CN1324867A - Catalyst composition for hydrogenating conjugated diolefine polymer and the polymer hydrogenating process - Google Patents
Catalyst composition for hydrogenating conjugated diolefine polymer and the polymer hydrogenating process Download PDFInfo
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- CN1324867A CN1324867A CN 00107660 CN00107660A CN1324867A CN 1324867 A CN1324867 A CN 1324867A CN 00107660 CN00107660 CN 00107660 CN 00107660 A CN00107660 A CN 00107660A CN 1324867 A CN1324867 A CN 1324867A
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Abstract
A method for hydrogenating conjugated diene polymer includes hydrogenation of the said polymer in the presence of hydrogen gas and hydrogenation catalyst composite. Said hydrogenation catalyst composite includes at least one kind of titanium compound, at least one kind of silane selected from monomer type silane, polymer type silane, ring silane and silazane, and at least one selective metal compound.
Description
The present invention relates to a kind of improved catalyst composition that is used for the hydrogenating conjugated diolefine polymkeric substance, wherein conjugated diene polymer is by the polymerization of conjugated diene monomer (as divinyl or isoprene) or copolymerization and make.The present invention be more particularly directed to have excellent activity, highly selective and be used for the catalyst composition of hydrogenating conjugated diolefine polymkeric substance cheaply.
Specifically, the present invention relates to a kind of catalyst composition and a kind of method that is used for this conjugated diene polymer of hydrogenation that is used for hydrogenating conjugated diolefine polymkeric substance (making), to improve weathering resistance, thermotolerance and the oxidation-resistance of polymkeric substance by the polymerization of conjugated diene monomer or polymerization.
Use conjugated diene (as divinyl, isoprene) to carry out polymerization or copolymerization with the preparation synthetic rubber, oneself is widely used in industrial for the commerce manufacturing.Basically, these polymkeric substance can use emulsification (radical polymerization) or solution (anionic polymerization) method to prepare.Two kinds of methods all can produce and contain the conjugated diene polymer (multipolymer) that two keys are closed in insatiable hunger on the main polymer chain.These insatiable hungers are closed two keys and can be vulcanized again, to improve the toughness of material.Yet, be easy to oxidizedly because two keys are closed in these insatiable hungers, and cause material (being exposed to ozone) under high temperature or weather-proof test to have unsettled shortcoming.Particularly, the vinylbenzene conjugated diene block copolymer (as SBS, SIS) its not under the sulphided state as thermoplastic elastomer, shock-resistant modification agent with when cooperating additive, be considered to be necessary to improve its thermostability and weather-proof stable defect of insufficient.
The deficiency of thermostability and weather-proof stability can be by removing or reducing insatiable hunger on the polymer bonds and close two keys and improved.Close two keys by the hydrogenated olefins insatiable hunger, can obtain being almost lipid structure than stabilization of polymer.Generally speaking, can use heterogeneous or homogeneous catalyst reduces insatiable hunger and closes two keys.Heterogeneous catalyst has lower hydrogenation activity, therefore needs higher temperature of reaction, higher reaction pressure and relatively large heterogeneous catalyst when reaction, so more uneconomical.Except the problems referred to above, carve the also feasible not only meeting hydrogenation on the olefinic double bonds of needs reaction of severe reaction conditions, and also can hydrogenation on the arene double bonds.As a result, can produce unwanted polymer architecture, it contains unwanted part cyclohexyl structure (being got by the phenyl ring hydrogenation on the polymkeric substance major key), and has unwanted semi-crystalline nature.Therefore, industrial pressing for developed the polymkeric substance that can be used for hydrogenating conjugated diolefine, and has the homogeneous catalyst system of high reactivity and highly selective (not can the two keys of hydrogenation of aromatics).
Use the method for bicyclic pentadiene titanium compound as catalysts, be the reaction of a kind of known valid homogeneous hydrogenation (such as in the following document announcement: M.F.Sloan et al.in Journalof American Chemical Society1965,85,4014-4018, Y.Tajima, et al.inJournal of Organic Chemistry, 1968,33,1689-1690, British patent2,134,909, Japanese patent61,28507). this catalyst system has excellent activity and splendid selectivity for the two keys of hydrogenated olefins.Yet because the stability of this catalyst system is not good, reaction is difficult to reproduce.
1985, people such as Kishimoto were at USP4, and 501, disclose in 857, in the presence of at least a bicyclic pentadiene titanium compound and at least a hydrocarbon lithium compound, carry out the hydrogenation of olefinic double bonds, wherein the hydrocarbon lithium compound can be used in combination with the anion active chain end.1987, people such as Kishimoto were again at US P4, disclosed in 673,714, used bicyclic pentadiene diaryl titanium compound to come the hydrogenating conjugated diolefine base polymer, and did not need to add alkyl lithium compounds.The bicyclic pentadiene titanium compound that above-mentioned these two methods are all used high density is as catalyzer, and is therefore very uneconomical.Nineteen ninety, people such as Teramoto are at USP4, disclose in 980,421, use identical titanium compound and combination to use alkoxy compound, can obtain similar hydrogenation activity.1991, people such as Chamberlain were at USP5, disclosed in 039,755, used hydrogen to stop reactive bond, then added the bicyclic pentadiene titanium compound so that hydrogenation carries out.The problem of aforesaid method is that hydrogen is not very effective for the termination of reactive bond end, so hydrogenation is difficult to reproduce.1992, people such as Chamberlain are at USP5,132,372 and 5, disclose similar method for hydrogenation in 173,537, it is to use hydrogen to stop the reactive bond end, then add bicyclic pentadiene titanium compound and extra catalyst promoting agent (methyl benzoate), so that the hydrogenation of conjugated diene polymer is more effective.
All above-mentioned catalyst compositions all are to use lithium alkylide (the static lithium hydride that produces on the spot) or alkoxy lithium compound to activate the bicyclic pentadiene titanium compound, so that the hydrogenation of conjugated diene polymer is more effective.Must be noted that in the presence of lithium, also can cause the bicyclic pentadiene titanium compound by the reduction of Ti (IV) to Ti (III), this can cause the decomposition of catalyst component and the reduction of catalyst activity and stability.Therefore, on the viewpoint of economy, be starved of a kind of catalyst composition of exploitation, it can avoid the decomposition of active catalyst (bicyclic pentadiene titanium compound), and as long as uses little amount of catalyst that stable and effective hydrogenation result can be provided.
The object of the present invention is to provide a kind of catalyst composition that is used for the hydrogenating conjugated diolefine polymkeric substance, it has high hydrogenation activity and selectivity.And minimum catalyst component arranged.
Another object of the present invention is to provide a kind of method of hydrogenating conjugated diolefine polymkeric substance, its do not have the hydrocarbon lithium compound in the presence of, have high hydrogenation activity and selectivity.
The present invention relates to a kind of catalyst composition, it comprises:
(a) at least a titanium compound, shown in (a):
R in the formula
1And R
2Can be identical or different, represent halogen atom, alkyl, aryl, aralkyl, cycloalkyl, aryloxy, alkoxyl group or carbonyl,
Cp* represents cyclopentadienyl or formula C
5R
5Derivative, R in the formula
5Can be identical or different, represent hydrogen atom, alkyl, aralkyl and aryl;
(b) at least a silane, it is selected from following substances:
(ⅰ) haplotype silane, shown in (ⅰ):
X in the formula
1, X
2And X
3Can be identical or different, represent hydrogen atom, halogen atom, alkyl, aryl, aralkyl, cycloalkyl, aryloxy, alkoxyl group, acyloxy or carboxyl,
(ⅱ) polymer-type silane, shown in (ⅱ):
R represents hydrogen atom, halogen atom, alkyl, aryl, aralkyl, cycloalkyl, aryloxy or alkoxyl group in the formula, and n 〉=0,
(ⅲ) cyclic silane, shown in (ⅲ):
R represents hydrogen atom, halogen atom, alkyl, aryl, aralkyl, cycloalkyl, aryloxy or alkoxyl group in the formula, and n is the integer of 2-5,
And
(ⅳ) silazane, as shown in the formula (ⅳ) or (ⅴ):
R in the formula
a, R
b, R
cCan be identical or different, represent hydrogen atom, halogen atom, alkyl, aryl, aralkyl, cycloalkyl, aryloxy or alkoxyl group; And optionally comprise
(c) at least a metallic compound, it is selected from organo-aluminium compound, organo-magnesium compound, organolithium compound, organic zinc compound, lithium hydride and formula LiOR
3R in the formula
3Represent alkyl, aryl, aralkyl or cycloalkyl.
One advantage of catalyst composition of the present invention is that this catalyst composition has higher reactivity for the hydrogenation of olefinic double bonds.Therefore, the titanium material total amount in the adding reaction can reduce, so the reaction of less expensive can be provided.Another advantage of catalyst composition of the present invention is because the stability of catalyst system is improved, can make the olefinic double bonds of conjugated diene polymer that high conversion and highly selective are arranged.
The invention provides have hyperergy, selectivity and stability the catalyst composition that is used for the hydrogenating conjugated diolefine polymkeric substance.Disclosed catalyst composition uses commercial available composition (silane component), and catalyst stability, catalyst activity and transformation efficiency are improved.As a result, the total amount of catalyst component can reduce, and can make the manufacturing cost of hydrogenation process reduce.
The invention still further relates to a kind of method that is used for the hydrogenating conjugated diolefine polymkeric substance, it comprises: this polymkeric substance of hydrogenation in the presence of hydrogen and hydrogenation catalyst composition, and this hydrogenation catalyst composition is drawn together:
(a) at least a titanium compound, shown in (a):
R in the formula
1And R
2Can be identical or different, represent halogen atom, alkyl, aryl, aralkyl, cycloalkyl, aryloxy, alkoxyl group or carbonyl,
Cp* represents cyclopentadienyl or formula C
5R
5Derivative, R in the formula
5Can be identical or different, represent hydrogen atom, alkyl, aralkyl and aryl:
(b) at least a silane, it is selected from following substances:
(ⅰ) haplotype silane, shown in (ⅰ):
X in the formula
1, X
2And X
3Can be identical or different, represent hydrogen atom, halogen atom, alkyl, aryl, aralkyl, cycloalkyl, aryloxy, alkoxyl group, acyloxy or carboxyl,
(ⅱ) polymer-type silane, shown in (ⅱ):
R represents hydrogen atom, halogen atom, alkyl, aryl, aralkyl, cycloalkyl, aryloxy or alkoxyl group in the formula, and n 〉=0,
(ⅲ) cyclic silane, shown in (ⅲ):
R represents hydrogen atom, halogen atom, alkyl, aryl, aralkyl, cycloalkyl, aryloxy or alkoxyl group in the formula, and n is the integer of 2-5,
And
(ⅳ) silazane, as shown in the formula (ⅳ) or (ⅴ):
R in the formula
a, R
b, R
cCan be identical or different, represent hydrogen atom, halogen atom, alkyl, aryl, aralkyl, cycloalkyl, aryloxy or alkoxyl group; And optionally comprise
(c) at least a metallic compound, it is selected from organo-aluminium compound, organo-magnesium compound, organolithium compound, organic zinc compound, lithium hydride and formula LiOR
3, R in the formula
3Represent alkyl, aryl, aralkyl or cycloalkyl.
Cp* in the formula (a) represents cyclopentadienyl or formula C
5R
5Derivative, R in the formula
5Can be identical or different, represent hydrogen atom, alkyl, aralkyl and aryl.The Cp* example that is fit to is cyclopentadienyl and pentamethyl-cyclopentadienyl.Based on industrial obtain just, preferably use cyclopentadienyl as Cp*.
The suitable titanium compound example of formula (a) is: dicyclic pentylene titanium dichloride, bicyclic pentadiene dibrominated titanium, bicyclic pentadiene two titanium iodide, bicyclic pentadiene bifluoride titanium, bicyclic pentadiene dicarbapentaborane titanium, bicyclic pentadiene dimethyl titanium, bicyclic pentadiene diethyl titanium, bicyclic pentadiene dipropyl (comprising sec.-propyl) titanium, the bicyclic pentadiene dibutyl (comprises normal-butyl, sec-butyl, the tertiary butyl) titanium, bicyclic pentadiene dibenzyl titanium, bicyclic pentadiene phenylbenzene titanium, bicyclic pentadiene dimethoxy titanium, bicyclic pentadiene diethoxy titanium, bicyclic pentadiene dipropoxy titanium, bicyclic pentadiene dibutoxy titanium, bicyclic pentadiene two phenoxide titaniums, bicyclic pentadiene methyl titanium chloride, bicyclic pentadiene methyl titanium bromide, bicyclic pentadiene methyl titanium iodide, bicyclic pentadiene methyl titanium fluoride, two pentamethyl-cyclopentadienyl titanium dichloride, two pentamethyl-cyclopentadienyl dibrominated titaniums, two pentamethyl-cyclopentadienyl two titanium iodide, two pentamethyl-cyclopentadienyl bifluoride titaniums, two pentamethyl-cyclopentadienyl dicarbapentaborane titaniums, two pentamethyl-cyclopentadienyl dibutyl (comprise normal-butyl, sec-butyl, the tertiary butyl) titanium, two pentamethyl-cyclopentadienyl dibenzyl titaniums, two pentamethyl-cyclopentadienyl phenylbenzene titaniums and composition thereof.Because be easier to operation, air stability, reach commercial getting, preferable titanium compound is a dicyclic pentylene titanium dichloride.
The example of the suitable haplotype silane of formula (ⅰ) is: dimethyl dichlorosilane (DMCS), ethyl dichlorosilane, the propyl group dichlorosilane, the butyl dichlorosilane, diphenyl dichlorosilane, dimethylchlorosilane, the diethyl chlorosilane, the dipropyl chlorosilane, the dibutyl chlorosilane, diphenyl chlorosilane, the dimethyl methyl TMOS, dimethylethoxysilane, the dimethyl propylene TMOS, the dimethyl butyrate TMOS, benzyloxy-dimethyl silane, the diethyl Ethoxysilane, diethyl propoxy-silane, the diethyl butoxy silane, diethyl benzyloxy silane, the dipropyl methoxy silane, the dipropyl Ethoxysilane, dipropyl propoxy-silane, the dipropyl butoxy silane, dipropyl benzyloxy silane, the dibutyl methoxy silane, the dibutyl Ethoxysilane, dibutyl propoxy-silane, the dibutyl butoxy silane, dibutyl benzyloxy silane, the diphenylmethyl TMOS, the phenylbenzene Ethoxysilane, the diphenylprop TMOS, the phenylbenzene butoxy silane, phenylbenzene benzyloxy silane, dimethylsilane, diethylsilane, dipropyl silane, dibutyl silane, diphenyl silane, diphenylmethylsilane, diphenyl-ethyl silane, the diphenylprop base silane, phenylbenzene butyl silane, trimethyl silane, triethyl silicane, tripropyl silane, tributyl silane, tri-phenyl-silane, methyl-monosilane, ethylsilane, propyl silane, butyl silane, phenyl silane and methyl diacetoxy silane.
The n value of formula (ⅱ) is big or equals 0, preferably between 0 and 100.
The example of the suitable polymer-type silane of formula (ⅱ) is: polymethyl hydrogen siloxane, poly-ethyl hydrogen siloxane, poly-propyl group hydrogen siloxane, poly-butyl hydrogen siloxane, polyphenylene hydrogen siloxane and 1,1,3,3-tetramethyl disiloxane.
The example of the suitable cyclic silane of formula (ⅲ) is: methyl hydrogen cyclosiloxane, ethyl hydrogen cyclosiloxane, propyl group hydrogen cyclosiloxane, butyl hydrogen cyclosiloxane and phenyl hydrogen cyclosiloxane.
The example of the suitable silazane of formula (ⅳ) is: 1,1,3, and 3-tetramethyl-disilazane, 1,1,3,3-tetraethyl-disilazane, 1,1,3,3-tetrapropyl disilazane, 1,1,3,3-tetrabutyl disilazane and 1,1,3,3-tetraphenyl disilazane.
The example of the organo-aluminium compound that is fit to is: trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, triphenyl aluminum, diethyl aluminum chloride, ethylaluminum dichloride, methylaluminum sesquichloride (methylaluminium sesquichloride), ethyl sesquialter aluminum chloride (ethylaluminum sesquichloride), ADEH, diisobutyl aluminium hydride, triphenyl aluminum and three (2-ethylhexyl) aluminium.
The example of the organo-magnesium compound that is fit to is: dimethyl magnesium, magnesium ethide, methyl-magnesium-bromide, methylmagnesium-chloride, ethylmagnesium bromide, ethylmagnesium chloride, phenyl-magnesium-bromide, phenyl-magnesium-chloride and dimethyl chlorination magnesium.
The example of the organic zinc compound that is fit to is: zinc ethyl, bicyclic pentadiene zinc and phenylbenzene zinc.
The LiOR that is fit to
3The example of compound is: methoxyl group lithium, oxyethyl group lithium, positive propoxy lithium, lithium isopropoxide, n-butoxy lithium, clock butoxy lithium, tert.-butoxy lithium, pentyloxy lithium, hexyloxy lithium, heptan oxygen base lithium, octyloxy lithium, phenoxy group lithium, 4-methylphenoxy lithium, 2,6-di-t-butyl-4-methylphenoxy lithium and benzyloxy lithium.
The example of the organolithium compound that is fit to is: lithium methide, lithium ethide, n-propyl lithium, sec.-propyl lithium, n-Butyl Lithium, s-butyl lithium, tert-butyl lithium, n-pentyl lithium, phenyl lithium, benzyl lithium, two lithium compounds (for example 1,4-two lithiums-normal butane) and have the living anion polymerization thing of active lithium on polymer bonds.
Lithium hydride of the present invention can use its primitive form, or can produce on the spot in static state, that is, having the active conjugated diene polymer of active lithium end, its end is produced lithium hydride by hydrogen institute's hydrogenation.In order to have good hydrogenation activity, it is preferable using the static lithium hydride that produces on the spot.
Even do not have metallic compound (c) in the presence of, that is, have only use titanium compound (a) and silane (b), catalyst composition still can demonstrate good hydrogenation activity and selectivity.
The mol ratio of silane (b) and titanium compound (a) can be 0.01/1 to 200/1, and preferably 0.1/1 to 100/1.Silane of the present invention (b) can improve the stability of catalyst system, and makes olefinic double bonds have high conversion and highly selective, and hydrogenation has reproducibility.Stability with catalyst composition of high hydrogenation activity may be because the formation of the silica-based titanium complex of following formula bicyclic pentadiene:
A* is silicone base (silicone group) in the formula, and (b) derives by silane, for example
If needed, metallic compound (c) can become to assign to use as the additional catalyst of titanium compound (a) and silane (b) for other purposes, for example in order to alleviate the purpose of the negative impact of impurity in the conjugated diene polymer in hydrogenation process.Polar compound, for example tetrahydrofuran (THF), triethylamine, N, N, N ', N '-Tetramethyl Ethylene Diamine and ethylene glycol dimethyl ether also can be used as extra catalyst component.
Wherein the mol ratio of silane (b) and titanium compound (a) is 0.01/1 to 200/1.The mol ratio of metallic compound (c) and titanium compound (a) can be 0/1 to 100/1, is preferably 0.5/1 to 25/1, most preferably is 1/1 to 10/1.If mol ratio (c)/(a) greater than 100/1, then can be tended to cause the gel and the undesired second order reaction of polymkeric substance, and can reduce catalyst activity.
Have the catalyst composition of the present invention of above-mentioned mol ratio, higher reactivity is arranged for olefinic double bonds.Therefore, the titanium composition total amount that adds in the reaction can reduce, and the reaction process of less expensive can be provided.
Known conjugated diene polymer can use free radical or anionic catalyst and make.This polymkeric substance can use totally (bulk), solution or emulsifying technology and prepare.In general, when using the solution anionic techniques, the method for making of conjugated diene polymer is, will contact simultaneously by one or more monomers of polymeric, or monomer is contacted together with anionoid polymerization initiator (as I A family metal, its alkanes, amides, silanol ester class (silanolates), naphthalene class, hexichol class and anthracene derivative) in order.Preferably use organic alkali metal compound, in the solvent that is fit to, in temperature-150 ℃ to 300 ℃ of reactions down, preferably in 0 ℃ to 100 ℃ reaction down of temperature.
Catalyzer of the present invention can be applicable on all polymkeric substance with alkene unsaturated double-bond.Best, this catalyzer is applied on the conjugated diene polymer.The number-average molecular weight of described polymkeric substance is generally 500 to 1,000, between 000.This conjugated diene polymer comprises the homopolymer of conjugated diene, the multipolymer of different conjugated dienes, and the multipolymer of at least a conjugated diene and at least a olefinic monomer.The conjugated diene that is used to make these conjugated diene polymers has 4 to 12 carbon atoms usually.Object lesson comprises: 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-divinyl, 1,3-pentadiene, 2-methyl isophthalic acid, 3-pentadiene, 1,3-hexadiene and 4,5-diethyl-1,3-butadiene, wherein preferably, the homopolymer of 1,3 divinyl and/or isoprene or multipolymer, because 1,3-divinyl and isoprene have the advantage on the industrial application, and the elastomerics that can obtain having advantageous property, so they are particularly suitable for using.
Catalyzer of the present invention preferably can be applicable to the hydrogenation of the multipolymer that made by the copolymerization of at least a conjugated diene and at least a olefinic monomer.The preferable conjugated diene that is used to prepare this multipolymer as mentioned above.As for olefinic monomer, all can all can use with the olefinic monomer that this conjugated diolefin copolymer closes, and the aromatic hydrocarbons that ethene replaces is particularly suitable for.The object lesson that is used to make the aromatic hydrocarbons that the ethene of this analog copolymer replaces comprises: vinylbenzene, t-butyl styrene, alpha-methyl styrene, p-methylstyrene, divinylbenzene, 1,1-diphenylethlene, N, the N-dimethyl-to amino-ethyl vinylbenzene and N, the N-diethyl-to amino-ethyl vinylbenzene etc.Certainly, preferably use vinylbenzene.The object lesson of the multipolymer of the aromatic hydrocarbons that conjugated diene and ethene replace comprises butadiene/styrene copolymers and isoprene/styrol copolymer, because these two kinds of multipolymers can provide the hydrogenated copolymer of high industrial value, therefore is particularly suitable for.
The multipolymer of the aromatic hydrocarbons that conjugated diene and ethene replace comprises the random copolymers of monomer stochastic distribution in whole polymer chain, decrescence type (tapered) segmented copolymer, segmented copolymer and graft copolymer fully.In these polymkeric substance, in order to make multipolymer show to can be used as the character of thermoplastic elastomer, segmented copolymer is particularly suitable.
Such segmented copolymer comprises (a) at least a polymer blocks A that is mainly the aromatic hydrocarbons that ethene replaces, and (b) at least a particularly polymer blocks B of 1,3-butadiene and/or isoprene of conjugated diene that is mainly.Block A can comprise a little conjugated diene, and B block also can comprise the aromatic hydrocarbons that a little ethene replaces.Segmented copolymer not only comprises straight chain type, and comprises so-called branched chain type, radial pattern and star type, is by using coupler to come coupling straight chain block polymer and forming.Be applicable to that segmented copolymer of the present invention preferably contains the aromatic hydrocarbons of the ethene replacement of 5% to 95% weight, preferably, principal constituent is that the content of the polymer blocks A of vinylbenzene replacement is 0 to 90 weight %.The unitary micro-structure of the conjugated diene of segmented copolymer has 1 of 6%-80 weight %, the 2-ethylene content, and in other words, among the polymer blocks B 1, the 2-ethylene content is 6 weight % to 80 weight %, preferably 20%-70%.When the segmented copolymer that meets these requirements was hydrogenated, its alkene partly had good elasticity, and therefore, not only industrial useful, and soltion viscosity is low, is easy to by separating in the reaction solvent.Therefore, but hydrogenant segmented copolymer very economical ground is manufactured.
Generally speaking, hydrogenation can be in the solvent that is fit to, carry out under (preferably at 50 ℃ under 90 ℃), the hydrogen partial pressure 1psig to 1200psig (preferably 100 to 200psig) under 0 ℃ to 120 ℃ of the temperature.Normally used catalyst concn is the extremely per 100 gram polymkeric substance 20mM of per 100 gram polymkeric substance 0.001mM (mmole), and be 10 to 360 minutes the duration of contact under the hydrogenation conditions.
Catalyst component of the present invention can add separately in the solution of conjugated diene polymer, or in advance with some catalyst component pre-mixings.
Reaction can be carried out in stirred tank reactor or ring formula (loop) reactor, wherein is drawn out of by reactor by institute's hydrogenant solution mixture,, introduces in the reactor again and contacts with hydrogen with pump circulation via heat exchanger.Reaction can continous way or intermittent type carry out.Catalyzer of the present invention can add in the reaction medium, the pattern of solution that perhaps can above-mentioned inert organic solvents.
Hydrogenation process related to the present invention can body or solution methods carry out.In solution methods, the inert solvent that is used for the anionoid polymerization process can directly use without the additional purification program.Thus, the invention provides better simply reaction process, can use identical reaction medium to carry out anionic polymerisation and hydrogenation simultaneously.Generally speaking, can use the used solvent of any known preparation conjugated diene polymer.The solvent that is fit to comprises straight chain heptane, octane etc., with and alkyl-substituted derivatives, and comprise cyclic aliphatic hydrocarbon, for example pentamethylene, hexanaphthene, suberane and alkyl thereof replace and the derivative of aryl replacement, and comprise the aromatic hydrocarbons that aryl and alkyl replace, for example benzene, naphthalene, toluene, dimethylbenzene and derivative thereof, and comprise hydrogenant aromatic hydrocarbons, for example tetraline (tetralin), naphthane (decalin) and derivative thereof, and comprise straight chain and cyclic ether, for example dimethyl ether, methyl ethyl ether, Anaesthetie Ether, tetrahydrofuran (THF) and derivative thereof.
Behind the hydrogenation, can use alcohols (as methyl alcohol, ethanol or Virahol) to make reaction soln quenching (quench), to precipitate required hydropolymer.Can filter, dry in a vacuum, and collect the polymer product of gained, and obtain the required product of higher degree.It should be noted that because the hyperergy of catalyst system of the present invention only needs a spot of catalyst component in the hydrogenation, therefore can not need carry out extra deashing (deashing) process, to remove catalyst component.
By correct selection hydrogenation conditions, hydrogenation catalyst of the present invention can make the alkene insatiable hunger close the hydrogenation that two keys have a great deal of.Catalyzer further makes two keys hydrogenatable to required amount of hydrogenation.In the hydrogenation of conjugated diene polymer, its amount of hydrogenation is, the insatiable hunger of conjugated diene unitary at least 50% (preferably at least 90%) is closed two keys and is hydrogenated.Under the situation of the multipolymer of the aromatic hydrocarbons that conjugated diene and ethene replace, its amount of hydrogenation is, the insatiable hunger of the conjugated diene of original multipolymer unitary at least 50% (preferably 90%) is closed two keys and is hydrogenated, and two keys of 10% or following (preferably 5% or following) of the aromatic hydrocarbons of original multipolymer part are hydrogenated.
The hydrogenation per-cent that two keys are closed in the alkene insatiable hunger can be recorded by infrared absorption spectrum.Containing under the situation of aromatic hydrocarbons, can merge and use ultra-violet absorption spectrum and NMR spectrum to wait to measure.
The present invention will be described in detail with reference to following examples.But the embodiment of the invention and preferred embodiment are not in order to limit the scope of the invention.
A, preparation feedback catalyzer:
Embodiment 1:
With dimethyl bicyclic pentadiene titanium (dimethyl titanocene) (a) and formula (ⅰ), (ⅱ), (ⅲ) or silane (ⅳ) (b) in inert solvent (as toluene or hexanaphthene), make up, generate filbert to brown solution.Remove volatile matter, and dry in vacuum, separablely go out catalyzer.
The reacted constituent of preparation catalyzer is listed in the table below:
Table 1: the catalyst component of preparation active catalyst
1. the molecular weight of methyl hydrogen cyclosiloxane=240
2. polymethyl hydrogen siloxane
aMolecular weight=420
3. polymethyl hydrogen siloxane
bMolecular weight=5000
Embodiment 2:
Metallic compound (c) (lithium alkylide or alkyl magnesium) adding is contained in the inertia solution of bicyclic pentadiene titanium chloride (a) and formula (ⅰ), (ⅱ), (ⅲ) or silane (ⅳ) (b), make to produce active catalyst on the spot, and obtain hydrogenation catalyst.Reacted constituent is listed in the table below:
Table 2: the catalyst component of preparation active catalyst
| ????13 | N-Butyl Lithium (10.0mmol) | ????Cp 2TiCl 2????(0.25g；1.0mmol) | Methyl diacetoxy silane (0.97g; 6.0mmol) | Toluene (20ml) |
| ????14 | N-Butyl Lithium (10.0mmol) | ????Cp 2TiCl 2????(0.25g；1.0mmol) | Methyl hydrogen cyclosiloxane (0.36g; 1.5mmol 1) | Toluene (20ml) |
| ????15 | N-Butyl Lithium (10.0mmol) | ????Cp 2TiCl 2????(0.25g；1.0mmol) | Polymethyl hydrogen siloxane a (0.48g; 1.1mmol 2) | Toluene (20ml) |
| ????16 | N-Butyl Lithium (10.0mmol) | ????Cp 2TiCl 2????(0?25g；1.0mmol) | Polymethyl hydrogen siloxane b????(0.48g；0.096mmol 3) | Toluene (20ml) |
| ????17 | ?EtMgBr (12.0mmol) | ????Cp 2TiCl 2????(0.25g；1.0mmol) | Polymethyl hydrogen siloxane a????(0.48g；1.1mmol 2) | Toluene (20ml) |
1. the molecular weight of methyl hydrogen cyclosiloxane=240
2. polymethyl hydrogen siloxane
aMolecular weight=420
3. polymethyl hydrogen siloxane
bMolecular weight=5000
B. elastomeric hydrogenation
Embodiment 3:
Prepared catalyst component among the embodiment 1 is diluted in toluene or hexanaphthene, to form the catalyst solution (being as the criterion) of 0.01M with Ti concentration.The catalyst solution of gained is directly used in the hydrogenation of styrene butadiene styrene (SBS) polymkeric substance.The preparation method of SBS polymkeric substance (straight-chain block copolymer, number-average molecular weight are 100,000) is earlier through the anionoid polymerization step, then to stop living chain with Virahol, filtration then, drying overnight under vacuum.The SBS polymkeric substance contains the styrene units of 30wt%, the butadiene unit of 70wt% (containing 1 of 25wt%, 2-ethene structure).Then, restrain the SBS polymer dissolution in the hexanaphthene of 125ml with 15.The SBS/ cyclohexane solution of gained is directly used in hydrogenation.Use hexanaphthene to be reaction solvent, in the autoclave of 500ml, in H
2Under the pressure 200psi, 60 ℃, carry out the hydrogenation of SBS polymkeric substance.React on H
2After keeping 60 minutes under the pressure 200psi, 60 ℃, make the reaction soln quenching with Virahol.Filter, in 40 ℃ of dryings overnight down, and obtain hydrogenated products.Then with the total conversion rate of IR spectroscopic analysis olefinic double bonds.Hydrogenation the results are shown in following table.
Table 3: the catalyzer that uses embodiment 1 to make carries out the hydrogenation of SBS polymkeric substance
| Catalyzer sequence number (used volume) | The net weight of butadiene unit (g) | The transformation efficiency of butadiene unit (%) | The transformation efficiency of catalyzer (mole number of the moles butadiene/catalyst system therefor of conversion) | Hydrogenation selectivity * (%) |
| ?1(1.2ml) | ????10.5 | ????92 | ????14900 | ????99 |
| ?2(1.2ml) | ????10.5 | ????76 | ????12300 | ????99 |
| ?3(1.2ml) | ????10.5 | ????96 | ????15500 | ????99 |
| ?4(1.2ml) | ????10.5 | ????64 | ????10300 | ????99 |
| ?5(1.2ml) | ????10.5 | ????99 | ????16000 | ????99 |
| ?6(1.2ml) | ????10.5 | ????99 | ????16000 | ????99 |
| ?7(1.2ml) | ????10.5 | ????99 | ????16000 | ????99 |
* hydrogenation optionally is calculated as, (moles butadiene of conversion)/(moles butadiene of conversion)+(the two key mole numbers of the benzyl of conversion)
Embodiment 4:
Prepared catalyst component among the embodiment 2 is diluted in toluene or hexanaphthene, to form the catalyst solution (being as the criterion) of 0.01M with Ti concentration.The catalyst solution of gained is directly used in the hydrogenation of styrene butadiene styrene (SBS) polymkeric substance.Identical among SBS polymkeric substance and the embodiment 3.Use hexanaphthene to be reaction solvent, in the autoclave of 500ml, in H
2Under the pressure 200psi, 60 ℃, carry out the hydrogenation of SBS polymkeric substance.React on H
2After keeping 60 minutes under the pressure 200psi, 60 ℃, make the reaction soln quenching with Virahol.Filter, in 40 ℃ of dryings overnight down, and obtain hydrogenated products.Then with the total conversion rate of IR spectroscopic analysis olefinic double bonds.Hydrogenation the results are shown in following table.
Table 4: the catalyzer that uses embodiment 2 to make carries out the hydrogenation of SBS polymkeric substance
| Catalyzer sequence number (used volume) | The net weight of butadiene unit (g) | The transformation efficiency of butadiene unit (%) | The transformation efficiency of catalyzer (mole number of the moles butadiene/catalyst system therefor of conversion) | Hydrogenation selectivity * (%) |
| ????8(1.2ml) | ????10.5 | ????90 | ????14600 | ????99 |
| ????9(1.2ml) | ????10.5 | ????86 | ????13900 | ????99 |
| ???10(1.2ml) | ????10.5 | ????78 | ????12700 | ????99 |
| ?11(1.2ml) | ????10.5 | ????99 | ????16000 | ????99 |
| ?12(1.2ml) | ????10.5 | ????95 | ????15400 | ????99 |
| ?13(1.2ml) | ????10.5 | ????52 | ????8400 | ????99 |
| ?14(1.2ml) | ????10.5 | ????93 | ????15100 | ????99 |
| ?15(1.2ml) | ????10.5 | ????99 | ????16000 | ????99 |
| ?15(0.8ml) | ????10.5 | ????99 | ????24100 | ????99 |
| ?16(1.2ml) | ????10.5 | ????99 | ????16000 | ????99 |
| ?17(1.2ml) | ????10.5 | ????98 | ????15900 | ????99 |
* hydrogenation optionally is calculated as, (moles butadiene of conversion)/(moles butadiene of conversion)+(the two key mole numbers of the benzyl of conversion)
Embodiment 5:
Repeat the hydrogenation of embodiment 4, but directly use by the prepared SBS polymkeric substance of anionic polymerization not purified (the SBS polymers soln still contains the active lithium chain end).Hydrogenation the results are shown in following table.
Table 5: hydrogenation with SBS polymkeric substance of active anion chain end
| Catalyzer sequence number (used volume) | The net weight of butadiene unit (g) | The transformation efficiency of butadiene unit (%) | The transformation efficiency of catalyzer (mole number of the moles butadiene/catalyst system therefor of conversion) | Hydrogenation selectivity * (%) |
| ??8(1.2ml) | ????8.75 | ????90 | ????12200 | ????99 |
| ?10(1.2ml) | ????8.75 | ????99 | ????13300 | ????99 |
| ?11(1.2ml) | ????8.75 | ????94 | ????12700 | ????99 |
| ?13(1.2ml) | ????8.75 | ????84 | ????11300 | ????99 |
| ?14(1.2ml) | ????8.75 | ????91 | ????12300 | ????99 |
| ?15(1.2ml) | ????8.75 | ????99 | ????13300 | ????99 |
| ?15(0.8ml) | ????8.75 | ????99 | ????20100 | ????99 |
* hydrogenation optionally is calculated as, (moles butadiene of conversion)/(moles butadiene of conversion)+(the two key mole numbers of the benzyl of conversion)
Embodiment 6:
Use No. 14 catalyzer as the hydrogenation of catalyzer, but use different temperature of reaction, H with repetition embodiment 5
2Pressure and reaction times.Hydrogenation the results are shown in following table.
Table 6: use No. 14 catalyzer to carry out the hydrogenation of SBS
| Catalyzer sequence number (all volumes) | The net weight of butadiene unit (g) | Temperature of reaction (℃) | Reaction pressure (psi) | Reaction times (branch) | The transformation efficiency of butadiene unit (%) | The transformation efficiency of catalyzer | Hydrogenation selectivity * (%) |
| ?15(1.2ml) | ????8.75 | ????40 | ????200 | ????40 | ????64 | ?8600 | ????99 |
| ?15(1.2ml) | ????8.75 | ????40 | ????200 | ????80 | ????99 | ?13300 | ????99 |
| ?15(1.2ml) | ????8.75 | ????40 | ????100 | ????80 | ????59 | ?7780 | ????99 |
| ?15(1.2ml) | ????8.75 | ????40 | ????100 | ????180 | ????99 | ?13300 | ????99 |
| ?15(1.2ml) | ????8.75 | ????40 | ????300 | ????40 | ????99 | ?13300 | ????99 |
| ?15(1.2ml) | ????8.75 | ????40 | ????400 | ????25 | ????99 | ?13300 | ????99 |
| ?15(1.2ml) | ????8.75 | ????60 | ????200 | ????60 | ????99 | ?13300 | ????99 |
| ?15(1.2ml) | ????8.75 | ????60 | ????100 | ????90 | ????99 | ?13300 | ????99 |
* hydrogenation optionally is calculated as, (moles butadiene of conversion)/(moles butadiene of conversion)+(the two key mole numbers of the benzyl of conversion)
Comparing embodiment 1
Repeat the hydrogenation of embodiment 3, but use Cp
2Ti (Me)
2Be catalysts.React on H
2After keeping 60 minutes under the pressure 200psi, 60 ℃, make the reaction soln quenching with Virahol.Filter, in 40 ℃ of dryings overnight down, and obtain hydrogenated products.Total conversion rate with IR spectroscopic analysis olefinic double bonds is 45% then, is equivalent to catalyzer transformation efficiency 7250.
Comparing embodiment 2
Repeat the hydrogenation of embodiment 4, but use Cp
2TiCl
2Be catalysts.React on H
2After keeping 60 minutes under the pressure 200psi, 60 ℃, make the reaction soln quenching with Virahol.Filter, in 40 ℃ of dryings overnight down, and obtain hydrogenated products.Total conversion rate with IR spectroscopic analysis olefinic double bonds is 28% then, is equivalent to catalyzer transformation efficiency 4500.
Though the present invention discloses as above with preferred embodiment; right its is not that any person skilled in the art is under the situation that does not deviate from the spirit and scope of the present invention in order to qualification the present invention; change of having done and retouching all should belong within the scope of protection of the invention.
Claims (15)
1. method that is used for the hydrogenating conjugated diolefine polymkeric substance, it comprises: this polymkeric substance of hydrogenation in the presence of hydrogen and hydrogenation catalyst composition is characterized in that this hydrogenation catalyst composition comprises:
(a) at least a titanium compound, shown in (a):
R in the formula
1And R
2Can be identical or different, represent halogen atom, alkyl, aryl, aralkyl, cycloalkyl, aryloxy, alkoxyl group or carbonyl;
Cp* represents cyclopentadienyl or formula C
5R
5Derivative, R in the formula
5Can be identical or different, represent hydrogen atom, alkyl, aralkyl and aryl;
(b) at least a silane, it is selected from following substances:
(ⅰ) haplotype silane, shown in (ⅰ):
X in the formula
1, X
2And X
3Can be identical or different, represent hydrogen atom, halogen atom, alkyl, aryl, aralkyl, cycloalkyl, aryloxy, alkoxyl group, acyloxy or carboxyl,
(ⅱ) polymer-type silane, shown in (ⅱ):
R represents hydrogen atom, halogen atom, alkyl, aryl, aralkyl, cycloalkyl, aryloxy or alkoxyl group in the formula, and n 〉=0,
(ⅲ) cyclic silane, shown in (ⅲ):
R represents hydrogen atom, halogen atom, alkyl, aryl, aralkyl, cycloalkyl, aryloxy or alkoxyl group in the formula, and n is the integer of 2-5,
And
(ⅳ) silazane, as shown in the formula (ⅳ) or (ⅴ):
R in the formula
a, R
b, R
cCan be identical or different, represent hydrogen atom, halogen atom, alkyl, aryl, aralkyl, cycloalkyl, aryloxy or alkoxyl group; And optionally comprise
(c) at least a metallic compound, it is selected from organo-aluminium compound, organo-magnesium compound, organolithium compound, organic zinc compound, lithium hydride and formula LiOR
3, R in the formula
3Represent alkyl, aryl, aralkyl or cycloalkyl.
2. the method for claim 1, wherein said Cp* is a cyclopentadienyl.
3. the method for claim 1, wherein said titanium compound is selected from: dicyclic pentylene titanium dichloride, bicyclic pentadiene dibrominated titanium, bicyclic pentadiene two titanium iodide, bicyclic pentadiene bifluoride titanium, bicyclic pentadiene dicarbapentaborane titanium, bicyclic pentadiene dimethyl titanium, bicyclic pentadiene diethyl titanium, bicyclic pentadiene dipropyl titanium, bicyclic pentadiene dibutyl titanium, bicyclic pentadiene dibenzyl titanium, bicyclic pentadiene phenylbenzene titanium, bicyclic pentadiene dimethoxy titanium, bicyclic pentadiene diethoxy titanium, bicyclic pentadiene dipropoxy titanium, bicyclic pentadiene dibutoxy titanium, bicyclic pentadiene two phenoxide titaniums, bicyclic pentadiene methyl titanium chloride, bicyclic pentadiene methyl titanium bromide, bicyclic pentadiene methyl titanium iodide, bicyclic pentadiene methyl titanium fluoride and composition thereof.
4. the method for claim 1, the active conjugated diene polymer that wherein said organolithium compound is selected from lithium methide, lithium ethide, n-propyl lithium, sec.-propyl lithium, n-Butyl Lithium, s-butyl lithium, tert-butyl lithium, n-pentyl lithium, phenyl lithium, benzyl lithium and has active lithium.
5. the method for claim 1, wherein said haplotype silane is selected from: dimethyl dichlorosilane (DMCS), ethyl dichlorosilane, the propyl group dichlorosilane, the butyl dichlorosilane, diphenyl dichlorosilane, dimethylchlorosilane, the diethyl chlorosilane, the dipropyl chlorosilane, the dibutyl chlorosilane, diphenyl chlorosilane, the dimethyl methyl TMOS, dimethylethoxysilane, the dimethyl propylene TMOS, the dimethyl butyrate TMOS, benzyloxy-dimethyl silane, the diethyl Ethoxysilane, diethyl propoxy-silane, the diethyl butoxy silane, diethyl benzyloxy silane, the dipropyl methoxy silane, the dipropyl Ethoxysilane, dipropyl propoxy-silane, the dipropyl butoxy silane, dipropyl benzyloxy silane, the dibutyl methoxy silane, the dibutyl Ethoxysilane, dibutyl propoxy-silane, the dibutyl butoxy silane, dibutyl benzyloxy silane, the diphenylmethyl TMOS, the phenylbenzene Ethoxysilane, the diphenylprop TMOS, the phenylbenzene butoxy silane, phenylbenzene benzyloxy silane, dimethylsilane, diethylsilane, dipropyl silane, dibutyl silane, diphenyl silane, diphenylmethylsilane, diphenyl-ethyl silane, the diphenylprop base silane, phenylbenzene butyl silane, trimethyl silane, triethyl silicane, tripropyl silane, tributyl silane, tri-phenyl-silane, methyl-monosilane, ethylsilane, propyl silane, butyl silane, phenyl silane and methyl diacetoxy silane.
6. the method for claim 1, wherein said polymer-type silane is selected from: polymethyl hydrogen siloxane, poly-ethyl hydrogen siloxane, poly-propyl group hydrogen siloxane, poly-butyl hydrogen siloxane, polyphenylene hydrogen siloxane and 1,1,3,3-tetramethyl disiloxane.
7. the method for claim 1, wherein said cyclic silane is selected from: methyl hydrogen cyclosiloxane, ethyl hydrogen cyclosiloxane, propyl group hydrogen cyclosiloxane, butyl hydrogen cyclosiloxane and phenyl hydrogen cyclosiloxane.
8. the method for claim 1, wherein said silazane is selected from: 1,1,3,3-tetramethyl-disilazane, 1,1,3,3-tetraethyl-disilazane, 1,1,3,3-tetrapropyl disilazane, 1,1,3,3-tetrabutyl disilazane and 1,1,3,3-tetraphenyl disilazane.
9. the method for claim 1, the number-average molecular weight of wherein said polymkeric substance is 500 to 1,000, between 000.
10. the method for claim 1, wherein said polymkeric substance is the homopolymer or the multipolymer of 1,3-butadiene and/or isoprene.
11. method as claimed in claim 10, wherein said polymkeric substance is a segmented copolymer, containing at least one principal constituent is that polymer blocks A and at least one principal constituent that vinylbenzene replaces is 1, the polymer blocks B of 3-divinyl and/or isoprene, the content of block A in this segmented copolymer is 0 to 90 weight %, and 1 in the B block, 2-ethylene content are 6 weight % to 80 weight %.
12. the method for claim 1, the content of wherein said titanium compound are to contain the titanium compound of 0.001 mmole to 20 mmole in this polymkeric substance of every 100g.
13. the method for claim 1, wherein the mol ratio of silane (b) and titanium compound (a) is 0.01/1 to 200/1.
14. the method for claim 1, wherein the mol ratio of metallic compound (c) and titanium compound (a) is 0/1 to 100/1.
15. the method for claim 1, wherein said metallic compound (c) is selected from organolithium compound and organo-magnesium compound.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100354319C (en) * | 2004-12-03 | 2007-12-12 | 台橡股份有限公司 | Hydrogenation catalyst composition and method for hydrogenating conjugate diene polymer |
| US7700694B2 (en) | 2006-04-28 | 2010-04-20 | Tsrc Corporation | Catalyst composition and method for hydrogenating a polymer having a conjugated diene |
| CN101829600A (en) * | 2010-04-01 | 2010-09-15 | 台橡股份有限公司 | Hydrogenation catalyst composition and hydrogenation method thereof |
| CN102558442A (en) * | 2010-12-31 | 2012-07-11 | 奇美实业股份有限公司 | Modified conjugated diene-vinyl aromatic hydrocarbon copolymer and method for producing same |
| US9346719B2 (en) | 2009-07-24 | 2016-05-24 | Industrial Technology Research Institute | Catalyst systems and selective hydrogenation processes |
| CN115608420A (en) * | 2021-07-16 | 2023-01-17 | 沈阳化工研究院有限公司 | Styrene conjugated diene polymer hydrogenation catalyst prepared rapidly and continuously and preparation method thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100376604C (en) * | 2004-10-29 | 2008-03-26 | 中国石油化工股份有限公司 | Olefin polymerization catalyst and its uses |
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2000
- 2000-05-24 CN CN 00107660 patent/CN1130382C/en not_active Expired - Lifetime
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100354319C (en) * | 2004-12-03 | 2007-12-12 | 台橡股份有限公司 | Hydrogenation catalyst composition and method for hydrogenating conjugate diene polymer |
| US7700694B2 (en) | 2006-04-28 | 2010-04-20 | Tsrc Corporation | Catalyst composition and method for hydrogenating a polymer having a conjugated diene |
| US9346719B2 (en) | 2009-07-24 | 2016-05-24 | Industrial Technology Research Institute | Catalyst systems and selective hydrogenation processes |
| CN101829600A (en) * | 2010-04-01 | 2010-09-15 | 台橡股份有限公司 | Hydrogenation catalyst composition and hydrogenation method thereof |
| CN101829600B (en) * | 2010-04-01 | 2012-08-29 | 台橡股份有限公司 | Hydrogenation catalyst composition and hydrogenation method thereof |
| CN102558442A (en) * | 2010-12-31 | 2012-07-11 | 奇美实业股份有限公司 | Modified conjugated diene-vinyl aromatic hydrocarbon copolymer and method for producing same |
| CN102558442B (en) * | 2010-12-31 | 2015-03-18 | 奇美实业股份有限公司 | Modified conjugated diene-vinyl aromatic hydrocarbon copolymer and method for producing same |
| CN115608420A (en) * | 2021-07-16 | 2023-01-17 | 沈阳化工研究院有限公司 | Styrene conjugated diene polymer hydrogenation catalyst prepared rapidly and continuously and preparation method thereof |
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