (c) and hydrogenation catalyst (a) is 0.1 to 50.
29, hydrogenation catalyst composition according to claim 28 also comprises a conjugation diene polymer, it is characterized in that this conjugated diolefin polymer with respect to 100 grams, and the usage quantity of hydrogenation catalyst (a) is 0.0001 to 50mmol.
30, hydrogenation catalyst composition according to claim 28 is characterized in that this hydrogenation catalyst (a) is molybdenyl dichloride (cyclopentadienyl) titanium, molybdenyl dichloride (1-fluorenyl) titanium, molybdenyl dichloride (1-indenyl) titanium, two (1-fluorenyl) titaniums of dibrominated, two (1-indenyl) titaniums of dibrominated, two (cyclopentadienyl) titaniums of dimethyl, two (cyclopentadienyl) titaniums of diethyl, two (cyclopentadienyl) titaniums of dimethanol, two (indenyl) titaniums of dimethanol, two (fluorenyl) titaniums of dimethanol, two (cyclopentadienyl) titaniums of diethoxy, two (cyclopentadienyl) titaniums of dibutoxy, two (cyclopentadienyl) titaniums of two phenoxy groups, two (cyclopentadienyl) titaniums of benzyloxy, two (cyclopentadienyl) titaniums of diphenol oxygen base, two (cyclopentadienyl) titanium or derivatives thereofs of dicarboxyl.
31, hydrogenation catalyst composition according to claim 28 is characterized in that this hydrogenation catalyst (a) is molybdenyl dichloride (cyclopentadienyl) titanium.
32, hydrogenation catalyst composition according to claim 28 is characterized in that this hydrogenation catalyst (b) is the compound shown in the general formula (II), and X 1, X 2And X 3Among at least one is C 1～C 12Alkoxyl group or C 1～C 12Cycloalkyloxy.
33, hydrogenation catalyst composition according to claim 28 is characterized in that this hydrogenation catalyst (b) is the compound shown in the general formula (II), and X 1, X 2And X 3Among the two is C 1～C 12Alkoxyl group or C 1～C 12Cycloalkyloxy, and another person is phenyl or alkyl.
34, hydrogenation catalyst composition according to claim 28 is characterized in that this hydrogenation catalyst (b) is three (n-propane oxygen base) phenyl silicon, three (different third alkoxyl group) phenyl silicon, three (normal butane oxygen base) phenyl silicon, three (isobutyl alkoxyl group) phenyl silicon, three (Skellysolve A oxygen base) phenyl silicon, three (isoamyl alkoxyl group) phenyl silicon, three (n-propane oxygen base) methyl silicon, three (different third alkoxyl group) ethyl silicon, three (second alkoxyl group) ylmethyl tin, three (second alkoxyl group) methyl tin, three (n-propane oxygen base) ylmethyl tin, three (different third alkoxyl group) methyl tin, three (normal butane oxygen base) methyl tin, three (isobutyl alkoxyl group) methyl tin or its combinations.
35, hydrogenation catalyst composition according to claim 28 is characterized in that this hydrogenation catalyst (b) is the compound shown in the general formula (II), and X 1, X 2And X 3Among one be C 1～C 12Alkoxyl group or C 1～C 12Cycloalkyloxy, and the two is a phenyl in addition.
36, hydrogenation catalyst composition according to claim 35 is characterized in that in this hydrogenation catalyst (b) being two (n-propane oxygen base) two (phenyl) silicon, two (normal butane oxygen base) two (phenyl) silicon, two (isoamyl alkoxyl group) two (phenyl) silicon, two (n-propane oxygen base) two (phenyl) tin or its combination.
37, hydrogenation catalyst composition according to claim 28 is characterized in that this hydrogenation catalyst (b) is the compound shown in the general formula (II), and X 1, X 2And X 3Be identical or different C 1～C 12Alkoxyl group or C 1～C 12Cycloalkyloxy.
38,, it is characterized in that this hydrogenation catalyst (b) is four (C according to the described hydrogenation catalyst composition of claim 37 1～C 12Alkoxyl group) silicon, four (C 1～C 12Alkoxyl group) tin or its combination.
39, according to the described hydrogenation catalyst composition of claim 38, it is characterized in that this hydrogenation catalyst (b) is four (hexane oxygen base) silicon, four (n-propane oxygen base) silicon, four (different third alkoxyl group) silicon, four (normal butane oxygen base) silicon, four (Zhong Ding alkoxyl group) silicon, four (isobutyl alkoxyl group) silicon, four (Skellysolve A oxygen base) silicon, four (isoamyl alkoxyl group) silicon, four (1-methylbutane oxygen base) silicon, four (2-methylbutane oxygen base) silicon, four (1,2-dimethyl propylene alcoxyl base) silicon, four (neopentane oxygen base) silicon, four (normal hexane oxygen base) silicon, four (dissident's alkoxyl group) silicon, four (1,1-dimethyl butyrate alcoxyl base) silicon, four (2,2-dimethyl butyrate alcoxyl base) silicon, four (3,3-dimethyl butyrate alcoxyl base) silicon, four (n-undecane oxygen base) silicon, four (n-dodecane oxygen base) silicon, four (hexane oxygen base) tin, four (n-propane oxygen base) tin, four (different third alkoxyl group) tin, four (normal butane oxygen base) tin, four (Zhong Ding alkoxyl group) tin, four (isobutyl alkoxyl group) tin, four (Skellysolve A oxygen base) tin or its combination.
40, hydrogenation catalyst composition according to claim 28 is characterized in that being the compound shown in the general formula (III) at this hydrogenation catalyst (b), and X 1And X 2At least one is C 1～C 12Alkoxyl group or C 1～C 12Cycloalkyloxy.
41, according to the described hydrogenation catalyst composition of claim 37, it is characterized in that this hydrogenation catalyst (b) is the compound shown in the general formula (III), and X 1And X 2Be identical or different C 1～C 12Alkoxyl group or C 1～C 12Cycloalkyloxy.
42,, it is characterized in that this hydrogenation catalyst (b) is three (C according to the described hydrogenation catalyst composition of claim 41 1～C 12Alkoxyl group) aluminium or three (C 1～C 12Alkoxyl group) gallium.
43,, it is characterized in that this hydrogenation catalyst (b) is three (hexane oxygen base) aluminium, three (n-propane oxygen base) aluminium, three (different third alkoxyl group) aluminium, three (normal butane oxygen base) aluminium, three (Zhong Ding alkoxyl group) aluminium, three (isobutyl alkoxyl group) aluminium, three (hexane oxygen base) gallium, three (n-propane oxygen base) gallium, three (different third alkoxyl group) gallium, three (normal butane oxygen base) gallium, three (Zhong Ding alkoxyl group) gallium or its combinations according to the described hydrogenation catalyst composition of claim 42.
44, according to the described hydrogenation catalyst composition of claim 2, it is characterized in that this hydrogenation catalyst (c) is trimethyl aluminium, triethyl aluminum, tri-n-n-propyl aluminum, triisopropylaluminiuand, tri-butyl aluminum, three (sec-butyl) aluminium, three (isobutyl-) aluminium, three (n-pentyl) aluminium, three (isopentyl) aluminium, three (n-hexyl) aluminium, three (isohexyl) aluminium, three (1-methyl amyl) aluminium, three (2,5-dimethyl octyl group) aluminium, three (2,6-dimethyl octyl group) aluminium or triphenyl aluminum.
45, hydrogenation catalyst composition according to claim 28 is characterized in that this hydrogenation catalyst (c) is a triisobutyl aluminium.
46, hydrogenation catalyst composition according to claim 28 is characterized in that the mol ratio of this hydrogenation catalyst (b) and hydrogenation catalyst (a) is 2 to 15.
47, hydrogenation catalyst composition according to claim 28 is characterized in that the mol ratio of this hydrogenation catalyst (c) and hydrogenation catalyst (a) is 2 to 15.
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