CN100564402C - The method of hydrogenating polymer containing conjugated diene unit and hydrogenation catalyst composition thereof - Google Patents

The method of hydrogenating polymer containing conjugated diene unit and hydrogenation catalyst composition thereof Download PDF

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CN100564402C
CN100564402C CNB2006100070832A CN200610007083A CN100564402C CN 100564402 C CN100564402 C CN 100564402C CN B2006100070832 A CNB2006100070832 A CN B2006100070832A CN 200610007083 A CN200610007083 A CN 200610007083A CN 100564402 C CN100564402 C CN 100564402C
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siloxanes
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hydrogenation
cyclopentadienyl
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CN101016348A (en
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林福
蔡智光
刘顺安
蔡敬诚
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Taiwan Synthetic Rubber Corp
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Abstract

A kind of method of hydrogenating polymer containing conjugated diene unit and hydrogenation catalyst composition thereof, it comprises the conjugated diene unit polymkeric substance that contains that is dissolved in a passivity organic solvent or contain in the passivity organic solvent of part ethers, amine polar compound is reacted with hydrogen that this contains the unsaturated double-bond of conjugated diene unit in the conjugated diene unit polymkeric substance with selective hydration in the presence of a hydrogenation catalyst composition.Hydrogenation catalyst composition of the present invention comprises (a) two (cyclopentadienyl, indenyl, fluorenyl or derivatives thereof) titanium compound or its mixture; (b) compound shown in formula (II) or the formula (III), or its mixture hydrogenation catalyst of the present invention (b) is the compound that comprises at least shown in formula (II) or formula (III), or both mixtures: formula (II) formula (III); Wherein formula (II) is a chain-like structure, and formula (III) is a ring texture, and R is C 1～C 12Alkyl, thiazolinyl, amido, halogen, X 1, X 2Be C 1～C 12Alkyl, C 1～C 12Epoxy alkyl, aromatic base, alkylaryl, carbonyl, n＞1, m＞2 and (c) organometallic compound.

Description

The method of hydrogenating polymer containing conjugated diene unit and hydrogenation catalyst composition thereof
Technical field
The present invention relates to a kind of method and catalyst composition thereof of hydrogenating polymer containing conjugated diene unit, be particularly to use special catalyst composition to come the method for hydrogenating polymer containing conjugated diene unit.
Background technology
Industrially carry out single 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 quite 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.Especially being used in conjugated diolefine and vinylaromatic hydrocarbon (vinyl aromatic hydrocarbon) is the polymkeric substance that physical crosslinking exists for monomer carries out the polymeric thermoplastic rubber, 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 the intensive restriction.
With conjugated diolefine and vinylaromatic hydrocarbon is the available hydrogenant method of improvement of defectives such as monomeric multipolymer weathering resistance, 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 for example is carbon, silica, alumina, lime carbonate etc., and metal is generally the compound that Ni, Pd, Pt etc. are formed.
(2) homogeneous catalyst, for example (a) Ziegler (Ziegler) catalyzer system 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 the homogeneous phase catalyst compare, its activity is lower, thus for desired hydrogenization, 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 active center easily, so contacting of reactant and catalyzer is quite difficult near non-hydropolymer.And this type of catalyst 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 desire hydrogenation contained the multipolymer of conjugated diolefine and vinylaromatic hydrocarbon, optionally the unsaturated double bond of the conjugated diene unit in the hydrogenated copolymer was 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 that because polymkeric substance is adsorbed on the heterogeneous catalyst by brute force, it is impossible desiring to remove fully.
And in the method for using Ziegler catalyst catalysis system, reaction ties up in fact and takes place on the uniform dielectric, so the hydrogenation of multipolymer can be carried out under the pressure of appropriateness and temperature condition.And, via filling a part selection hydrogenant condition, unitary pair of key of possible selective hydrogenation of conjugated diolefine and can the unitary aromatic nucleus of hydrogenated vinyl aromatic hydrocarbon, the catalyst consumption of its use higher (need higher catalyst concn) but, be difficult in the product by gained catalyst being removed fully, thereby the consumption that causes the unstable of product and remove the energy that causes in the catalyst process.
Traditionally, the method for using homogeneous catalyst to come hydrogenating polymer containing conjugated diene unit is described below:
For example United States Patent (USP) case 4980421 is delivered the selective hydrogenation of the unsaturated double-bond that contains the conjugated diene unit polymkeric substance, be utilize comprise two (cyclopentadienyl) titanium (+4) compound, alcoxyl lithiumation thing (LiOR), 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 hydrogenating polymer containing conjugated diene unit, the polymkeric substance after the hydrogenation has outstanding rerum natura and weathering resistance.
Deliver in the United States Patent (USP) 5244980 and will have the active conjugated diene unit polymkeric substance that contains, after the hydrogen termination, add organic alkali metal (particularly organolithium metal), and add Typee (Tebbe) catalyst.According to meaning good hydrogenation effect is arranged.
The catalyst combination that discloses in the United States Patent (USP) 5886108, has the active conjugated diene unit polymkeric substance that contains, under the condition that adds hydroxy, carbon oxygen base or ester group, at least a two (cyclopentadienyl) titanium (+4) compound and trimethyl aluminium react compound Typee (Tebbe) catalyst of formation for a long time, participate in hydrogenation according to meaning with this compound, have good hydrogenation efficiency.
The catalyst combination of delivering in the United States Patent (USP) 5985995, has the active conjugated diene unit polymkeric substance that contains, under the condition that adds alkyl halide silicon or alkyl tin halide, at least there are two (cyclopentadienyl) titanium compounds of benzyloxy, according to calling down, have quite good hydrogenation efficiency in this catalyst combination.
Deliver the selective hydrogenation that contains conjugated diene unit polymkeric substance 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 that this catalyst system has the ability of hydrogenated conjugated diene polymer and multipolymer thereof about the composition of a kind of bicyclic pentadiene titanium compound and aluminium or magnesium and alkali-metal a kind of organometallic compound under the existence of the polar compound that is contained in alkali-metal alkoxide and ether, ketone and other type.
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, its compound for containing the compound of carbon back (Carbonyl) or containing 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 United States Patent (USP) 6313230 and the People's Republic of China's patent 00107660.4, its catalyst combination is at least two (cyclopentadienyl) titanium (+a 4) compound, and comprising tool Si-H functional group's compound, tool is known this catalyst combination has suitable help for promoting hydrogenation efficiency.But thus the embodiment of patent as can be known the hydrogenation top temperature be about 60 ℃, and easy inactivation when this catalyst is combined in the high temperature hydrogenation, thereby when hydrogenation, must remove a large amount of reaction heat, otherwise hydrogenation ratio is not good, and this catalyst is combined in that the following storage time of nitrogen environment is not long, and catalyst activity fails easily, must use in the short period of time in the utmost point after the allotment, otherwise hydrogenation efficiency is wayward, so hydrogenation catalyst composition should not be suitable for the production of continous way processing procedure.
As mentioned above, though existing many kinds of catalyst compositions can be used for hydrogenated conjugated diene polymer, right the present invention researches and develops new method for hydrogenation, it has stable and catalyst composition that be easy to store, uses the catalyst composition of this low metering, and successfully hydrogenation contains the polymkeric substance of conjugated diene unit, and this catalyst is combined under the higher temperature of reaction, still have quite high catalyst activity,, be not highly suitable for business-like volume production because of too high temperature of reaction causes the catalyst inactivation.
Summary of the invention
The object of the present invention is to provide a kind of method and catalyst composition thereof of hydrogenating polymer containing conjugated diene unit, only need to use a spot of hydrogenation catalyst composition, hydrogenated conjugated diene polymer successfully, and demonstrate suitable activity.Because employed catalyst concentration is very low, therefore do not need from hydropolymer, to remove catalyst, promoted economic benefit greatly.Moreover hydrogenation of the present invention is very fast, in having good reproducibility as a result under temperature and the pressure widely.
For achieving the above object, the invention provides a kind of stablizing and catalyst composition that is easy to store and the method for utilizing its hydrogenated conjugated diene polymer that carries out.
Hydrogenation catalyst composition of the present invention comprises following hydrogenation catalyst:
(a) titanium compound shown in formula (I) or its mixture:
Figure C20061000708300121
Formula (I)
Wherein
R 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
A represents cyclopentadienyl, fluorenyl, indenyl or derivatives thereof;
(b) for comprising compound or its both mixture shown in formula (II) or formula (III) at least:
Figure C20061000708300131
Formula (II) formula (III);
Wherein formula (II) is a chain-like structure, and formula (III) is a ring texture, and wherein R is C 1～C 12Alkyl, X 1, X 2Be C 1～C 12Alkyl, C 1～C 12Epoxy alkyl, aromatic base, C 1～C 12Alkylaryl, carbonyl, n＞1, m＞2;
(c) organometallic compound.
Described composition, wherein this hydrogenation catalyst a is the halogenide of two (cyclopentadienyl and derivative thereof) titaniums.
Described composition, wherein this hydrogenation catalyst a is two (cyclopentadienyl) bifluoride titaniums [bis (cyclopentadienyl) titanium difluoride], two (cyclopentadienyl) titanium dichloride, two ((2,4-phenylbenzene phosphatization cyclopentadienyl)) bifluoride titanium, two ((2,4-dimethyl phosphatization cyclopentadienyl) bifluoride titanium, two ((2,4-phenylbenzene phosphatization cyclopentadienyl)) titanium dichloride, two (cyclopentadienyl) titanium dichloride of dimethoxyization, two ((2,4-dimethyl phosphatization cyclopentadienyl)) titanium dichloride, two (cyclopentadienyl) dibrominated titanium, two ((2,4-phenylbenzene phosphatization cyclopentadienyl)) dibrominated titanium, two ((2,4-dimethyl phosphatization cyclopentadienyl)) dibrominated titanium, two (ethylization cyclopentadienyl) titanium dichloride, two (n-propyl cyclopentadienyl) titanium dichloride, two (normal-butyl cyclopentadienyl) titanium dichloride, two (2-ethylhexyl cyclopentadienyl) titanium dichloride, (dimethylsilylene)-bis (η 5-2,4-cyclopentadien-1-ylidene), (ethylene)-bis (η 5-2,4-cyclopentadien-1-ylidene).
Described composition, wherein this hydrogenation catalyst a is the hydrocarbon oxygen organic compound of two (cyclopentadienyl and derivative thereof) titanium.
Described composition, wherein this hydrogenation catalyst a is two (cyclopentadienyl) titaniums of dimethyl, two (cyclopentadienyl) titaniums [bis (cyclopentadienyl) titanium dimethoxy] of diformazan alcohol radical, diformazan alcohol radical two ((2,4-phenylbenzene phosphatization cyclopentadienyl)) titanium, diformazan alcohol radical two ((2,4-dimethyl phosphatization cyclopentadienyl)) titanium, two (cyclopentadienyl) titaniums of diethoxy, diethoxy two ((2,4-phenylbenzene phosphatization cyclopentadienyl)) titanium, diethoxy two ((2,4-dimethyl phosphatization cyclopentadienyl)) titanium, two phenoxy groups two ((2,4-phenylbenzene phosphatization cyclopentadienyl)) titanium, two ((2,4-dimethyl phosphatization the cyclopentadienyl)) titaniums of two phenoxy groups.
Described composition, wherein this hydrogenation catalyst a is the halide compound of two (fluorenyl, indenyl or derivatives thereof base) titaniums.
Described composition, wherein this hydrogenation catalyst a is two (fluorenyl) titanium dichloride [bis (1-fluorenyl) titanium dichloride], two (1-indenyl) titanium dichloride [bis (1-indenyl) titanium dichloride], two (dimethoxy fluorenyl) titanium dichloride, two (fluorenyl) bifluoride titanium, two (indenyl) bifluoride titanium, two (dimethoxy fluorenyl) bifluoride titanium, two (fluorenyl) dibrominated titanium, two (indenyl) dibrominated titanium, two (dimethoxy fluorenyl) titanium, two (indenyl) dibrominated titanium.
Described composition, wherein this hydrogenation catalyst a is the hydrocarbon oxygen organic compound of two (fluorenyl, indenyl or derivatives thereof base) titaniums
Described composition, wherein this hydrogenation catalyst a is two (fluorenyl) titaniums of dimethyl, two (fluorenyl) titaniums of dimethoxy, two (indenyl) titaniums of dimethoxy, two (dimethoxy fluorenyl) titaniums of dimethoxy, two (indenyl) titaniums of dimethoxy, two (fluorenyl) titaniums of diformazan alcohol radical, two (indenyl) titaniums of diformazan alcohol radical, two (dimethoxy fluorenyl) titaniums of diformazan alcohol radical, two (indenyl) titaniums of diformazan alcohol radical, two (fluorenyl) titaniums of two phenoxy groups, two (indenyl) titaniums of two phenoxy groups, two (dimethoxy fluorenyl) titaniums of two phenoxy groups, two (indenyl) titaniums of two phenoxy groups.
Described composition, wherein this hydrogenation catalyst b is the compound shown in the formula (II), X 1, X 2At least one is C 1～C 12Alkyl, C 1～C 12Epoxy alkyl.
Described composition, wherein this hydrogenation catalyst b is poly-(dimethyl) siloxanes, poly-(diethyl) siloxanes, poly-(dibutyl) siloxanes of poly-(dipropyl) siloxanes, poly-(diamyl) siloxanes, poly-(dihexyl) siloxanes, poly-(diheptyl) siloxanes, poly-(dioctyl) siloxanes, poly-(dinonyl) siloxanes, poly-(two certain herbaceous plants with big flowers bases) siloxanes, poly-(methyl epoxy group(ing)) siloxanes, poly-(ethyl epoxy group(ing)) siloxanes, poly-(propyl epoxy) siloxanes, poly-(butyl epoxy group(ing)) siloxanes, poly-(amyl group epoxy group(ing)) siloxanes, poly-(hexyl epoxy group(ing)) siloxanes, poly-(heptyl epoxy group(ing)) siloxanes.
Described composition, wherein this hydrogenation catalyst b is the compound shown in the formula (II), and X 1, X 2At least one is respectively aromatic base or C 1～C 12Alkylaryl.
Described composition wherein is poly-(aminomethyl phenyl) siloxanes among this hydrogenation catalyst II, poly-(ethylphenyl) siloxanes, poly-(propyl group phenyl) siloxanes, poly-(butyl phenyl) siloxanes, poly-(amyl group phenyl) siloxanes, poly-(hexyl phenyl) siloxanes, poly-(heptyl phenyl) siloxanes, poly-(octyl phenyl) siloxanes, poly-(nonyl phenyl) siloxanes, poly-(certain herbaceous plants with big flowers base phenyl) siloxanes, poly-(methylbenzene methyl) siloxanes, poly-(ethylbenzyl) siloxanes, poly-(propylbenzene methyl) siloxanes, poly-(butylbenzene methyl) siloxanes, poly-(amylbenzene methyl) siloxanes, poly-(hexyl benzene methyl) siloxanes, poly-(heptyl benzene methyl) siloxanes, poly-(octyl group phenmethyl) siloxanes, poly-(nonyl benzene methyl) siloxanes, poly-(certain herbaceous plants with big flowers base phenmethyl) siloxanes, poly-(methylbenzene ethyl) siloxanes, poly-(ethylbenzene ethyl) siloxanes, poly-(propylbenzene ethyl) siloxanes, poly-(butylbenzene ethyl) siloxanes, poly-(amylbenzene ethyl) siloxanes, poly-(hexyl benzene ethyl) siloxanes, poly-(heptyl benzene ethyl) siloxanes, poly-(octyl group styroyl) siloxanes.
Described composition, wherein this hydrogenation catalyst b is the compound shown in the formula II, and X 1, X 2At least one is respectively carbonyl.
Described composition, wherein this hydrogenation catalyst b is poly-(methyl carbonyl) siloxanes, poly-(ethyl carbonyl) siloxanes, poly-(propyl group carbonyl) siloxanes, poly-(butyl carbonyl) siloxanes, poly-(amyl group carbonyl) siloxanes.
Described composition is the compound shown in the formula III at this hydrogenation catalyst b wherein, and X 1And X 2Be identical or different C 1～C 12Alkyl or C 1～C 12Cycloalkyloxy.
Described composition, wherein this hydrogenation catalyst b is poly-ring (dimethyl) siloxanes, poly-ring (diethyl) siloxanes, poly-ring (dipropyl) siloxanes, poly-ring (dibutyl) siloxanes, poly-ring (diamyl) siloxanes, poly-ring (dihexyl) siloxanes, poly-ring (diheptyl) siloxanes, poly-ring (dioctyl) siloxanes, poly-ring (dinonyl) siloxanes, poly-ring (two certain herbaceous plants with big flowers bases) siloxanes, poly-ring (methylethyl) siloxanes, poly-ring (methyl-propyl) siloxanes, poly-ring (methyl butyl) siloxanes, poly-ring (methyl amyl) siloxanes, poly-ring (methyl epoxy group(ing)) siloxanes, poly-ring (ethyl epoxy group(ing)) siloxanes, poly-ring (propyl epoxy) siloxanes, poly-ring (butyl epoxy group(ing)) siloxanes, poly-ring (amyl group epoxy group(ing)) siloxanes, poly-ring (hexyl epoxy group(ing)) siloxanes.
Described composition, wherein organometallic compound comprises R 4Li, R 4R 5Mg, R 4R 5R 6Al and composition thereof, wherein R 4Be C 1～C 12Alkyl, alkoxyl group or C 6～C 12Aromatic base or its alkoxyl group, hydrogen atom, R 5, R 6Can be identical or different substituting group, and be C 1～C 12Alkyl or C 6～C 12Aromatic base, hydrogen atom or halogen atom, R 4, R 5, R 6Be not methyl simultaneously.
Described composition, wherein mixture is R 4Li and R 4R 5Mg mixture, R 4Li and R 4R 5R 6The Al mixture.
Described composition, the mol ratio of wherein any organometallic compound and titanium compound is greater than 1.
Described composition, wherein this organo-aluminium compound or its mixture are triethyl aluminum, tri-n-n-propyl aluminum, triisopropylaluminiuand, tri-butyl aluminum, three (second 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, diethylaluminum chloride, ethylaluminium dichloride, the chlorination tri-propyl aluminum, chlorination dibutyl aluminium, di-isobutyl aluminum chloride, dichloride butyl aluminium or its combination.
Described composition, wherein this hydrogenation catalyst is triisobutyl aluminium and triethyl aluminum.
Described composition, wherein this organolithium compound or its mixture for just-propyl lithium, sec.-propyl lithium, n-Butyl Lithium, isobutyl-lithium, tertiary butyl lithium, n-pentyl lithium, phenyl lithium, tolyl lithium; The hydrocarbon polymer of two lithiums is 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 of 4-, 4,4 tetraphenyl butane, 1,3-or 1, two (1-lithium-3 methyl amyl) benzene or its combinations of 4-.
Described composition, wherein this hydrogenation catalyst is n-Butyl Lithium and isobutyl-lithium.
Described composition, wherein this organo-magnesium compound or its mixture be two normal-butyl magnesium, two isobutyl-magnesium, two n-propyl magnesium, two isopropyl-magnesium, two octyl group magnesium, dicyclohexyl magnesium, two 2-ethylhexyl magnesium, normal-butyl isobutyl-magnesium, normal-butyl octyl group magnesium, normal-butyl 2-ethylhexyl magnesium with and combination.
Described composition is wherein for using the mixture of organoaluminum and organolithium simultaneously.
Described composition, it is right that the terminal group that wherein contains conjugated diene unit polymkeric substance itself has active carbon-lithium ion.
Described composition, the terminal group that wherein contains conjugated diene unit polymkeric substance itself has active carbon-lithium ion to stopping activity through deactivators.
Described composition, wherein deactivators comprises: water, alcohols, organic acid, ketone or Organohalogen compounds.
Described composition wherein contains the conjugated diene unit polymkeric substance and is the polymkeric substance by anionoid polymerization, radical polymerization, polycoordination, cationoid polymerisation gained.
Described composition, wherein the addition sequence of hydrogenation catalyst a, b and c is catalyst b to be added contain in the conjugated diene unit polymers soln, adds the mixing solutions of catalyst a and c again.
Described composition, wherein the addition sequence of hydrogenation catalyst a, b and c is catalyst b to be mixed the back adding contain in the conjugated diene unit polymers soln with c, adds the mixing solutions of catalyst a and c again.
Described composition, the addition sequence of hydrogenation catalyst a, b and c wherein, be simultaneously or different sequencing add respectively and contain in the conjugated diene unit polymers soln.
Described composition, wherein with respect to this conjugated diolefin polymer of 100 grams, the usage quantity of hydrogenation catalyst a is between 0.001 to 50mmole.
Described composition, wherein with respect to this conjugated diolefin polymer of 100 grams, the usage quantity of hydrogenation catalyst a is between 0.002 to 10mmole
Described composition, wherein the mol ratio of this hydrogenation catalyst b and hydrogenation catalyst a is 0.1 to 50.
Described composition wherein contains conjugated diene unit polymer molecule weight range between 1000 to 1000000.
The method of hydrogenating polymer containing conjugated diene unit provided by the invention, the homopolymer that this conjugated diene unit polymkeric substance is a conjugated diolefine or with the unitary multipolymer of vinylaromatic hydrocarbon, this conjugated diolefin polymer that is dissolved in the passivity organic solvent reacts with hydrogen in the presence of a hydrogenation catalyst a, b, c composition, and this contains the unsaturated double-bond of conjugated diolefine in the conjugated diene unit unit polymkeric substance to select hydrogenation.
Described method, wherein this hydrogenation be between 0 ℃ to 250 ℃ of temperature of reaction, hydrogen pressure is 1 to 150kg/cm 2Carry out in the scope.
Described method, wherein the hydrogenation ratio of the unsaturated double-bond of this conjugated diene unit is for more than at least 50%.
Described method, wherein the hydrogenation ratio of the unsaturated double-bond of this conjugated diene unit is for more than at least 90%.
Described method wherein can make the hydrogenation ratio of the two keys of the unitary phenyl ring of vinylaromatic hydrocarbon be lower than 30%.
Described method, the hydrogenation ratio of the two keys of the unitary phenyl ring of therein ethylene base aromatic hydrocarbon is lower than 10%.
Described method, wherein used hydrogenation catalyst composition is for a kind of hydrogenation catalyst is applied to conjugated diene unit list polymers or vinylaromatic hydrocarbon unit and conjugated diene unit multipolymer.
Described method, therein ethylene base aromatic hydrocarbon unit and conjugated diene unit multipolymer are styrene-butadiene copolymer, styrene-isoprene multipolymer, vinylbenzene-(divinyl/isoprene) multipolymer.
Described method, therein ethylene base aromatic hydrocarbon unit and conjugated diene unit multipolymer are block (block), out of order (Random), progressive block (Taper) arrangement.
Described method, wherein styrene-butadiene copolymer is styrene-ethylene-butylene-styrene multipolymer (SEBS) after the hydrogenation.
Described method, wherein the styrene-isoprene multipolymer is styrene-ethylene-propylene-styrene multipolymer (SEPS) after the hydrogenation.
Described method, wherein vinylbenzene after the hydrogenation-(divinyl/isoprene) multipolymer is styrene-ethylene-ethylene-propylene-styrol copolymer (SEEPS).
Description of drawings
Fig. 1 shows the infrared spectrum of SBS polymkeric substance before and after hydrogenation of the embodiment of the invention 5.
Fig. 2 shows the infrared spectrum of SBS polymkeric substance before and after hydrogenation of comparing embodiment 1.
Fig. 3 shows the infrared spectrum of SIS polymkeric substance before and after hydrogenation of the embodiment of the invention 22.
Embodiment
For structure of the present invention, working method and feature can be become apparent, especially exemplified by preferred embodiment, and conjunction with figs., be described in detail below:
Hydrogenation catalyst composition of the present invention, it comprises hydrogenation catalyst (a)～(c), and wherein hydrogenation catalyst (a) comprises the titanium compound shown in the formula (I) or its mixture:
Formula (I)
Wherein:
R 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 10Aromatic series alkoxyl group (arylalkoxy) and aromatic series alkyl (arylalkyl), carboxyl (carboxyl) ,～CH 2P (phenyl) 2,～CH 2Si (C 1～C 5Alkyl) 3Or～P (phenyl) 2
A represents identical or different cyclopentadienyl, indenyl, fluorenyl or above-mentioned derivative.
According to the present invention, A can for example be C 5R 7R 8R 9R 10R 11(cyclopentadienyl or derivatives thereof), wherein R 7, R 8, R 9, R 10, R 11Can be identical or different substituting groups, and the optional hydrogen of doing for oneself, halogen atom, alkyl, aryl radical or carboxyl (carboxyl) ,-CH 2P (phenyl) 2,-CH 2Si (C 1～C 5Alkyl) 3Or-P (phenyl) 2
Be applicable to that hydrogenation catalyst of the present invention (a) is the compound shown in the formula (I), wherein just two (cyclopentadienyls, indenyl, fluorenyl and derivative thereof) halogenide of titanium, this type of specific embodiment comprises two (cyclopentadienyl) bifluoride titaniums [bis (cyclopentadienyl) titanium difluoride], two (cyclopentadienyl) titanium dichloride, two ((2,4-phenylbenzene phosphatization cyclopentadienyl)) bifluoride titanium, two ((2,4-dimethyl phosphatization cyclopentadienyl)) bifluoride titanium, two ((2,4-phenylbenzene phosphatization cyclopentadienyl)) titanium dichloride, two (cyclopentadienyl) titanium dichloride of dimethoxyization, two ((2,4-dimethyl phosphatization cyclopentadienyl)) titanium dichloride, two (cyclopentadienyl) dibrominated titanium, two ((2,4-phenylbenzene phosphatization cyclopentadienyl)) dibrominated titanium, two ((2,4-dimethyl phosphatization cyclopentadienyl)) dibrominated titanium, two (ethylization cyclopentadienyl) titanium dichloride, two (n-propyl cyclopentadienyl) titanium dichloride, two (normal-butyl cyclopentadienyl) titanium dichloride, two (2-ethylhexyl cyclopentadienyl) titanium dichloride, (dimethylsilylene)-bis (η 5-2,4-cyclopentadien-1-ylidene), (ethylene)-bis (η 5-2,4-cyclopentadien-1-ylidene).
According to hydrogenation catalyst of the present invention (a) is the compound shown in the formula (I), wherein with regard to the hydrocarbon oxygen organic compound of two (cyclopentadienyl and derivative thereof) titaniums, this type of specific embodiment comprises two (cyclopentadienyl) titaniums of dimethyl, two (cyclopentadienyl) titaniums [bis (cyclopentadienyl) titanium dimethoxy] of diformazan alcohol radical, diformazan alcohol radical two ((2,4-phenylbenzene phosphatization cyclopentadienyl)) titanium, diformazan alcohol radical two ((2,4-dimethyl phosphatization cyclopentadienyl)) titanium, two (cyclopentadienyl) titaniums of diethoxy, diethoxy two ((2,4-phenylbenzene phosphatization cyclopentadienyl)) titanium, diethoxy two ((2,4-dimethyl phosphatization cyclopentadienyl)) titanium, two phenoxy groups two ((2,4-phenylbenzene phosphatization cyclopentadienyl)) titanium, two ((2,4-dimethyl phosphatization the cyclopentadienyl)) titaniums of two phenoxy groups.
According to hydrogenation catalyst of the present invention (a) is the compound shown in the formula (I), wherein just two (fluorenyls, indenyl or derivatives thereof base) halogenide of titanium, this type of specific embodiment comprise two (fluorenyl) titanium dichloride [bis (1-fluorenyl) titanium dichloride], two (1-indenyl) titanium dichloride [bis (1-indenyl) titanium dichloride], two (dimethoxy fluorenyl) titanium dichloride, two (indenyl) titanium dichloride, two (fluorenyl) bifluoride titanium, two (indenyl) bifluoride titanium, two (dimethoxy fluorenyl) bifluoride titanium, two (indenyl) bifluoride titanium, two (fluorenyl) dibrominated titanium, two (indenyl) dibrominated titanium, two (dimethoxy fluorenyl) titanium, two (indenyl) dibrominated titanium.In addition according to two (fluorenyls, indenyl or derivatives thereof base) the hydrocarbon oxygen organic compound of titanium, this type of specific embodiment comprises two (fluorenyl) titaniums of dimethyl, two (fluorenyl) titaniums of dimethoxy, two (indenyl) titaniums of dimethoxy, two (dimethoxy fluorenyl) titaniums of dimethoxy, two (indenyl) titaniums of dimethoxy, two (fluorenyl) titaniums of diformazan alcohol radical, two (indenyl) titaniums of diformazan alcohol radical, two (dimethoxy fluorenyl) titaniums of diformazan alcohol radical, two (indenyl) titaniums of diformazan alcohol radical, two (fluorenyl) titaniums of two phenoxy groups, two (indenyl) titaniums of two phenoxy groups, two (dimethoxy fluorenyl) titaniums of two phenoxy groups, two (indenyl) titaniums of two phenoxy groups, the so-called derived system refers at indenyl herein, fluorenyl, or on the ring of cyclopentadienyl one or several hydrogen are replaced by a substituting group, this substituting group can example be a methyl, methoxyl group, right-the 3rd-butyl phenyl, pentafluorophenyl group, trifluorophenyl, difluorophenyl or 3,5-(tributyl)-groups such as 4-p-methoxy-phenyl.The example of preferable hydrogenation catalyst (a) is two (cyclopentadienyl) titanium dichloride.
Hydrogenation catalyst of the present invention (b) is the compound that comprises at least shown in formula (II) or formula (III), or both mixtures:
Formula (II) formula (III);
Wherein formula (II) is a chain-like structure, and formula (III) is a ring texture, and R is C 1～C 12Alkyl, X 1, X 2Be C 1～C 12Alkyl, C 1～C 12Epoxy alkyl, aromatic base, C 1～C 12Alkylaryl, carbonyl, X 1, X 2Be identical or different substituting group, n＞1, m＞2.
According to the present invention, this hydrogenation catalyst (b) is the compound shown in the formula (II), X 1, X 2At least one is C 1～C 12Alkyl, C 1～C 12Epoxy alkyl.For example, X 1And X 2Be C 1～C 12Alkyl, this type of object lesson comprise poly-(dimethyl) siloxanes, poly-(diethyl) siloxanes, poly-(dipropyl) siloxanes, poly-(dibutyl) siloxanes, poly-(diamyl) siloxanes, poly-(dihexyl) siloxanes, poly-(diheptyl) siloxanes, poly-(dioctyl) siloxanes, poly-(dinonyl) siloxanes, poly-(two certain herbaceous plants with big flowers bases) siloxanes, poly-(methylethyl) siloxanes, poly-(methyl-propyl) siloxanes, poly-(methyl butyl) siloxanes, poly-(methyl amyl) siloxanes, poly-(methyl hexyl) siloxanes, poly-(methylheptyl) siloxanes, poly-(Methyl Octyl) siloxanes, poly-(methyl nonyl) siloxanes, poly-(methyl certain herbaceous plants with big flowers base) siloxanes, poly-(ethyl propyl) siloxanes, poly-(ethyl-butyl) siloxanes, poly-(ethyl pentyl group) siloxanes, poly-(ethylhexyl) siloxanes, poly-(ethyl heptyl) siloxanes, poly-(ethyl octyl group) siloxanes, poly-(ethyl nonyl) siloxanes, poly-(ethyl certain herbaceous plants with big flowers base) siloxanes, poly-(propyl group butyl) siloxanes, poly-(propyl group amyl group) siloxanes, poly-(propyl group hexyl) siloxanes, poly-(propylheptyl) siloxanes, poly-(propyl group octyl group) siloxanes, poly-(propyl group nonyl) siloxanes, poly-(propyl group certain herbaceous plants with big flowers base) siloxanes, poly-(butyl amyl group) siloxanes, poly-(butyl hexyl) siloxanes, poly-(butyl heptyl) siloxanes, poly-(butyl octyl) siloxanes, poly-(butyl nonyl) siloxanes, poly-(butyl certain herbaceous plants with big flowers base) siloxanes, poly-(amyl group hexyl) siloxanes, poly-(amyl group heptyl) siloxanes, poly-(amyl group octyl group) siloxanes, poly-(amyl group nonyl) oxygen alkane, poly-(amyl group certain herbaceous plants with big flowers base) siloxanes, poly-(hexyl heptyl) siloxanes, poly-(hexyl octyl group) siloxanes, poly-(hexyl nonyl) siloxanes, poly-(hexyl certain herbaceous plants with big flowers base) siloxanes, poly-(heptyl octyl group) siloxanes, poly-(heptyl nonyl) siloxanes, poly-(heptyl certain herbaceous plants with big flowers base) siloxanes, poly-(octyl group nonyl) siloxanes, poly-(octyl group certain herbaceous plants with big flowers base) siloxanes, poly-(nonyl certain herbaceous plants with big flowers base) siloxanes.For example, X 1And X 2Be respectively C 1～C 12Alkyl, and C 1～C 12Epoxy alkyl, this type of object lesson comprises poly-(dimethyl epoxy group(ing)) siloxanes, poly-(diepoxy ethyl) siloxanes, poly-(diepoxy propyl group) siloxanes, poly-(diepoxy butyl) siloxanes, poly-(diepoxy amyl group) siloxanes, poly-(diepoxy hexyl) siloxanes, poly-(diepoxy heptyl) siloxanes, poly-(diepoxy octyl group) siloxanes, poly-(diepoxy nonyl) siloxanes, poly-(diepoxy certain herbaceous plants with big flowers base) siloxanes, poly-(methyl epoxy methyl) siloxanes, poly-(ethyl epoxy methyl) siloxanes, poly-(propyl group epoxy methyl) siloxanes, poly-(butyl epoxy methyl) siloxanes, poly-(amyl group epoxy methyl) siloxanes, poly-(hexyl epoxy methyl) siloxanes, poly-(heptyl epoxy methyl) siloxanes, poly-(octyl group epoxy methyl) siloxanes, poly-(nonyl epoxy first) siloxanes, poly-(certain herbaceous plants with big flowers basic ring oxygen methyl) siloxanes, poly-(methyl epoxy ethyl) siloxanes, poly-(ethyl epoxy ethyl) siloxanes, poly-(propyl group epoxy ethyl) siloxanes, poly-(butyl epoxy ethyl) siloxanes, poly-(amyl group epoxy ethyl) siloxanes, poly-(hexyl epoxy ethyl) siloxanes, poly-(heptyl epoxy ethyl) siloxanes, poly-(octyl group epoxy ethyl) siloxanes, poly-(nonyl epoxy ethyl) siloxanes, poly-(certain herbaceous plants with big flowers basic ring oxygen ethyl) siloxanes, poly-(methyl 1 epoxypropyl) siloxanes, poly-(ethyl 1 epoxypropyl) siloxanes, poly-(propyl group 1 epoxypropyl) siloxanes, poly-(butyl 1 epoxypropyl) siloxanes, poly-(amyl group 1 epoxypropyl) siloxanes, poly-(hexyl 1 epoxypropyl) siloxanes, poly-(heptyl 1 epoxypropyl) siloxanes, poly-(octyl group 1 epoxypropyl) siloxanes, poly-(nonyl 1 epoxypropyl) siloxanes, poly-(certain herbaceous plants with big flowers base 1 epoxypropyl) siloxanes, poly-(methyl 2 epoxypropyl) siloxanes, poly-(ethyl 2 epoxypropyl) siloxanes, poly-(propyl group 2 epoxypropyl) siloxanes, poly-(butyl 2 epoxypropyl) siloxanes, poly-(amyl group 2 epoxypropyl) siloxanes, poly-(hexyl 2 epoxypropyl) siloxanes, poly-(heptyl 2 epoxypropyl) siloxanes, poly-(octyl group 2 epoxypropyl) siloxanes, poly-(nonyl 2 epoxypropyl) siloxanes, poly-(certain herbaceous plants with big flowers base 2 epoxypropyl) siloxanes, poly-(methyl 1-epoxy normal-butyl) siloxanes, poly-(ethyl 1-epoxy normal-butyl) siloxanes, poly-(propyl group 1-epoxy normal-butyl) siloxanes, poly-(butyl 1-epoxy normal-butyl) siloxanes, poly-(amyl group 1-epoxy normal-butyl) siloxanes, poly-(hexyl 1-epoxy normal-butyl) siloxanes, poly-(heptyl 1-epoxy normal-butyl) siloxanes, poly-(octyl group 1-epoxy normal-butyl) siloxanes, poly-(nonyl 1-epoxy normal-butyl) siloxanes, poly-(certain herbaceous plants with big flowers base 1-epoxy normal-butyl) siloxanes, poly-(methyl 2-epoxy normal-butyl) siloxanes, poly-(ethyl 2-epoxy normal-butyl) siloxanes, poly-(propyl group 2-epoxy normal-butyl) siloxanes, poly-(butyl 2-epoxy normal-butyl) siloxanes, poly-(amyl group 2-epoxy normal-butyl) siloxanes, poly-(hexyl 2-epoxy normal-butyl) siloxanes, poly-(heptyl 2-epoxy normal-butyl) siloxanes, poly-(octyl group 2-epoxy normal-butyl) siloxanes, poly-(nonyl 2-epoxy normal-butyl) siloxanes, poly-(certain herbaceous plants with big flowers base 2-epoxy normal-butyl) siloxanes, poly-(methyl 1-epoxy second butyl) siloxanes, poly-(ethyl 1-epoxy second butyl) siloxanes, poly-(propyl group 1-epoxy second butyl) siloxanes, poly-(butyl 1-epoxy second butyl) siloxanes, poly-(amyl group 1-epoxy second butyl) siloxanes, poly-(hexyl 1-epoxy second butyl) siloxanes, poly-(heptyl 1-epoxy second butyl) siloxanes, poly-(octyl group 1-epoxy second butyl) siloxanes, poly-(nonyl 1-epoxy second butyl) siloxanes, poly-(certain herbaceous plants with big flowers base 1-epoxy second butyl) siloxanes, poly-(methyl 2-epoxy second butyl) siloxanes, poly-(ethyl 2-epoxy second butyl) siloxanes, poly-(propyl group 2-epoxy second butyl) siloxanes, poly-(butyl 2-epoxy second butyl) siloxanes, poly-(amyl group 2-epoxy second butyl) siloxanes, poly-(hexyl 2-epoxy second butyl) siloxanes, poly-(heptyl 2-epoxy second butyl) siloxanes, poly-(octyl group 2-epoxy second butyl) siloxanes, poly-(nonyl 2-epoxy second butyl) siloxanes, poly-(certain herbaceous plants with big flowers base 2-epoxy second butyl) siloxanes, poly-(methyl 1-epoxy isobutyl-) siloxanes, poly-(ethyl 1-epoxy isobutyl-) siloxanes, poly-(propyl group 1-epoxy isobutyl-) siloxanes, poly-(butyl 1-epoxy isobutyl-) siloxanes, poly-(amyl group 1-epoxy isobutyl-) siloxanes, poly-(hexyl 1-epoxy isobutyl-) siloxanes, poly-(heptyl 1-epoxy isobutyl-) siloxanes, poly-(octyl group 1-epoxy isobutyl-) siloxanes, poly-(nonyl 1-epoxy isobutyl-) siloxanes, poly-(certain herbaceous plants with big flowers base 1-epoxy isobutyl-) siloxanes, poly-(methyl 2-epoxy isobutyl-) siloxanes, poly-(ethyl 2-epoxy isobutyl-) siloxanes, poly-(propyl group 2-epoxy isobutyl-) siloxanes, poly-(butyl 2-epoxy isobutyl-) siloxanes, poly-(amyl group 2-epoxy isobutyl-) siloxanes, poly-(hexyl 2-epoxy isobutyl-) siloxanes, poly-(heptyl 2-epoxy isobutyl-) siloxanes, poly-(octyl group 2-epoxy isobutyl-) siloxanes, poly-(nonyl 2-epoxy isobutyl-) siloxanes, poly-(certain herbaceous plants with big flowers base 2-epoxy isobutyl-) siloxanes, poly-(methyl epoxy tributyl) siloxanes, poly-(ethyl epoxy tributyl) siloxanes, poly-(propyl group epoxy tributyl) siloxanes, poly-(butyl epoxy tributyl) siloxanes, poly-(amyl group epoxy tributyl) siloxanes, poly-(hexyl epoxy tributyl) siloxanes, poly-(heptyl epoxy tributyl) siloxanes, poly-(octyl group epoxy tributyl) siloxanes, poly-(nonyl epoxy tributyl) siloxanes, poly-(certain herbaceous plants with big flowers basic ring oxygen tributyl) siloxanes, in addition, this hydrogenation catalyst (b) is the compound shown in the formula (II), and X 1, X 2Be respectively C 1～C 12Alkyl, and aromatic base.This type of object lesson comprises poly-(aminomethyl phenyl) siloxanes, poly-(ethylphenyl) siloxanes, poly-(propyl group phenyl) siloxanes, poly-(butyl phenyl) siloxanes, poly-(amyl group phenyl) siloxanes, poly-(hexyl phenyl) siloxanes, poly-(heptyl phenyl) siloxanes, poly-(octyl phenyl) siloxanes, poly-(nonyl phenyl) siloxanes, poly-(certain herbaceous plants with big flowers base phenyl) siloxanes.And X 1, X 2Be respectively C 1～C 12Alkyl, and C 1～C 12Alkylaryl.This type of object lesson comprises poly-(methylbenzene methyl) siloxanes, poly-(ethylbenzyl) siloxanes, poly-(propylbenzene methyl) siloxanes, poly-(butylbenzene methyl) siloxanes, poly-(amylbenzene methyl) siloxanes, poly-(hexyl benzene methyl) siloxanes, poly-(heptyl benzene methyl) siloxanes, poly-(octyl group phenmethyl) siloxanes, poly-(nonyl benzene methyl) siloxanes, poly-(certain herbaceous plants with big flowers base phenmethyl) siloxanes, poly-(methylbenzene ethyl) siloxanes, poly-(ethylbenzene ethyl) siloxanes, poly-(propylbenzene ethyl) siloxanes, poly-(butylbenzene ethyl) siloxanes, poly-(amylbenzene ethyl) siloxanes, poly-(hexyl benzene ethyl) siloxanes, poly-(heptyl benzene ethyl) siloxanes, poly-(octyl group styroyl) siloxanes, poly-(nonyl benzene ethyl) siloxanes, poly-(certain herbaceous plants with big flowers base styroyl) siloxanes, poly-(methyl 1-hydrocinnamyl) siloxanes, poly-(ethyl 1-hydrocinnamyl) siloxanes, poly-(propyl group 1-hydrocinnamyl) siloxanes, poly-(butyl 1-hydrocinnamyl) siloxanes, poly-(amyl group 1-hydrocinnamyl) siloxanes, poly-(hexyl 1-hydrocinnamyl) siloxanes, poly-(heptyl 1-hydrocinnamyl) siloxanes, poly-(octyl group 1-hydrocinnamyl) siloxanes, poly-(nonyl 1-hydrocinnamyl) siloxanes, poly-(certain herbaceous plants with big flowers base 1-hydrocinnamyl) siloxanes, poly-(methyl 2-hydrocinnamyl) siloxanes, poly-(ethyl 2-hydrocinnamyl) siloxanes, poly-(propyl group 2-hydrocinnamyl) siloxanes, poly-(butyl 2-hydrocinnamyl) siloxanes, poly-(amyl group 2-hydrocinnamyl) siloxanes, poly-(hexyl 2-hydrocinnamyl) siloxanes, poly-(heptyl 2-hydrocinnamyl) siloxanes, poly-(octyl group 2-hydrocinnamyl) siloxanes, poly-(nonyl 2-hydrocinnamyl) siloxanes, poly-(certain herbaceous plants with big flowers base 2-hydrocinnamyl) siloxanes, poly-(methyl 1-benzene normal-butyl) siloxanes, poly-(ethyl 1-benzene normal-butyl) siloxanes, poly-(propyl group 1-benzene normal-butyl) siloxanes, poly-(butyl 1-benzene normal-butyl) siloxanes, poly-(amyl group 1-benzene normal-butyl) siloxanes, poly-(octyl group 1-benzene normal-butyl) siloxanes, poly-(nonyl 1-benzene normal-butyl) siloxanes, poly-(certain herbaceous plants with big flowers base 1-benzene normal-butyl) siloxanes, poly-(methyl 2-benzene normal-butyl) siloxanes, poly-(ethyl 2-benzene normal-butyl) siloxanes, poly-(propyl group 2-benzene normal-butyl) siloxanes, poly-(butyl 2-benzene normal-butyl) siloxanes, poly-(amyl group 2-benzene normal-butyl) siloxanes, poly-(hexyl 2-benzene normal-butyl) siloxanes, poly-(heptyl 2-benzene normal-butyl) siloxanes, poly-(octyl group 2-benzene normal-butyl) siloxanes, poly-(nonyl 2-benzene normal-butyl) siloxanes, poly-(certain herbaceous plants with big flowers base 2-benzene normal-butyl) siloxanes, poly-(methyl 1-benzene second butyl) siloxanes, poly-(ethyl 1-benzene second butyl) siloxanes, poly-(propyl group 1-benzene second butyl) siloxanes, poly-(butyl 1-benzene second butyl) siloxanes, poly-(amyl group 1-benzene second butyl) siloxanes, poly-(hexyl 1-benzene second butyl) siloxanes, poly-(heptyl 1-benzene second butyl) siloxanes, poly-(octyl group 1-benzene second butyl) siloxanes, poly-(nonyl 1-benzene second butyl) siloxanes, poly-(certain herbaceous plants with big flowers base 1-benzene second butyl) siloxanes, poly-(methyl 2-benzene second butyl) siloxanes, poly-(ethyl 2-benzene second butyl) siloxanes, poly-(propyl group 2-benzene second butyl) siloxanes, poly-(butyl 2-benzene second butyl) siloxanes, poly-(amyl group 2-benzene second butyl) siloxanes, poly-(hexyl 2-benzene second butyl) siloxanes, poly-(heptyl 2-benzene second butyl) siloxanes, poly-(octyl group 2-benzene second butyl) siloxanes, poly-(nonyl 2-benzene second butyl) siloxanes, poly-(certain herbaceous plants with big flowers base 2-benzene second butyl) siloxanes, poly-(methyl 1-benzene isobutyl-) siloxanes, poly-(ethyl 1-benzene isobutyl-) siloxanes, poly-(propyl group 1-benzene isobutyl-) siloxanes, poly-(butyl 1-benzene isobutyl-) siloxanes, poly-(amyl group 1-benzene isobutyl-) siloxanes, poly-(hexyl 1-benzene isobutyl-) siloxanes, poly-(heptyl 1-benzene isobutyl-) siloxanes, poly-(octyl group 1-benzene isobutyl-) siloxanes, poly-(nonyl 1-benzene isobutyl-) siloxanes, poly-(certain herbaceous plants with big flowers base 1-benzene isobutyl-) siloxanes, poly-(methyl 2-benzene isobutyl-) siloxanes, poly-(ethyl 2-benzene isobutyl-) siloxanes, poly-(propyl group 2-benzene isobutyl-) siloxanes, poly-(butyl 2-benzene isobutyl-) siloxanes, poly-(amyl group 2-benzene isobutyl-) siloxanes, poly-(hexyl 2-benzene isobutyl-) siloxanes, poly-(heptyl 2-benzene isobutyl-) siloxanes, poly-(octyl group 2-benzene isobutyl-) siloxanes, poly-(nonyl 2-benzene isobutyl-) siloxanes, poly-(certain herbaceous plants with big flowers base 2-benzene isobutyl-) siloxanes, poly-(methylbenzene tributyl) siloxanes, poly-(ethylbenzene tributyl) siloxanes, poly-(propylbenzene tributyl) siloxanes, poly-(butylbenzene tributyl) siloxanes, poly-(amylbenzene tributyl) siloxanes, poly-(hexyl benzene tributyl) siloxanes, poly-(heptyl benzene tributyl) siloxanes, poly-(octyl group benzene tributyl) siloxanes, poly-(nonyl benzene tributyl) siloxanes, poly-(certain herbaceous plants with big flowers base benzene tributyl) siloxanes.In addition, according to another preferred embodiment of the present invention, this hydrogenation catalyst (b) can be the compound shown in the formula (III), and X 1, X 2At least one is C 1～C 12Alkyl, C 1～C 12Epoxy alkyl, for example, X 1And X 2Be C 1～C 12Alkyl, this type of object lesson comprise poly-ring (dimethyl) siloxanes, poly-ring (diethyl) siloxanes, poly-ring (dipropyl) siloxanes, poly-ring (dibutyl) siloxanes, poly-ring (diamyl) siloxanes, poly-ring (dihexyl) siloxanes, poly-ring (diheptyl) siloxanes, poly-ring (dioctyl) siloxanes, poly-ring (dinonyl) siloxanes, poly-ring (two certain herbaceous plants with big flowers bases) siloxanes, poly-ring (methylethyl) siloxanes, poly-ring (methyl-propyl) siloxanes, poly-ring (methyl butyl) siloxanes, poly-ring (methyl amyl) siloxanes, poly-ring (methyl hexyl) siloxanes, poly-ring (methylheptyl) siloxanes, poly-ring (Methyl Octyl) siloxanes, poly-ring (methyl nonyl) siloxanes, poly-ring (methyl certain herbaceous plants with big flowers base) siloxanes, poly-ring (ethyl propyl) siloxanes, poly-ring (ethyl-butyl) siloxanes, poly-ring (ethyl pentyl group) siloxanes, poly-ring (ethylhexyl) siloxanes, poly-ring (ethyl heptyl) siloxanes, poly-ring (ethyl octyl group) siloxanes, poly-ring (ethyl nonyl) siloxanes, poly-ring (ethyl certain herbaceous plants with big flowers base) siloxanes, poly-ring (propyl group butyl) siloxanes, poly-ring (propyl group amyl group) siloxanes, poly-ring (propyl group hexyl) siloxanes, poly-ring (propylheptyl) siloxanes, poly-ring (propyl group octyl group) siloxanes, poly-ring (propyl group nonyl) siloxanes, poly-ring (propyl group certain herbaceous plants with big flowers base) siloxanes, poly-ring (butyl amyl group) siloxanes, poly-ring (butyl hexyl) siloxanes, poly-ring (butyl heptyl) siloxanes, poly-ring (butyl octyl) siloxanes, poly-ring (butyl nonyl) siloxanes, poly-ring (butyl certain herbaceous plants with big flowers base) siloxanes, poly-ring (amyl group hexyl) siloxanes, poly-ring (amyl group heptyl) siloxanes, poly-ring (amyl group octyl group) siloxanes, poly-ring (amyl group nonyl) oxygen alkane, poly-ring (amyl group certain herbaceous plants with big flowers base) siloxanes, poly-ring (hexyl heptyl) siloxanes, poly-ring (hexyl octyl group) siloxanes, poly-ring (hexyl nonyl) siloxanes, poly-ring (hexyl certain herbaceous plants with big flowers base) siloxanes, poly-ring (heptyl octyl group) siloxanes, poly-ring (heptyl nonyl) siloxanes, poly-ring (heptyl certain herbaceous plants with big flowers base) siloxanes, poly-ring (octyl group nonyl) siloxanes, poly-ring (octyl group certain herbaceous plants with big flowers base) siloxanes, poly-ring (nonyl certain herbaceous plants with big flowers base) siloxanes.For example, X 1And X 2Be respectively C 1～C 12Alkyl, and C 1～C 12Epoxy alkyl, this type of object lesson comprise poly-ring (methyl epoxy group(ing)) siloxanes, poly-ring (ethyl epoxy group(ing)) siloxanes, poly-ring (propyl epoxy) siloxanes, poly-ring (butyl epoxy group(ing)) siloxanes, poly-ring (amyl group epoxy group(ing)) siloxanes, poly-ring (hexyl epoxy group(ing)) siloxanes, poly-ring (heptyl epoxy group(ing)) siloxanes, poly-ring (octyl group epoxy group(ing)) siloxanes, poly-ring (nonyl epoxy group(ing)) siloxanes.
When hydrogenation catalyst (b) is compound shown in the formula (II), except above-mentioned silicon compound, the object lesson of this hydrogenation catalyst (b) still comprises poly-(methyl carbonyl) siloxanes, poly-(ethyl carbonyl) siloxanes, poly-(propyl group carbonyl) siloxanes, poly-(butyl carbonyl) siloxanes, poly-(amyl group carbonyl) siloxanes, poly-(hexyl carbonyl) siloxanes, poly-(heptyl carbonyl) siloxanes, poly-(octyl group carbonyl) siloxanes, poly-(nonyl carbonyl) siloxanes, poly-(certain herbaceous plants with big flowers base carbonyl) siloxanes.
Hydrogenation catalyst of the present invention (c) is an organometallic compound.
Organometallic compound comprises R 4Li, R 4R 5Mg, R 4R 5R 6Al, R 4Li and R 4R 5Mg mixture, R 4Li and R 4R 5R 6The Al mixture.
R wherein 4Be C 1～C 12Alkyl, alkoxyl group or C 6～C 12Aromatic base or its alkoxyl group, hydrogen atom, R 5, R 6Can be identical or different substituting group, and be C 1～C 12Alkyl or C 6～C 12Aromatic base, hydrogen atom or halogen atom, but R 4, R 5, R 6Can not be methyl simultaneously.
According to hydrogenation catalyst composition of the present invention, the organoaluminum object lesson of this hydrogenation catalyst (c) comprising: triethyl aluminum, tri-n-n-propyl aluminum, triisopropylaluminiuand, tri-butyl aluminum, three (second butyl) aluminium, three (isobutyl-) aluminium, three tertiary butyl 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, three (2 ethylhexyl) aluminium, triphenyl aluminum, diethylaluminum chloride, ethylaluminium dichloride, the chlorination tri-propyl aluminum, chlorination dibutyl aluminium, di-isobutyl aluminum chloride, dichloride butyl aluminium etc.Preferable triethyl aluminum, triisopropylaluminiuand, tri-butyl aluminum or three (isobutyl-) aluminium, the diethylaluminum chloride of being chosen as.
According to hydrogenation catalyst composition of the present invention, the organolithium object lesson of this hydrogenation catalyst (c) comprising: just-and propyl lithium, sec.-propyl lithium, n-Butyl Lithium, isobutyl-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 of 4-, 4,4 tetraphenyl butane, 1,3-or 1, two (1-lithium-3 methyl amyl) benzene of 4-.
According to hydrogenation catalyst composition of the present invention, the organic-magnesium of this hydrogenation catalyst (c) mainly is selected from two alkylates of Grignard compound or magnesium, many magnesium compounds commercial be to be dissolved in inactive aliphatic hydrocarbon pattern with organo-magnesium compound to exist, more concrete example is two normal-butyl magnesium, two tertiary butyl magnesium, two isobutyl-magnesium, two n-propyl magnesium, two isopropyl-magnesium, two octyl group magnesium, dicyclohexyl magnesium, two 2-ethylhexyl magnesium, normal-butyl isobutyl-magnesium, normal-butyl octyl group magnesium, normal-butyl 2-ethylhexyl magnesium with and each other mixture.
Method for hydrogenation of the present invention is to contain the conjugated diene unit polymkeric substance with being dissolved in the passivity organic solvent or containing in the passivity organic solvent of part ethers, amine polar compound, in the presence of hydrogenation catalyst composition of the present invention, react, promptly comprise the hydrogenation catalyst (a) and (b), reach (c) with the unsaturated double-bond that contains conjugated diene unit in selective hydrogenation of conjugated diolefine polymer hydrogenation catalyst composition of the present invention with hydrogen.For example, gaseous hydrogen can be imported the desire hydrogenant and contain in the conjugated diene unit polymkeric substance, then, make hydrogen and polymkeric substance fill contacting of part 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.Ended in the active polymers soln as catalyst (b) is added, added catalyst (a) and mixing solutions (c) again.In addition, also can be earlier catalyst (b) be added and do not end in the active polymers soln, add the solution of catalyst (a) and the solution of catalyst (c) more respectively, also can (b) add in the polymkeric substance, and then add (a) and (c) reactant with (c) reaction back.And after all catalyst all are incorporated in the polymkeric substance, be stored in the atmospheric environment of passivity, keep a segment length time, catalyst 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, be used for dissolving hydrogenation catalyst and can be the straight or branched hydrocarbon polymer, for example pentane, hexane, heptane, octane and other analogue with the passivity organic solvent that contains the conjugated diene unit polymkeric substance; Or can be alicyclic hydrocarbon type, for example hexanaphthene, suberane and methyl suberane etc.Hexanaphthene, normal hexane are the examples that is fit to.The passivity organic solvent also can use arene, for example as benzene,toluene,xylene and ethylbenzene.
Preparation catalyst (a) and (b), the environment that reaches (c) should carry out under blunt gas 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 catalyst to lose activity.And if relate to the process that catalyst must be pre-mixed, its temperature is preferably in 0～250 ℃, and the too high then catalyst of temperature can inactivation, can not lose activity though temperature is crossed low then catalyst itself, and activity is too low does not have the hydrogenation ability on the contrary.
According to the present invention, carry out used the containing the conjugated diene unit polymkeric substance and can make of hydrogenation, anionic polymerization for example, cationic polymerization, radical polymerization, overall polymerization, solution polymerization process, emulsion polymerization method according to the technology of previously known.During polymerization, preferably using organolithium compound is preferable selection as the catalyst initiator, and obtains reactive polymer, and it has carbon lithium ion 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 just comprising-propyl lithium, sec.-propyl lithium, n-Butyl Lithium, isobutyl-lithium, tertiary butyl lithium, n-pentyl lithium, phenyl lithium, tolyl lithium etc.The hydrocarbon polymer of two lithiums for example 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 of 4-, 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 the institute desire obtains polymkeric substance.
The term of employed among the present invention " containing the conjugated diene unit polymkeric substance " look like for being monomer institute polymeric homopolymer or multipolymer with the conjugated diolefine, and the end of molecular chain has active group or do not have active group.Active group is meant the free radical of carbon, the anion-radicals of carbon alkalimetal ion, the cation radical of carbon.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, the 3-pentadiene, 2-methyl 1,3-pentadiene, 1,3-hexadiene, 4,5-diethyl-1,3-octadiene, 3-butyl-1,3-octadiene and composition thereof, divinyl wherein, isoprene is preferable selection with (mixture of divinyl, isoprene).
Be applicable to styrene-ethylene-butylene-styrene (SEBS) segmented copolymer that hydrogenated styrene of the present invention/the butadienecopolymer the best is, hydrogenated styrene/isoprene copolymer the best is styrene-ethylene-propylene-styrene (SEPS) segmented copolymer, and hydrogenated styrene/(divinyl/isoprene mixture) multipolymer the best is styrene-ethylene-ethylene-propylene-vinylbenzene (SEEPS) segmented copolymer
According to the polymkeric substance preferred molecular weight scope that contains conjugated diene unit before the hydrogenation of the present invention is 1000 to 1000000.
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, alpha-methyl styrene, 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 (1) butadiene/styrene copolymers and (2) isoprene/styrol copolymer (3) divinyl/isoprene/cinnamic multipolymer.
In addition, can in the system that contains the conjugated diene unit polymkeric substance, add a kind of tertiary amine compound or ether compound, to improve the vinyl structure of conjugated diene unit.Compounds suitable for use comprises general tertiary amine compound, tetrahydrochysene Furans or Anaesthetie Ether etc.
The metered proportions of hydrogenation catalyst among the present invention (a), the conjugated diene unit polymkeric substance that contains with respect to 100g adds 0.0001 to 50mmole promptly enough, surpasses the 50mmole consumption and carries out, and do not meet economic benefit, and the metering that adds is too high, will make the program that needs to remove catalyst.The preferable consumption of hydrogenation catalyst (a) is that the conjugated diene unit polymkeric substance that contains of every 100g adds 0.002 to 10mmole.
The mole ratio of catalyst among the present invention (b) and catalyst (a) falls in 0.1～50 the scope preferable.If its mole 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 mole ratio can cause the step that the removal catalyst must be arranged greater than 50, and is easy to generate unnecessary secondary reaction, hinder the carrying out of hydrogenation on the contrary.The preferable mole ratio of catalyst (b) and catalyst (a) is between 1 to 15.
The mole ratio of catalyst among the present invention (c) and catalyst (a), preferable between falling into 0.1 to 50.If molar ratio is lower than 0.1, the ability of activation catalyst (a) can't be arranged, it is suitable not good that its relative hydrogenation efficiency seems.The mole ratio can produce unnecessary secondary reaction thing if surpass 50, causes the rapid decline of hydrogenation efficiency on the contrary, and the action of removing catalyst still must be arranged.
The temperature of reaction of hydrogenation of the present invention can be carried out in 0 ℃ to 250 ℃ 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 catalyst (a), and its practice does not also meet economic benefit.If the temperature that is higher than 250 ℃ is carried out, can cause the phenomenon of catalyst inactivation, 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 200 ℃.
The hydrogen pressure of preferable hydrogenization is 1Kg/cm 2To 150Kg/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 150Kg/cm 2The time, hydrogenation temperature rises and stops hydrogenation fast.Better hydrogenation pressure with 1 to 50Kg/cm 2Be advisable.Under above-mentioned hydrogenation conditions, the consumption of catalyst can successively decrease along with the increase of hydrogen pressure, and in order to reach the effect that reduces the catalyst amount, it is good can selecting higher hydrogenation pressure.
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 that will contain the conjugated diene unit polymkeric substance 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 diene unit can be stable reach more than 50%, even can reach to more than 90%, and the degree of hydrogenation of the two keys of aromatic hydrocarbon phenyl ring even can be to below 10% below 30% in the vinyl aromatic hydrocarbons unit.This shows that catalyst composition used in the present invention has very good catalyst selectivity.The hydrogenation turnover ratio is understood at the partly available infrared spectrum analysis of conjugated diene unit, 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 hydrogenating polymer containing conjugated diene unit can be arranged, quite gratifying hydrogenation effect is arranged.And most catalyst 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 capable.
One big characteristic of catalyst composition of the present invention is the use of hydrogenation accelerator (b), the existence of this thing can reach the effect of stablizing other catalyst and promoting other catalyst activity, so after containing catalyst composition adding of the present invention in the conjugated diene unit polymkeric substance, can store for some time under the condition of blunt gas gas still has suitable activity, this time generally can reach to more than 1 hour, and reproducibility is very good, another characteristic is the existence of this thing, can impel this catalyst to be combined under the higher temperature of reaction, still have quite high catalyst activity, do not cause catalyst to lose activity, quite be fit to the commercial production demand because of temperature of reaction is too high.
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.
The preparation of embodiment 1:SBS co-polymer
Have in the sleeve pipe reactor of agitator in 10L, the hexanaphthene of filling 5400 grams, the n-Butyl Lithium (n-butyl lithium) of 7.4mmole and the tetrahydrochysene Furans of 252mmole, and, under 45 ℃, carry out polyreaction in the vinylbenzene that wherein add 96 grams.The 1,3-butadiene that adds 400 grams after this reaction again reacts, and the vinylbenzene that adds 96 grams after the reaction again continues to aggregate into a kind of solid content 9.5 to 9.9%, the triblock copolymer compound of the SBS (styrene-butadiene-styrene) of molecular weight 23 to 250,000.
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 of 2L, remain under the environment of nitrogen, adding poly-(diethyl) siloxanes (25 ℃ of the about 150cp at of viscosity) of 0.22mmole and 0.32mmole isobutyl-lithium under room temperature respectively fills part and stirs, being pre-mixed two (normal-butyl cyclopentadienyl) titanium dichloride of 0.16mmole and the toluene solvant of 20ml in addition treats to dissolve fully, add the 0.66mmole triethyl aluminum again, add again in the SBS polymkeric substance of above-mentioned preparation, in wherein being blown into hydrogen, making partly, pressure reaches 25Kg/cm 2, under 100 ℃, carry out hydrogenization.Hydrogenation ratio after 4 hours can arrive 85%.
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 of 2L, remain under the environment of nitrogen, add entry and make terminator, addition is 1.4mmole, adding poly-(dimethyl) siloxanes (25 ℃ of the about 300cpat of viscosity) of 0.22mmole and 0.96mmole tertiary butyl lithium under room temperature respectively fills part and stirs, being pre-mixed two (the 2-ethylhexyl cyclopentadienyl) titanium dichloride of 0.16mmole and the toluene solvant of 20ml in addition treats to dissolve fully, 1.0mmole diethylaluminum chloride add again in the SBS polymkeric substance of above-mentioned preparation, in wherein being blown into hydrogen, making partly, pressure reaches 25Kg/cm 2, can arrive 96% in carrying out the hydrogenation ratio of hydrogenization after 8 hours under 100 ℃.
Embodiment 4
Get the polymers soln 1000g of the SBS triblock copolymer of preparation among the embodiment 1, move in the withstand voltage hydrogenation groove of 2L, remain under the environment of nitrogen, the methyl alcohol that adds 1.4mmole is made terminator, adding poly-(dimethyl) siloxanes (the about 13000cp at25 of viscosity ℃) of 0.06mmole and 0.90mmole isobutyl-lithium under room temperature respectively fills part and stirs, being pre-mixed two (normal-butyl cyclopentadienyl) titanium dichloride of 0.06mmole and the toluene solvant of 20ml in addition treats to dissolve fully, 0.25mmole triethyl aluminum add again in the SBS polymkeric substance of above-mentioned preparation, in wherein being blown into hydrogen, making partly, pressure reaches 25Kg/cm 2, can arrive 98% in carrying out the hydrogenation ratio of hydrogenization after 16 hours under 100 ℃.
Embodiment 5
Get the polymers soln 1000g of the SBS triblock copolymer of preparation among the embodiment 1, move in the withstand voltage hydrogenation groove of 2L, remain under the environment of nitrogen, adding poly-(dimethyl) siloxanes (25 ℃ of the about 25000cp at of viscosity) of 0.11mmole and 0.16mmole n-Butyl Lithium under room temperature respectively fills part and stirs, being pre-mixed two (cyclopentadienyl) titanium dichloride of 0.08mmole and the toluene solvant of 20ml in addition treats to dissolve fully, add again in the SBS polymkeric substance of above-mentioned preparation, in wherein being blown into hydrogen, making partly, pressure reaches 25Kg/cm 2, under 100 ℃, carry out hydrogenization.After 2 hours, record the hydrogenation ratio of hydrogenation ratio arrival after 76%, 4 hour and can arrive 96%.
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 4 hours, can find that the crest that above-mentioned wavelength place manifests significantly disappears, the hydrogenation ratio (the single bonded hydrogenation ratio of 1,3-butadiene) that measure this moment is 96%.The data preparation of hydrogenation is in table 1.
Embodiment 6
Get the polymers soln 1000g of the SBS triblock copolymer of preparation among the embodiment 1, move in the withstand voltage hydrogenation groove of 2L, remain under the environment of nitrogen, under room temperature, end the activity of multipolymer with the water of 1.23mmole, adding poly-(dimethyl) siloxanes (the about 20cp at25 of viscosity ℃) of 0.11mmole and 0.16mmole n-Butyl Lithium then respectively fills part and stirs, be pre-mixed two (cyclopentadienyl) titanium dichloride of 0.08mmole and the toluene solvant of 20ml in addition and treat to dissolve fully back adding 0.50mmole triethyl aluminum, add again in the SBS polymkeric substance of above-mentioned preparation, in wherein being blown into hydrogen, making partly, pressure reaches 25Kg/cm 2, under 100 ℃, carry out hydrogenization.Hydrogenation ratio after 4 hours can arrive 97%.The data preparation of hydrogenation is in table 1.
Embodiment 7
Get the polymers soln 1000g of the SBS triblock copolymer of preparation among the embodiment 1, move in the withstand voltage hydrogenation groove of 2L, remain under the environment of nitrogen, poly-(dimethyl) siloxanes (25 ℃ of the about 40000cp at of viscosity) that adds 0.11mmole fills part and stirs, be pre-mixed two (cyclopentadienyl) titanium dichloride of 0.08mmole and the diethylaluminum chloride of 0.4mmole in addition, treat to dissolve fully, add again in the SBS polymkeric substance of above-mentioned preparation, in wherein being blown into hydrogen, making partly, pressure reaches 25Kg/cm 2, under 100 ℃, carry out hydrogenization.Hydrogenation ratio after 5 hours can arrive 90%.The data preparation of hydrogenation is in table 1.
Embodiment 8
Get the polymers soln 1000g of the SBS triblock copolymer of preparation among the embodiment 1, move in the withstand voltage hydrogenation groove of 2L, remain under the environment of nitrogen, poly-(dimethyl) siloxanes (25 ℃ of the about 150cp at of viscosity) that adds 0.11mmole fills part and stirs, be pre-mixed two (cyclopentadienyl) titanium dichloride of 0.055mmole and the triethyl aluminum of 0.36mmole in addition, treat to dissolve fully, add again in the SBS polymkeric substance of above-mentioned preparation, in wherein being blown into hydrogen, making partly, pressure reaches 25Kg/cm 2, under 100 ℃, carry out hydrogenization.Hydrogenation ratio after 5 hours can arrive 93%.The data preparation of hydrogenation is in table 1.
Embodiment 9
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, poly-(dimethyl) siloxanes (25 ℃ of the about 300cp at of viscosity) of adding 0.11mmole and 0.16mole n-Butyl Lithium fill part and stir, be pre-mixed two (cyclopentadienyl) titanium dichloride of 0.055mmole and the triisobutyl aluminium of 0.33mmole in addition, treat to dissolve fully, add again in the SBS polymkeric substance of above-mentioned preparation, in wherein being blown into hydrogen, making partly, pressure reaches 25Kg/cm 2, under 100 ℃, carry out hydrogenization.Hydrogenation ratio after 24 hours can arrive 96%.The data preparation of hydrogenation is in table 1.
Embodiment 10
Get the polymers soln 1000g of the SBS triblock copolymer of preparation among the embodiment 1, move in the withstand voltage hydrogenation groove of 2L, remain under the environment of nitrogen, poly-(dimethyl) siloxanes (25 ℃ of the about 200cp at of viscosity) that adds 0.11mmole fills part and stirs, be pre-mixed two (cyclopentadienyl) titanium dichloride of 0.13mmole and the triethyl aluminum of 0.82mmole in addition, treat to dissolve fully, add again in the SBS polymkeric substance of above-mentioned preparation, in wherein being blown into hydrogen, making partly, pressure reaches 25Kg/cm 2, under 100 ℃, carry out hydrogenization.Hydrogenation ratio after 4 hours can arrive 96%.The data preparation of hydrogenation is in table 1.
Embodiment 11
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, poly-(dimethyl) siloxanes (25 ℃ of the about 150cp at of viscosity) that adds 0.15mmole fills part and stirs, be pre-mixed two (cyclopentadienyl) titanium dichloride of 0.1mmole and the triethyl aluminum of 0.4mmole in addition, treat to dissolve fully, add again in the SBS polymkeric substance of above-mentioned preparation, in wherein being blown into hydrogen, making partly, pressure reaches 25Kg/cm 2, under 100 ℃, carry out hydrogenization.Hydrogenation ratio after 4 hours can arrive 97%.The data preparation of hydrogenation is in table 1.
Embodiment 12
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, poly-(dimethyl) siloxanes (25 ℃ of the about 3000cp at of viscosity) that adds 0.2mmole fills part and stirs, be pre-mixed two (cyclopentadienyl) titanium dichloride of 0.07mmole and the triethyl aluminum of 1.0mmole in addition, treat to dissolve fully, add again in the SBS polymkeric substance of above-mentioned preparation, in wherein being blown into hydrogen, making partly, pressure reaches 25Kg/cm 2, under 100 ℃, carry out hydrogenization.Hydrogenation ratio after 4 hours can arrive 96%.The data preparation of hydrogenation is in table 1.
Embodiment 13
Get the polymers soln 1000g of the SBS triblock copolymer of preparation among the embodiment 1, move in the withstand voltage hydrogenation groove of 2L, remain under the environment of nitrogen, gather (dimethyl) siloxanes (25 ℃ of the about 150cp at of viscosity) in 10 milliliters hexanaphthene in allotment 0.07mmole under the room temperature, two 0.03mmole (cyclopentadienyl) titanium dichloride in 10 milliliters hexanaphthene and the triisobutyl aluminium of 0.15mmole at 10 milliliters cyclohexane solution, add respectively in the SBS polymers soln of above-mentioned preparation, in wherein being blown into hydrogen, making partly, pressure reaches 25Kg/cm 2, under 100 ℃, carry out hydrogenization.Hydrogenation ratio after 24 hours can arrive 97%.The data preparation of hydrogenation is in table 1.
Embodiment 14
Get the polymers soln 1000g of the SBS triblock copolymer of preparation among the embodiment 1, move in the withstand voltage hydrogenation groove of 2L, remain under the environment of nitrogen, in the poly-hexanaphthene of (dimethyl) siloxanes 0.15mmole of allotment under the room temperature at 10ml, be pre-mixed poly-(dimethyl) siloxanes (25 ℃ of the about 50cp at of viscosity) 0.15mmole and 0.2mmole n-Butyl Lithium in addition in the hexanaphthene of 10ml, and the triisobutyl aluminium of two (cyclopentadienyl) titanium dichloride of 0.08mmole and 0.4mmole is at 20 milliliters hexanaphthene, add respectively in the SBS polymkeric substance of above-mentioned preparation, in wherein being blown into hydrogen, making partly, pressure reaches 25Kg/cm 2, under 100 ℃, carry out hydrogenization.Hydrogenation ratio after 4 hours can arrive 97%.The data preparation of hydrogenation is in table 1.
Embodiment 15
As the identical method of embodiment 10, in the poly-hexanaphthene of (diethyl) siloxanes (25 ℃ of the about 150cp at of viscosity) of allotment 0.13mmole under the room temperature at 10ml, be pre-mixed two (cyclopentadienyl) titanium dichloride of 0.08mmole in addition in 10 milliliters hexanaphthene suspended substance, and the triisobutyl aluminium of 0.4mmole is at 10 milliliters hexanaphthene, add respectively in the SBS polymers soln of above-mentioned preparation, in wherein being blown into hydrogen, making partly, pressure reaches 40Kg/cm 2, under 100 ℃, carry out hydrogenization.Hydrogenation ratio after 2 hours can arrive 97%.The data preparation of hydrogenation is in table 1.
Embodiment 16
As the identical method of embodiment 10, but will gather (diethyl) siloxanes and change poly-(methyl epoxy group(ing)) siloxanes (25 ℃ of the about 100cp at of viscosity) of 0.165mmole in the hexanaphthene of 10ml, be pre-mixed two (cyclopentadienyl) titanium dichloride of 0.09mole in addition in 10 milliliters hexanaphthene suspended substance, and the triisobutyl aluminium of 0.45mmole is at 10 milliliters hexanaphthene, add respectively in the SBS polymers soln of above-mentioned preparation, in wherein being blown into hydrogen, making partly, pressure reaches 25Kg/cm 2, under 100 ℃, carry out hydrogenization.After 1 hour, record the hydrogenation ratio of hydrogenation ratio arrival after 90%, 2 hour and can arrive 96%.The data preparation of hydrogenation is in table 1.
Embodiment 17
As the same method of embodiment 10, but will gather (dimethyl) siloxanes and change poly-(aminomethyl phenyl) siloxanes (25 ℃ of the about 50cp at of viscosity) of 0.2mmole in the hexanaphthene of 10ml, be pre-mixed two (cyclopentadienyl) titanium dichloride of 0.09mole in addition in 10 milliliters hexanaphthene suspended substance, and the triisobutyl aluminium of 0.45mmole is at 10 milliliters hexanaphthene, add respectively in the SBS polymers soln of above-mentioned preparation, in wherein being blown into hydrogen, making partly, pressure reaches 25Kg/cm 2, carry out hydrogenization in 100 ℃.Hydrogenation ratio can reach 96% after 3 hours.The data preparation of hydrogenation is in table 1.
Embodiment 18
As the same method of embodiment 10, but will gather poly-ring (dimethyl) siloxanes (25 ℃ of the about 250cp at of viscosity) that (dimethyl) siloxanes changes 0.3mmole in the hexanaphthene of 10ml, be pre-mixed two (cyclopentadienyl) titanium dichloride of 0.08mmole in addition in 10 milliliters hexanaphthene suspended substance, and the triisobutyl aluminium of 0.45mmole is at 10 milliliters hexanaphthene, add respectively in the SBS polymers soln of above-mentioned preparation, in wherein being blown into hydrogen, making partly, pressure reaches 25Kg/cm 2, carry out hydrogenation in 100 ℃.After 1 hour, hydrogenation ratio can reach 95% after recording hydrogenation ratio and arriving hydrogenation ratio after 65%, 2 hour and can arrive 86%, 3 hour.The data preparation of hydrogenation is in table 1.
Embodiment 19
As the same method of embodiment 10, but will gather (dimethyl) siloxanes and change poly-(methylbenzene methyl) siloxanes (25 ℃ of the about 350cp at of viscosity) of 0.275mmole in the hexanaphthene of 10ml, be pre-mixed two (cyclopentadienyl) titanium dichloride of 0.085mmole in addition in 10 milliliters hexanaphthene suspended substance, and the triisobutyl aluminium of 0.8mmole is at 10 milliliters hexanaphthene, add respectively in the SBS polymers soln of above-mentioned preparation, in wherein being blown into hydrogen, making partly, pressure reaches 25Kg/cm 2, carry out hydrogenization in 100 ℃.After 1 hour, hydrogenation ratio can reach 96% after recording hydrogenation ratio and arriving hydrogenation ratio after 65%, 2 hour and can arrive 76%, 3 hour.The data preparation of hydrogenation is in table 1.
Embodiment 20
As the same method of embodiment 10, but will gather (dimethyl) siloxanes and change poly-(methyl carbonyl) siloxanes (25 ℃ of the about 1000cp at of viscosity) of 0.3mmole in the hexanaphthene of 10ml, be pre-mixed two (cyclopentadienyl) titanium dichloride of 0.09mmole in addition in 10 milliliters hexanaphthene suspended substance, and the triisobutyl aluminium of 0.45mmole is at 10 milliliters hexanaphthene, add respectively in the SBS polymers soln of above-mentioned preparation, in wherein being blown into hydrogen, making partly, pressure reaches 25Kg/cm 2, carry out hydrogenization in 100 ℃.Hydrogenation ratio can reach 96% after 3 hours.The data preparation of hydrogenation is in table 1.
Embodiment 21
As the same method of embodiment 10, but will gather (dimethyl) siloxanes and change poly-(propyl group phenyl) siloxanes (25 ℃ of the about 1500cp at of viscosity) of 0.35mmole in the hexanaphthene of 10ml, be pre-mixed two (cyclopentadienyl) titanium dichloride of 0.08mmole in addition in 10 milliliters hexanaphthene suspended substance, and the triisobutyl aluminium of 0.48mmole is at 10 milliliters hexanaphthene, add respectively in the SBS polymers soln of above-mentioned preparation, in wherein being blown into hydrogen, making partly, pressure reaches 25Kg/cm 2, in carrying out hydrogenization under with 100 ℃ under this condition.After 1 hour, hydrogenation ratio can reach 96% after recording hydrogenation ratio and arriving hydrogenation ratio after 35%, 2 hour and can arrive 76%, 3 hour.The data preparation of hydrogenation is in table 1.
Embodiment 22
As the same method of embodiment 10, but will gather poly-ring (diethyl) siloxanes (25 ℃ of the about 800cp at of viscosity) that (dimethyl) siloxanes changes 0.35mmole in the hexanaphthene of 10ml, be pre-mixed two (cyclopentadienyl) titanium dichloride of 0.08mmole in addition in 10 milliliters hexanaphthene suspended substance, and the triisobutyl aluminium of 0.44mmole is at 10 milliliters hexanaphthene, add respectively in the SBS polymers soln of above-mentioned preparation, in wherein being blown into hydrogen, making partly, pressure reaches 25Kg/cm 2, in carrying out hydrogenization under with 100 ℃ under this condition.Hydrogenation ratio can reach 96% after hydrogenation ratio after 2 hours can arrive 86%, 3 hour.The data preparation of hydrogenation is in table 1.
Embodiment 23
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, the step of adding catalyst is with embodiment 3, add respectively in the SBS polymkeric substance of above-mentioned preparation, under the environment of nitrogen, place after 48 hours, in wherein being blown into hydrogen again, making partly, pressure reaches 25Kg/cm 2, under 100 ℃, carry out hydrogenization.After 30 minutes, hydrogenation ratio can reach 96% after recording hydrogenation ratio and arriving hydrogenation ratio after 62%, 1 hour and arrive 85%, 1.5 hour, and the data preparation of hydrogenation is in table 1.
Embodiment 24
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 poly-(dimethyl) siloxanes (25 ℃ of the about 5000cp at of the viscosity) hexanaphthene of 0.45mmole of allotment under the room temperature at 10ml, be pre-mixed poly-(dimethyl) siloxanes 0.45mmole and 0.8mmole n-Butyl Lithium in addition in the hexanaphthene of 10ml, and the triisobutyl aluminium of two (indenyl) titanium dichloride of 0.24mmole and 1.6mmole is at 20 milliliters hexanaphthene, add respectively in the SBS polymkeric substance of above-mentioned preparation, in wherein being blown into hydrogen, making partly, pressure reaches 25Kg/cm 2, under 100 ℃, carry out hydrogenization.Hydrogenation ratio after 4 hours can arrive 96%.The data preparation of hydrogenation is in table 1.
Embodiment 25
Get the polymers soln 1000g of the SBS triblock copolymer of preparation among the embodiment 1, move in the withstand voltage hydrogenation groove of 2L, remain under the environment of nitrogen, adding poly-(dimethyl) siloxanes (25 ℃ of the about 1500cp at of viscosity) of 0.30mmole and 1.50mmole tertiary butyl lithium under room temperature respectively fills part and stirs, being pre-mixed two (cyclopentadienyl) titanium dichloride of 0.20mmole and the toluene solvant of 20ml in addition treats to dissolve fully, 1.8mmole the cyclohexane solution of two isobutyl-magnesium add again in the SBS polymkeric substance of above-mentioned preparation, in wherein being blown into hydrogen, making partly, pressure reaches 25Kg/cm 2, can arrive 91% in carrying out the hydrogenation ratio of hydrogenization after 8 hours under 100 ℃.
The preparation of embodiment 26:SIS co-polymer
Have in the double pipe heater of agitator in 10L, the hexanaphthene of filling 5400 grams, n-Butyl Lithium (n-butyl lithium) and the 9.5mmole THF (tetrahydrochysene Fu Nan) of 7.4mmole, and, under 45 ℃, carry out polyreaction in the vinylbenzene that wherein adds 96 grams.The Isoprene that add 445 grams in this reaction back react, and continue to aggregate into the triblock copolymer compound of a kind of SIS (styrene-isoprene-phenylethene) of solid content 9.5 to 9.9% molecular weight 22 to 240,000 after the reaction again in the vinylbenzene that add 96 grams.
Embodiment 27
Get the polymers soln 1000g of the SIS triblock copolymer of preparation among the embodiment 26, move in the withstand voltage hydrogenation groove of 2L, remain under the environment of nitrogen, gather (dimethyl) siloxanes (25 ℃ of the about 1500cp at of viscosity) in 10 milliliters hexanaphthene in allotment 0.15mmole under the room temperature, two 0.1mmole (cyclopentadienyl) titanium dichloride in 10 milliliters hexanaphthene and the triisobutyl aluminium of 0.5mmole at 10 milliliters cyclohexane solution, add respectively in the SIS polymers soln of above-mentioned preparation, in wherein being blown into hydrogen, making partly, pressure reaches 25Kg/cm 2, under 100 ℃, carry out hydrogenization.After 6 hours 3,4-vinyl hydrogenation ratio can arrive 100%, 1, and the hydrogenation ratio of the two key units of 4-reaches 92%.
Fig. 3 show before the hydrogenation and hydrogenation after the infrared spectrum of SIS polymkeric substance.This spectrum shows, the SIS triblock copolymer is before hydrogenation not, in wavelength 880cm -1Find the functional group place of 3.4-vinyl double bond, in wavelength 830cm -1Find 1.4 pairs of key places.After the hydrogenation 6 hours, the crest that can above-mentioned wavelength place manifests significantly disappears, measure this moment 3,4-vinyl hydrogenation ratio is 100%, 1, the hydrogenation ratio of the two key units of 4-is 92%.
Comparing embodiment
Below enumerating several comparing embodiments is used for doing a comparison with embodiments of the invention, it should be noted that, the employed hydrogenation catalyst composition of these comparing embodiments system does not comprise hydrogenation catalyst of the present invention (b), to further specify its feature of hydrogenation catalyst composition of the present invention and advantage.
Comparing embodiment 1
As the identical method of embodiment 13, but add poly-(dimethyl) siloxanes.Be pre-mixed two (cyclopentadienyl) titanium dichloride of 0.08mmole in 10 milliliters hexanaphthene suspended substance, and the triisobutyl aluminium of 0.4mmole is at 10 milliliters hexanaphthene, add respectively in the SBS polymers soln of above-mentioned preparation, in wherein being blown into hydrogen, making partly, pressure reaches 25Kg/cm 2, under 100 ℃, 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 5 hours, 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, import hydrogen and stir 30 minutes in advance, but do not add poly-(dimethyl) siloxanes.Be pre-mixed two (cyclopentadienyl) titanium dichloride of 0.08mmole in 10 milliliters hexanaphthene suspended substance, and the triisobutyl aluminium of 0.4mmole is at 10 milliliters hexanaphthene, add respectively in the SBS polymers soln of above-mentioned preparation, in wherein being blown into hydrogen, making partly, pressure reaches 25Kg/cm 2, under 100 ℃, carry out hydrogenization.After the hydrogenation 5 hours, 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 18%.The data preparation of hydrogenation is in table 1.
Comparing 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 of 2L, importing hydrogen stirred 30 minutes in advance, method as embodiment 13, but will gather (dimethyl) siloxanes and change the 0.22mmole n-Butyl Lithium into, be pre-mixed two (cyclopentadienyl) titanium dichloride of 0.08mmole in 10 milliliters hexanaphthene suspended substance, and the triisobutyl aluminium of 0.5mmole is at 10 milliliters hexanaphthene, add respectively in the SBS polymers soln of above-mentioned preparation, make the part pressure of hydrogen reach 25Kg/cm 2, carry out hydrogenation in 100 ℃.After 2 hours, record the hydrogenation ratio of hydrogenation ratio arrival after 25%, 5 hour and can arrive 27%.
Comparing embodiment 4
Get the polymers soln 1000g of the SBS triblock copolymer of preparation among the embodiment 1, move in the withstand voltage hydrogenation groove of 2L, method as embodiment 13, but will gather (dimethyl) siloxanes and change 0.22mmole 1 into, 1,3,3-tetramethyldisiloxane (compound that contains Si-H), be pre-mixed two (cyclopentadienyl) titanium dichloride of 0.09mmole in 10 milliliters hexanaphthene suspended substance, and the triisobutyl aluminium of 0.44mmole is at 10 milliliters hexanaphthene, add respectively in the SBS polymers soln of above-mentioned preparation, make the part pressure of hydrogen reach 25Kg/cm 2, carry out hydrogenation in 100 ℃.After 3 hours, recording hydrogenation ratio, to arrive the hydrogenation ratio that the hydrogenation ratio after 55%, 5 hour can reach after 57%, 8 hour still be 57%.This catalyst is combined under the high hydrogenation temperature and easily loses activity because of too high temperature of reaction makes catalyst.Can significantly find out the catalyst combination that United States Patent (USP) 6313230 and People's Republic of China's patent 00107660.4 are declared, under the environment of high temperature nitrogen, be easy to lose catalyst activity, and be not suitable for the production of continous way processing procedure.The data preparation of hydrogenation is in table 1
Comparing embodiment 5
Get the polymers soln 1000g of the SBS triblock copolymer of preparation among the embodiment 1, move in the withstand voltage hydrogenation groove of 2L, method as embodiment 23, but will gather (dimethyl) siloxanes and change 0.22mmole 1 into, 1,3,3-tetramethyldisiloxane (compound that contains Si-H) is pre-mixed two (cyclopentadienyl) titanium dichloride of 0.09mmole in 10 milliliters hexanaphthene suspended substance, and after the toluene solvant of 20ml treats to dissolve fully, the triisobutyl aluminium that adds 0.44mmole again, add respectively in the SBS polymers soln of above-mentioned preparation, under the environment of nitrogen, place after 48 hours, in wherein being blown into hydrogen again, make pressure reach 25Kg/cm 2, carry out hydrogenation in 100 ℃.After 3 hours, recording hydrogenation ratio the hydrogenation ratio 25%, 8 hour after of hydrogenation ratio arrival after 25%, 5 hour still is 25%.This catalyst is combined under the long storage time catalyst is lost activity.Can find out significantly that United States Patent (USP) 6313230 and People's Republic of China's patent 00107660.4 alleged catalyst make up, and are easy to lose catalyst activity, and are not suitable for the production of continous way processing procedure under long storage time environment.
The data preparation of hydrogenation is in table 1.
Comparing embodiment 6
As the identical method of embodiment 13, but add poly-(dimethyl) siloxanes.Be pre-mixed two (indenyl) titanium dichloride of 0.08mmole in 10 milliliters hexanaphthene suspended substance, and the triisobutyl aluminium of 0.4mmole is at 10 milliliters hexanaphthene, add respectively in the SBS polymers soln of above-mentioned preparation, in wherein being blown into hydrogen, making partly, pressure reaches 25Kg/cm 2, under 100 ℃, carry out hydrogenization, after 3 hours, recording hydrogenation ratio, to arrive the hydrogenation ratio that the hydrogenation ratio after 45%, 5 hour can reach after 57%, 8 hour still be 58%, this catalyst is combined under this hydrogen pressure, fails to reach ideal hydrogenation situation.
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 (%) Butadiene unit hydrogenation ratio (%) Phenyl ring hydrogenation ratio (%)
Embodiment 2 12.6 2.5 85 ＜5
Embodiment 3 3.2 0.8 96 ＜5
Embodiment 4 2.0 0.2 98 ＜5
Embodiment 5 2.7 0.2 96 ＜5
Embodiment 6 2.6 0.4 97 ＜5
Embodiment 7 8.2 1.8 90 ＜5
Embodiment 8 5.7 1.3 93 ＜5
Embodiment 9 3.1 0.8 96 ＜5
Embodiment 10 3.4 0.3 96 ＜5
Embodiment 11 3.4 1 97 ＜5
Embodiment 12 3.1 0.9 96 ＜5
Embodiment 13 2.2 0.8 97 ＜5
Embodiment 14 2.2 0.8 97 ＜5
Embodiment 15 2.2 0.8 97 ＜5
Embodiment 16 3.2 0.8 96 ＜5
Embodiment 17 3.3 0.8 96 ＜5
Embodiment 18 4.0 0.8 95 ＜5
Embodiment 19 3.4 0.8 96 ＜5
Embodiment 20 3.2 0.8 96 ＜5
Embodiment 21 3.0 0.8 96 ＜5
Embodiment 22 3.2 0.8 96 ＜5
Embodiment 23 3.0 0.8 96 ＜5
Embodiment 24 3.2 1.0 96 ＜5
Embodiment 25 7.7 1.0 91 ＜5
Comparing embodiment 1 76 0.9 23 ＜5
Comparing embodiment 2 81 1.0 18 ＜5
Comparing embodiment 3 72 0.9 27 ＜5
Comparing embodiment 4 54 2.7 43 ＜5
Comparing embodiment 5 70 5.9 25 ＜5
Comparing embodiment 6 38 3.9 58 ＜5
As shown in Table 1, utilize hydrogenation catalyst composition of the present invention to contain the hydrogenation of conjugated diene unit polymkeric substance, by finding after formula conversion infrared spectrometer (Perkin Elmer) detection suddenly, the trans double bond residual quantity that hydrogenant contains the conjugated diene unit polymkeric substance is lower than 5%, and 1,2-vinyl double bond residual quantity is lower than 5%, and the 1,3-butadiene hydrogenation ratio is greater than 80% (its method of calculation of embodiment 2～24-are as follows); 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 system to 1,3-butadiene is lower than below 25%.Method of calculation:
Figure C20061000708300432
T is functional group's optical density, T oBe functional group's baseline absorbance, the hydrogenation ratio of butadiene unit is (100-1,4Trans residual quantity %-1, a 2vinyl residual quantity).
Figure C20061000708300433
Figure C20061000708300434
T is functional group's optical density, T oBe functional group's baseline absorbance
Embodiment 28-33
Hydrogenant catalyst and metering 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) Butadiene unit hydrogenation ratio (%)
Embodiment 28 60 5 8 65
Embodiment 29 60 10 8 94
Embodiment 30 80 10 6 97
Embodiment 31 100 25 6 97
Embodiment 32 150 10 6 97
Embodiment 33 200 10 6 98
In sum, hydrogenation catalyst composition disclosed in this invention has superior hydrogenation ability for conjugated diolefin polymer, so only need 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, the activity of catalyst still has satisfactory stability and reproducibility, quite meets economic benefit.Moreover, catalyst composition of the present invention is in still having hydrogenation activity highly in the temperature system widely, therefore the method for hydrogenating polymer containing conjugated diene unit of the present invention can carried out under the temperature system widely, lose the activity of catalyst, therefore quite be adapted at operating under the operational condition of continous way production because of too high hydrogenation heat.
Though the present invention describes as above with preferred embodiment; right its is not in order to restriction the present invention, anyly has the knack of this technician, without departing from the spirit and scope of the present invention; change and retouching when doing, so protection scope of the present invention is when being as the criterion with the content that claim was defined.

Claims (46)

1. the catalyst composition of a hydrogenating polymer containing conjugated diene unit, this contains the homopolymer that the conjugated diene unit polymkeric substance is a conjugated diolefine or the multipolymer of conjugated diene unit and vinylaromatic hydrocarbon, and this hydrogenation catalyst composition comprises following hydrogenation catalyst:
(a) titanium compound shown in formula (I) or its mixture:
Figure C2006100070830002C1
Formula (I)
Wherein
R 1, R 2Be identical or different substituting group, and be hydrogen, halogen atom, C 1～C 8Alkyl, C 1～C 8Alkoxyl group, C 6～C 12Cycloalkyl, phenyl, phenoxy group, C 7～C 10Alkoxy aryl, C 7～C 10Aralkyl, carboxyl ,-CH 2P (phenyl) 2,-CH 2Si (C 1～C 5Alkyl) 3Or-P (phenyl) 2
A represents cyclopentadienyl, fluorenyl, indenyl or derivatives thereof; Described derivative is that on the ring of indenyl, fluorenyl or cyclopentadienyl one or several hydrogen are replaced by a substituting group;
(b) for comprising compound or its both mixture shown in formula (II) or formula (III) at least:
Figure C2006100070830002C2
Formula (II) formula (III);
Wherein formula (II) is a chain-like structure, and formula (III) is a ring texture, wherein R 3Be C 1～C 12Alkyl, X 1, X 2Be C 1～C 12Alkyl, C 1～C 12Epoxy alkyl, aromatic base or C 1～C 12Alkylaryl, n＞1, m＞2;
(c) organometallic compound.
2. composition as claimed in claim 1 is characterized in that, wherein this hydrogenation catalyst a is the halogenide of two (cyclopentadienyl and derivative thereof) titaniums; Described cyclopentadienyl derivative is that on the ring of cyclopentadiene one or several hydrogen are replaced by a substituting group.
3. composition as claimed in claim 2, it is characterized in that, wherein this hydrogenation catalyst a is two (cyclopentadienyl) bifluoride titaniums, two (cyclopentadienyl) titanium dichloride, two ((2,4-diphenylphosphine cyclopentadienyl)) bifluoride titanium, two ((2,4-dimethyl phosphine cyclopentadienyl)) bifluoride titanium, two ((2,4-diphenylphosphine cyclopentadienyl)) titanium dichloride, two (cyclopentadienyl) titanium dichloride of dimethoxyization, two ((2,4-dimethyl phosphine cyclopentadienyl)) titanium dichloride, two (cyclopentadienyl) dibrominated titanium, two ((2,4-diphenylphosphine cyclopentadienyl)) dibrominated titanium, two ((2,4-dimethyl phosphine cyclopentadienyl)) dibrominated titanium, two (ethylization cyclopentadienyl) titanium dichloride, two (n-propyl cyclopentadienyl) titanium dichloride, two (normal-butyl cyclopentadienyl) titanium dichloride or two (2-ethylhexyl cyclopentadienyl) titanium dichloride.
4. composition as claimed in claim 1, it is characterized in that, wherein this hydrogenation catalyst a is two (cyclopentadienyl) titaniums of dimethyl, two (cyclopentadienyl) titaniums of dimethoxy, two (cyclopentadienyl) titaniums of diethoxy, diethoxy two ((2,4-diphenylphosphine cyclopentadienyl)) titanium, diethoxy two ((2,4-dimethyl phosphine cyclopentadienyl)) titanium, two phenoxy groups two ((2,4-diphenylphosphine cyclopentadienyl)) two ((2,4-dimethyl phosphine cyclopentadienyl)) titaniums of titanium or two phenoxy groups.
5. composition as claimed in claim 1 is characterized in that, wherein this hydrogenation catalyst a is the halogenide of two (fluorenyl, indenyl or derivatives thereof) titaniums; Described derivative is that on the ring of indenyl, fluorenyl one or several hydrogen are replaced by a substituting group.
6. composition as claimed in claim 5, it is characterized in that wherein this hydrogenation catalyst a is two (fluorenyl) titanium dichloride, two (1-indenyl) titanium dichloride, two (dimethoxy fluorenyl) titanium dichloride, two (fluorenyl) bifluoride titanium, two (indenyl) bifluoride titanium, two (dimethoxy fluorenyl) bifluoride titanium, two (fluorenyl) dibrominated titanium, two (indenyl) dibrominated titanium, two (dimethoxy fluorenyl) titanium or two (indenyl) dibrominated titanium.
7. composition as claimed in claim 1, it is characterized in that wherein this hydrogenation catalyst a is two (fluorenyl) titaniums of dimethyl, two (fluorenyl) titaniums of dimethoxy, two (indenyl) titaniums of dimethoxy, two (dimethoxy fluorenyl) titaniums of dimethoxy, two (fluorenyl) titaniums of two phenoxy groups, two (indenyl) titaniums of two phenoxy groups, two (dimethoxy fluorenyl) titaniums of two phenoxy groups or two (indenyl) titaniums of two phenoxy groups.
8. composition as claimed in claim 1 is characterized in that, wherein this hydrogenation catalyst b is the compound shown in the formula (II), X 1, X 2At least one is C 1～C 12Alkyl or C 1～C 12Epoxy alkyl.
9. composition as claimed in claim 8, it is characterized in that wherein this hydrogenation catalyst b is poly-(dimethyl) siloxanes, poly-(diethyl) siloxanes, poly-(dipropyl) siloxanes, poly-(dibutyl) siloxanes, poly-(diamyl) siloxanes, poly-(dihexyl) siloxanes, poly-(diheptyl) siloxanes, poly-(dioctyl) siloxanes, poly-(dinonyl) siloxanes, poly-(didecyl) siloxanes, poly-(methyl epoxy group(ing)) siloxanes, poly-(ethyl epoxy group(ing)) siloxanes, poly-(propyl epoxy) siloxanes, poly-(butyl epoxy group(ing)) siloxanes, poly-(amyl group epoxy group(ing)) siloxanes, poly-(hexyl epoxy group(ing)) siloxanes or poly-(heptyl epoxy group(ing)) siloxanes.
10. composition as claimed in claim 1 is characterized in that, wherein this hydrogenation catalyst b is the compound shown in the formula (II), and X 1, X 2At least one is aromatic base or C 1～C 12Alkylaryl.
11. composition as claimed in claim 10, it is characterized in that, wherein be poly-(aminomethyl phenyl) siloxanes among this hydrogenation catalyst b, poly-(ethylphenyl) siloxanes, poly-(propyl group phenyl) siloxanes, poly-(butyl phenyl) siloxanes, poly-(amyl group phenyl) siloxanes, poly-(hexyl phenyl) siloxanes, poly-(heptyl phenyl) siloxanes, poly-(octyl phenyl) siloxanes, poly-(nonyl phenyl) siloxanes, poly-(decyl phenyl) siloxanes, poly-(methylbenzene methyl) siloxanes, poly-(ethylbenzyl) siloxanes, poly-(propylbenzene methyl) siloxanes, poly-(butylbenzene methyl) siloxanes, poly-(amylbenzene methyl) siloxanes, poly-(hexyl benzene methyl) siloxanes, poly-(heptyl benzene methyl) siloxanes, poly-(octyl group phenmethyl) siloxanes, poly-(nonyl benzene methyl) siloxanes, poly-(decyl phenmethyl) siloxanes, poly-(methylbenzene ethyl) siloxanes, poly-(ethylbenzene ethyl) siloxanes, poly-(propylbenzene ethyl) siloxanes, poly-(butylbenzene ethyl) siloxanes, poly-(amylbenzene ethyl) siloxanes, poly-(hexyl benzene ethyl) siloxanes, poly-(heptyl benzene ethyl) siloxanes or poly-(octyl group styroyl) siloxanes.
12. composition as claimed in claim 1 is characterized in that, wherein this hydrogenation catalyst b is the compound shown in the formula III, and X 1And X 2Be identical or different C 1～C 12Alkyl or C 1～C 12Cycloalkyloxy.
13. composition as claimed in claim 12, it is characterized in that wherein this hydrogenation catalyst b is poly-ring (dimethyl) siloxanes, poly-ring (diethyl) siloxanes, poly-ring (dipropyl) siloxanes, poly-ring (dibutyl) siloxanes, poly-ring (diamyl) siloxanes, poly-ring (dihexyl) siloxanes, poly-ring (diheptyl) siloxanes, poly-ring (dioctyl) siloxanes, poly-ring (dinonyl) siloxanes, poly-ring (didecyl) siloxanes, poly-ring (methylethyl) siloxanes, poly-ring (methyl-propyl) siloxanes, poly-ring (methyl butyl) siloxanes, poly-ring (methyl amyl) siloxanes, poly-ring (methyl epoxy group(ing)) siloxanes, poly-ring (ethyl epoxy group(ing)) siloxanes, poly-ring (propyl epoxy) siloxanes, poly-ring (butyl epoxy group(ing)) siloxanes, poly-ring (amyl group epoxy group(ing)) siloxanes or poly-ring (hexyl epoxy group(ing)) siloxanes.
14. composition as claimed in claim 1 is characterized in that, wherein this hydrogenation catalyst c is an organometallic compound, comprises organolithium compound R 4Li, organo-magnesium compound R 4R 5Mg, organo-aluminium compound R 4R 5R 6Al or its mixture, wherein R 4Be C 1～C 12Alkyl, C 1～C 12Alkoxyl group, C 6～C 12Aromatic base, C6～C12 alkoxy aryl or hydrogen atom, R5, R6 are identical or different substituting group, and are C1～C1 2Alkyl, C 6～C 12Aromatic base, hydrogen atom or halogen atom, R 4, R 5, R 6Be not methyl simultaneously.
15. the described composition as claim 14 is characterized in that, described mixture is R 4Li and R 4R 5Mg mixture or R 4Li and R 4R 5R 6The Al mixture.
16. composition as claimed in claim 1 is characterized in that, the mol ratio of organometallic compound and titanium compound or its mixture is greater than 1.
17. composition as claimed in claim 14, it is characterized in that, wherein this organo-aluminium compound or its mixture are 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, diethylaluminum chloride, ethylaluminium dichloride, the chlorination tri-propyl aluminum, chlorination dibutyl aluminium, di-isobutyl aluminum chloride, the combination of dichloride butyl aluminium or above-mentioned organo-aluminium compound.
18. composition as claimed in claim 17 is characterized in that, wherein this hydrogenation catalyst c is triisobutyl aluminium and triethyl aluminum.
19. composition as claimed in claim 14, it is characterized in that wherein this organolithium compound or its mixture are the combination of n-propyl lithium, sec.-propyl lithium, n-Butyl Lithium, isobutyl-lithium, tertiary butyl lithium, n-pentyl lithium, phenyl lithium, tolyl lithium or above-mentioned organolithium compound.
20. the composition as claim 19 is stated is characterized in that, wherein this hydrogenation catalyst c is n-Butyl Lithium and isobutyl-lithium.
21. composition as claimed in claim 14, it is characterized in that wherein this organo-magnesium compound or its mixture are the combination of two normal-butyl magnesium, two isobutyl-magnesium, two n-propyl magnesium, two isopropyl-magnesium, two octyl group magnesium, dicyclohexyl magnesium, two 2-ethylhexyl magnesium, normal-butyl isobutyl-magnesium, normal-butyl octyl group magnesium, normal-butyl 2-ethylhexyl magnesium or above-mentioned organo-magnesium compound.
22. composition as claimed in claim 14 is characterized in that, for using organo-aluminium compound R simultaneously 4R 5R 6Al and organolithium compound R 4The mixture of Li.
23. composition as claimed in claim 1 is characterized in that, it is right that the terminal group that contains conjugated diene unit polymkeric substance itself has active carbon-lithium ion.
24. composition as claimed in claim 1 is characterized in that, the terminal group that contains conjugated diene unit polymkeric substance itself has active carbon-lithium ion to stopping activity through deactivators.
25. composition as claimed in claim 24 is characterized in that, deactivators comprises: water, alcohols, organic acid, ketone or Organohalogen compounds.
26. composition as claimed in claim 1 is characterized in that, contains the conjugated diene unit polymkeric substance and be the polymkeric substance by anionoid polymerization, radical polymerization, polycoordination or cationoid polymerisation gained.
27. composition as claimed in claim 1 is characterized in that, the addition sequence of hydrogenation catalyst a, b and c is catalyst b to be added contain in the conjugated diene unit polymers soln, adds the mixing solutions of catalyst a and c again.
28. composition as claimed in claim 1 is characterized in that, the addition sequence of hydrogenation catalyst a, b and c is catalyst b to be mixed the back adding contain in the conjugated diene unit polymers soln with c, adds the mixing solutions of catalyst a and c again.
29. composition as claimed in claim 1 is characterized in that, the addition sequence of hydrogenation catalyst a, b and c, be simultaneously or different sequencing add respectively and contain in the conjugated diene unit polymers soln.
30. composition as claimed in claim 1 is characterized in that, wherein with respect to 100 the gram this contain the conjugated diene unit polymkeric substance, the usage quantity of hydrogenation catalyst a is between 0.001 to 50mmol.
31. composition as claimed in claim 1 is characterized in that, wherein with respect to 100 the gram this contain the conjugated diene unit polymkeric substance, the usage quantity of hydrogenation catalyst a is between 0.002 to 10mmol.
32. composition as claimed in claim 1 is characterized in that, wherein the mol ratio of this hydrogenation catalyst b and hydrogenation catalyst a is 0.1 to 50.
33. composition as claimed in claim 1 is characterized in that, contains conjugated diene unit polymer molecule weight range between 1000 to 1000000.
34. the method for a hydrogenating polymer containing conjugated diene unit, this contains homopolymer or conjugated diene unit and the unitary multipolymer of vinylaromatic hydrocarbon that the conjugated diene unit polymkeric substance is a conjugated diolefine, be dissolved in this conjugated diolefin polymer in the passivity organic solvent at a hydrogenation catalyst composition a, b, c, (a) titanium compound shown in formula (I) or its mixture:
Figure C2006100070830007C1
Formula (I)
Wherein
R 1, R 2Be identical or different substituting group, and be hydrogen, halogen atom, C 1～C 8Alkyl, C 1～C 8Alkoxyl group, C 6～C 12Cycloalkyl, phenyl, phenoxy group, C 7～C 10Alkoxy aryl, C 7～C 10Aralkyl, carboxyl ,-CH 2P (phenyl) 2,-CH 2Si (C 1～C 5Alkyl) 3Or-P (phenyl) 2
A is cyclopentadienyl, fluorenyl, indenyl or derivatives thereof; Described derivative is that on the ring of indenyl, fluorenyl or cyclopentadienyl one or several hydrogen are replaced by a substituting group;
(b) for to comprise as formula (II) at least or the compound (III) or its both mixture:
Figure C2006100070830007C2
Formula (II) formula (III)
Wherein formula (II) is a chain-like structure, and formula (III) is a ring texture, wherein R 3Be C 1～C 12Alkyl, X 1, X 2Be C 1～C 12Alkyl, C 1～C 12Epoxy alkyl, aromatic base, C 1～C 12Alkylaryl, n＞1, m＞2;
(c) existence of organometallic compound is reacted with hydrogen down, and this contains the unsaturated double-bond of conjugated diolefine in the conjugated diene unit polymkeric substance with selection hydrogenation.
35. method as claimed in claim 34 is characterized in that, wherein this hydrogenation be between 0 ℃ to 250 ℃ of temperature of reaction, hydrogen pressure is 1 to 150kg/cm 2Carry out in the scope.
36. method as claimed in claim 34 is characterized in that, the hydrogenation ratio of the unsaturated double-bond of this conjugated diolefine is for more than at least 50%.
37. method as claimed in claim 36 is characterized in that, the hydrogenation ratio of the unsaturated double-bond of this conjugated diolefine is for more than at least 90%.
38. method as claimed in claim 34 is characterized in that, the hydrogenation ratio of the two keys of the unitary phenyl ring of therein ethylene base aromatic hydrocarbon is lower than 30%.
39. method as claimed in claim 38 is characterized in that, the hydrogenation ratio of the two keys of the unitary phenyl ring of therein ethylene base aromatic hydrocarbon is lower than 10%.
40. method as claimed in claim 34 is characterized in that, used hydrogenation catalyst composition is applied to conjugated diene unit homopolymer or vinylaromatic hydrocarbon unit and conjugated diene unit multipolymer as hydrogenation catalyst.
41. method as claimed in claim 40 is characterized in that, vinylaromatic hydrocarbon unit and conjugated diene unit multipolymer are styrene-butadiene copolymer, styrene-isoprene multipolymer or vinylbenzene-(divinyl/isoprene) multipolymer.
42. method as claimed in claim 41 is characterized in that, vinylaromatic hydrocarbon unit and conjugated diene unit multipolymer are block or out of order arrangement.
43. method as claimed in claim 41 is characterized in that, styrene-butadiene copolymer is the styrene-ethylene-butylene-styrene multipolymer after the hydrogenation.
44. method as claimed in claim 41 is characterized in that, the styrene-isoprene multipolymer is styrene-ethylene-propylene-styrene multipolymer after the hydrogenation.
45. method as claimed in claim 41 is characterized in that, vinylbenzene after the hydrogenation-(divinyl/isoprene) multipolymer is styrene-ethylene-ethylene-propylene-styrol copolymer.
46. composition as claimed in claim 14 is characterized in that, organometallic compound comprises the hydrocarbon polymer of two lithiums, wherein the hydrocarbon polymer of two lithiums is 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 of 4-, 1,4,4 tetraphenyl butane, 1, two (1-lithium-3 methyl amyl) benzene or 1 of 3-, the combination of two (1-lithium-3 methyl amyl) benzene of 4-or above-mentioned pair of lithium hydrocarbon polymer.
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