CA1327421C - Hydrogenation process - Google Patents
Hydrogenation processInfo
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- CA1327421C CA1327421C CA000615412A CA615412A CA1327421C CA 1327421 C CA1327421 C CA 1327421C CA 000615412 A CA000615412 A CA 000615412A CA 615412 A CA615412 A CA 615412A CA 1327421 C CA1327421 C CA 1327421C
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Abstract
A B S T R A C T
HYDROGENATION PROCESS
A process for selectively hydrogenating a polymer containing ethylenic unsaturation and cyano groups with a catalyst prepared by combining one or more of certain palladium compounds and one or more aluminum compounds in a suitable solvent or diluent. The hydrogenation is accomplished in a suitable solvent for the polymer.
HYDROGENATION PROCESS
A process for selectively hydrogenating a polymer containing ethylenic unsaturation and cyano groups with a catalyst prepared by combining one or more of certain palladium compounds and one or more aluminum compounds in a suitable solvent or diluent. The hydrogenation is accomplished in a suitable solvent for the polymer.
Description
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HYDROGENATION PROCESS
This invention relates to a method for hydrogenating polymers containing ethylenic unsaturation. More particularly, this invention relates to a process for selectively hydrogenating ethylenic unsaturation contained in a polymer comprising ethylenic ' 5 unsaturation and one or more cyano groups.
Polymers containing both ethylenic unsaturation and cyano groups are, of course, well known in the prior art. Most frequently, such polymers are prepared by copolymerizing a poly-olefin, particularly a diolefin, and an ethylenically unsaturated i 10 nitrile such as acrylonitrile. Such polymers may also incorporate'j~3 other monomer units such as monomers which would incorporate .~ aromatic unsaturation into the polymer. Polymers prepared by -3 copolymerizing a con3ugated diolefin, particularly butadiene, with .:~ an ethylenically unsaturated nitrile, particularly acrylonitrile '-i 15 are, of course, well known in the prior art and such polymers have . been produced commercially for some time. Perhaps the most commonuse for such polymers is as a synthetic rubber but such polymers ~ are produced in a rather broad range of relative compositions over ,;'3 a broad range of molecular weights and have a wide range of end use .. ,l 20 applications. For example, such polymers are known to be useful in .~ fibers, packings, seals, tubes, membranes, sheaths and the like.
As is well known in the prior art, however, the polymer generally `1 cannot be used neat in many of these end use applications due to .~ poor oxygen and ozone resistance and to poor thermal stability.
It is, of course, known in the prior art to improve oxygen and . ozone resistance as well as thermal stability by selectively hydro-genating the polymer, thereby reducing the amount of ethylenic unsaturation contained therein. Earlier, heterogeneous catalysts . comprising a supported metal, such as taught in ~nited Kingdom Patents 2,011,911 and 2, 087,403, were used. Various metals or :
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, ., ~327~21 metal compounds, which may be used supported or unsupported, are also taught in U.S. Patent No. 3,700,637. These catalysts are not, ~ however, particularly active and many are not particularly : selective and, as a result, high degrees of ethylenic unsaturation ; 5 conversion frequently are not achievable without converting at least a portion of the cyano groups to amine groups. Later, mixed metal catalysts, particularly palladium in combination with one or more other metals, such as taught in U.S. Patent 4,337,329, have been used but these catalysts too are not particularly active and, again, many are not particularly selective. More recently, it has - been proposed to use a metal such as platinum, palladium, ruthenium ~j and the like supported on silica as taught in U.S. Patent 4,452,951 but these catalysts also frequently result in conversion of at least a portion of the cyano groups when a high degree of hydro-; 15 genation is achieved and the activity, particularly when Pd isi~ used, remains relatively low. Still more recently, it has beenproposed to use a catalyst prepared by combining a palladium carboxylate and a reducing agent such as hydrogen, as taught in U.S. Patent 4,510,293, but still conversion of the cyano groups to amine groups frequently occurs at high conversion. Moreover, this :l catalyst, particularly as prepared with hydrogen as the reducing agent, is not particularly active. Even more recently, it has been proposed to use various ruthenium compounds as taught in U.S.
Patent 4,631,315 and the use of various rhodium complexes is known ~,j 25 as taught in United Kingdom Patent 1,558,491 and U.S. Patent Nos. 3,700,637 and 4,647,627. At least certain of these latter ,ii . catalysts do facilitate particularly selective hydrogenation of such polymers but the catalyst metals are either rather expensive `' or in short supply. In light of these deficiencies, the need for ,,;
, 30 an improved catalyst composition comprising a metal or metals which ,, are at least reasonably available and which can be used to selectively hydrogenate polymers containing ethylenic unsaturation and one or more cyano groups which will permit relatively high , conversion ~saturation) of the ethylenic unsaturation in relatively ' ~
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short periods of time with reduced conversion of the cyano groups is believed to be readily apparent.
- It has now been discovered that the foregoing and other dis-advantages of the prior art processes for hydrogenating polymers ` 5 containing ethylenic unsaturation and cyano groups can be avoided, or at least reduced, with the process of this invention. This .~ invention therefore seeks to provide a process for selectively . hydrogenating a polymer comprising both ethylenic unsaturation and cyano groups. The invention also seeks to provide such a process which can yield a hydrogenated product having a significant portion of the ethylenic unsaturation converted (hydrogenated) with minimal conversion of cyano groups to amine groups. The invention also seeks to provide such a process which uses a catalyst prepared from materials which are readily available or easily obtained and a process wherein the selective hydrogenation may be accomplished ~ with relatively short contacting times.
:;-3 In accordance with the present invention, there is provided a i~ process for selectively hydrogenating a polymer comprising ~i ethylenic unsaturation and cyano groups comprising the steps of:
.. ~ 20 (a) contacting a polymer comprising ethylenic unsaturation and cyano groups with hydrogen in a first suitable solvent and in ~ the presence of a catalyst prepared by combining one or more ,i palladium compounds with one or more aluminum compounds in a second suitable solvent, which second suitable solvent may be the same or different from said first suitable solvent;
(b) maintaining the contact in step (a) for a sufficient period of time to permit conversion of at least a portion of the ethylenic unsaturation contained in said polymer; and (c) recovering an at least partially hydrogenated polymer.
In one form of the invention, the catalyst is prepared by - contacting one or more of certain palladium compounds with one or -1 more aluminum compounds selected from the group consisting of aluminum hydrides, aluminum alkyls and mixtures thereof. In an alternative preferred form of the invention, the catalyst is , , 35 prepared by contacting one or more palladium compounds with one or ::, '., . 1 ~ ,.
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more alkylalumoxanes in a suitable solvent. As a matter of convenience the one or more alkyl alumoxanes will frequently be referred to herein simply as alumoxanes.
The catalyst is prepared by com~ining the palladium compound .~ 5 or compounds and the aluminum compound or compounds in a suitable ' solvent. Hydrogenation of the polymer is suitably accomplished at ;: elevated temperatures and pressures and is also accomplished in a : suitable solvent.
The accompanying Figure is a graph showing the extent of ethylenic unsaturation conversion or hydrogenation at two different ;-~ nominal holding time periods as a function of the aluminum topalladium molar ratio used to prepare the hydrogenation catalyst.
~ As just indicated supra, the present invention relates to a i"~ process for selectively hydrogenating ethylenic unsaturation . 15 contained in a polymer comprising ethylenic unsaturation and one or more cyano groups. The hydrogenation is accomplished in the 3~ presence of a catalyst prepared by contacting one or more palladium .' compounds with one or more aluminum compounds in a suitable solvent.
.~ 20 In general, any polymer containing ethylenic unsaturation and . .i .~ one or more cyano groups may be hydrogenated with the method of ~ this invention. Polymers which may be hydrogenated, then, include , . .
addition polymers prepared by polymerizing one or more polyolefins, 'i particularly diolefins, which polymers also contain one or more :- 25 cyano groups. The cyano groups may be incorporated into the ,i polymer by copolymerizing one or more ethylenically unsaturated , ;!,, -` nitriles with the polyolefin or polyolefins. The cyano groups may ~, also be incorporated by grafting one or more ethylenically unsaturated nitriles onto a polymer containing ethylenic ~ 30 unsaturation. The cyano group may further be incorporated by :-1, reacting a polymer containing ethylenic unsaturation with a compound capable of adding a cyano group into the polymer. For example, one or more cyano groups may be introduced into a polymer containing metal atoms by reaction with Cl-C=N, as taught, for - 35 exa=p1e, in U.S. ~atent 3O. 3,13~,716. The poly=ers whlch =ay be , .1 , . . . , - :. .
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~ --` 1327421 .. hydrogenated with the process of this invention may also contain aromatic unsaturation. As is well known, aromatic unsaturation may be incorporated into a polymer by copolymerizing a monomer containing aromatic unsaturation such as a monoalkenyl aromatic hydrocarbon.
.~ As is well known in the prior art, polymers comprising poly-~ olefin monomer units as well as polymers containing both polyolefin ., monomer units and monoalkenyl aromatic hydrocarbon monomer units .i may be prepared by polymerizing the monomers in bulk, solution or.~ 10 emulsion. In general, any of the polymerization initiators or ~, catalysts known in the prior art may be used to effect the polymerization. Suitable catalysts, then, include free radical, ~, anionic snd cationic initiators or polymerization catalysts. As is i' well known however the anionic and cationic initiators are not acceptable for use in emuls$on polymerization. As is also well e known in the prior art, ethylenically unsaturated nitriles do not ' lend themselves to polymerization or copolymerization with anionic and cationic initiators. Polymers prepared by copolymerizing one . !
or more polyolefin monomers and one or more ethylenically i 20 unsaturated nitriles are, then, most generally, prepared with free -~ radical initiators or catalysts. Moreover, copolymers containing-, one or more ethylenically unsaturated nitrile monomer units are most frequently prepared using emulsion techniques. When the polymer to be hydrogenated with the method of the present invention .~ 25 is, then, a copolymer containing one or more ethylenically un-'~:'J, saturated nitriles, which copolymer is prepared by direct co-i"'~! polymerization, as opposed to grafting or modification, emulsion techniques will generally be used, as will a free radical -~ initiator. Such polymers may be random, tapered or block. When - 30 the polymer to be hydrogenated, on the other hand, is a graft or~l modified copolymer the base polymer containing ethylenic un-''J saturation may first be prepared using any of the known techniques ;.~ and an ethylenically unsaturated nitrile then grafted thereon using a free radical initiator or the cyano group incorporated via direct ;, 35 or indirect reaction between a base polymer containing ethylenic ' . .
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unsaturation or ethylenic and aromatic unsaturation and a compound capable of adding a cyano group into the polymer. Again, the base ; polymer, when not a homopolymer, may be random, tapered or block.
While the method of the present invention may be used to selectively hydrogenate any polymer containing ethylenic , ..
unsaturation and one or more cyano groups and, optionally, aromatic ~; unsaturation, the method of this invention will be used most frequently to selectively hydrogenate copolymers of one or more ~l conjugated diolefins and one or more ethylenically unsaturated `'~t1 10 nitriles; copolymers of one or more monoalkenyl aromatic hydro-', l ' carbon monomers, one or more conjugated diolefins and one or more .l ethylenically unsaturated nitriles; graft copolymers wherein one or more ethylenically unsaturated nitriles are grafted onto a base ~ polymer of one or more conjugated diolefins or a base copolymer of :~ 15 one or more monoalkenyl aromatic hydrocarbon monomers and one or more conjugated diolefins; modified copolymers of one or more conjugated diolefins and modified copolymers of one or more mono-alkenyl aromatic hydrocarbon monomers and one or more conjugated .; diolefins; said polymers being modified by reacting the polymer or a derivative thereof with a compound capable of adding a cyano . group into the polymer. Each of these polymers may be prepared ~ using methods well known in the prior art. In general, the *'~ molecular weight and relative composition of the polymers hydro-,i genated with the method of this invention are not critical. It is, ~ 25 however, important that the polymer be soluble in a suitable -.i solvent for effecting the hydrogenation and this requirement could limit the maximum useful polymer molecular weight or the . composition thereof with any given solvent.
In general, any of the palladium compounds known to be useful 3o in the preparation of catalysts for the hydrogenation of ethylenic unsaturation can be used separately or in combination to prepare the catalyst of this invention. Suitable compounds, then, include ; palladium carboxylates having the formula (RC00) Pd, where R is a ,l hydrocarbyl radical having from l to about 50 carbon atoms, ~ 35 preferably from about 5 to 30 carbon atoms, and n is a number ,, ....
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satisfying the valence of the Pd; palladium chelates containing from about 3 to about 50 carbon atoms, preferably from about 3 to about 20 carbon atoms; alkoxides having the formula (RCO)nPd wherein R is a hydrocarbon radical having from 1 to about 50 carbon ~- 5 atoms, preferably about 5 to about 30 carbon atoms, and n is a number satisfying the valence of the Pd; salts of sulfur-containing !...... , acids having the general formula Pd(S0x) and partial esters . thereof; and palladium salts of aliphatic and aromatic sulfonic .~ acids having the general formula Pd~R'S03) wherein R' is an13 aliphatic or aromatic radical having from 1 to about 20 carbon atoms and n is a number satisfying the valence of Pd. The carboxylates useful in preparing the catalyst of this invention `.` include palladium salts of hydrocarbon aliphatic acids, hydrocarbon ` cycloaliphatic acids and hydrocarbon aromatic acids. Examples of hydrocarbon aliphatic acids include hexanoic acid, ethylhexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, dodecanoic acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, rhodinic acid and the like. Examples of hydrocarbon aromatic acids include benzoic acid and alkyl-substituted aromatic acids in which the alkyl substitution has from - 1 to about 20 carbon atoms. Examples of cycloaliphatic acids . include naphthenic acid, cyclohexylcarboxylic acid, abietic-type resin acids and the like. Suitable chelating agents which may be combined with various palladium compounds thereby yielding a palladium chelate compound useful in the preparation of the -' catalyst of this invention include ~-ketones, ~-hydroxycarboxylic acids, ~-hydroxy carboxylic acids, ~-hydroxycarbonyl compounds and the like. Examples of ~-ketones which may be used include - acetylacetone, 1,3-hexanedione, 3,5-nonadione, methylacetoacetate, - 30 ethylacetoacetate and the like. Examples of ~-hydroxycarboxylic acid which may be used include lactic acid, glycolic acid, ~-hydroxyphenylacetic acid, o-hydroxy-o-phenylacetic acid, u-hydroxycyclohexylacetic acid and the like. Examples of ~-hydroxycarboxylic acids include salicylic acid, alkyl-substituted ' 35 salicyclic acids and the like. Examples of ~-hydroxylcarbonyl :~' '.i ,~
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compounds that may be used include salicylaldehyde, o-hydrsxy-acetophenone and the like. The metal alkoxides which are useful in preparing catalysts of this invention include palladium alkoxides of hydrocarbon aliphatic alcohols, hydrocarbon cycloaliphatic alcohols and hydrocarbon aromatic alcohols.
Examples of hydrocarbon aliphatic alcohols include hexanol, ,.
i ethylhexanol, heptanol, octanol, nonanol, decanol, dodecanol and ;~, the like. The palladium metal salts of sulfur-containing acids ` and partial esters thereof include palladium salts of sulfonic . . .
' 10 acid, sulfuric acid, sulphurous acid, partial esters thereof and the like. Of the aliphatic and aromatic acids salts, salts of ;,"
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' sulfonic acid and the like are particularly useful.
In general, any one or more of the aluminum compounds known to be useful in preparing a hydrogenation catalyst may be ,; used to prepare the hydrogenation catalyst used in the method of - this invention. Suitable aluminum compounds, then, include those aluminum compounds having the general formula: Al(R)3; wherein . each R may be the same or a different radical selected from H and hydrocarbyl radicals having from 1 to about 20 carbon atoms.
Preferably, each R will be an alkyl radical having from 1 to about 5 carbon atoms.
A further preferred group of suitable aluminum compounds are the alkylalumoxane compounds known to be useful in the preparation of olefin polymerization catalysts as taught, for ~-~ example, in U.S. ~atent No. 4,665,208, may be used separately or ' in combination in preparing the hydrogenation catalyst of this ~ .
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invention. Alumoxane compounds useful in preparing the catalyst of this invention may be cyclic or linear. Cyclic alumoxanes may be represented by the general formula (R-Al-O)m while linear alumoxanes may be represented by the general formula R2AlO-(R-Al-O)-nAlR2. In both of the general formulae each R and/or each R2 will be the same or a different alkyl group having from 1 to about 8 carbon atoms, preferably from 1 to about 5 carbon . .
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: 1327~L21 , 9 .~ atoms, such as, for example, methyl, ethyl, propyl, butyl and pentyl; m is an integer from about 3 to about 40 and n is an integer from about 1 to about 40. In a preferred embodiment of the present invention, the one or more alkylalumoxanes will be a blend ~` 5 of cyclic and linear alumoxanes wherein each R will be methyl, m will be a number from about 3 to about 20 and n will be a number ^ from about 10 to about 20. As is well known alumoxanes may be prepared by reacting an aluminum alkyl with water. Generally, the ; resulting product will be a mixture of both linear and cyclic compounds.
As is well known, contacting of the aluminum alkyl and water ; may be accomplished in several ways. For example, the aluminum . alkyl may first be dissolved in a suitable solvent such as toluene i~ or an aliphatic hydrocarbon and the solution then contacted with a similar solvent containing relatively minor amounts of moisture.
; Alternatively, an aluminum alkyl may be contacted with a hydrated salt such as hydrated copper sulfate or ferrous sulfate. Uhen this method is used, a hydrated ferrous sulfate is frequently used.
, According to this method, a dilute solution of aluminum alkyl in a suitable solvent such as toluene is contacted with hydrated ferrous sulfate. In general, about 1 mole of hydrated ferrous sulfate will be contacted with from about 6 to about 7 moles of the aluminum trialkyl. ~hen aluminum trimethyl is the aluminum alkyl actually used, methane will be evolved as conversion of the aluminum alkyl to an alumoxane occurs.
In general, the hydrogenation catalyst useful in the hydro-, .
genation process of this invention will be prepared by combining the palladium compound or compounds and the aluminum co~pound or compounds in a suitable solvent or diluent. In general, the palladium and aluminum compounds will be combined so as to provide an Al:Pd atomic ratio within the range from about 0.1:1 to about `~ 1.5:1, although when alumoxanes are used the range can suitably be up to about 20:1. In general, the contacting will be accomplished at a temperature within the range from about 20 to about 100C in an inert or reducing atmosphere. In general, any solvent or ,~ , . .. . ..
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`~` 1327~21 - 10 - ' diluent that does not react with either the palladium or aluminum compounds used to prepare the catalyst may be used during the preparation of said catalyst. It will, of course, frequently be most convenient to prepare the catalyst in the same solvent in which the polymer is dissolved and in which the subsequent hydro-genation will occur and such solvents may be used to prepare the catalyst used in the method of this invention. Suitable solvents for the polymers which may be hydrogenated with the process of this ii invention are discussed infra. Catalysts prepared in an ether solvent are, however, significantly more active than catalysts prepared in hydrocarbon. The use of an ether solvent in preparing the catalyst is, therefore, preferred. In general, any linear or cyclic ether having from two to about 20 carbon atoms and from l to about 3 oxygen atoms may be used. Diethers having from about 4 to about lO carbon atoms are particularly effective and are preferred.
In general, the palladium and aluminum compounds used to prepare the hydrogenation catalyst may be, and preferably will be, combined in a separate vessel but each of the components could be separately introduced into the hydrogenation reaction vessel so long as the temperature at which these components are contacted is within the range heretofore specified. In general, contacting times within the range from about l to about 120 minutes will be sufficient to effect reduction of the palladium compound or compounds or other-wise produce an active catalyst.
In general, the hydrogenation will be accomplished with the polymer in solution. In general, any of the solvents known in the prior art to be useful for dissolving copolymers containing one or more conjugated diolefins, optionally one or more alkenyl aromatic hydrocarbons, and one or more cyano groups may be used to effect the hydrogenation in the process of this invention. Suitable solvents, then, include linear and cyclic ethers such as diethyl ether, tetrahydrofuran, and the like; halogenated, particularly chlorinated, aromatic hydrocarbons such as chlorobenzene, dichloro-benzene, methylchlorobenzene and the like; aliphatic and cyclic ketones such as acetone, methylethyl ketone, diethyl ketone, ,1 '';
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: butanone, pentanone, cyclopentanone, cyclohexanone and the like.
i,i In general, the hydrogenation will be accomplished at a temperature within the range from about 20C to about 175C at a total pressure .-~ within the range from about 50 psig to about 1,000 psig and at a ,i 5 hydrogen partial pressure within the range from about 50 psig to about 950 psig. In general, the catalyst or the components thereof will be added during hydrogenation in a concentration sufficient to .1 provide from about 0.4 to about 40 mmoles (gm moles) of palladium per lb. oi polymer. In general, contacting at hydrogenation ~ 10 conditions will be continued for a nominal holding time within the .-: range from about 10 to about 360 minutes. With respect to the .; .
`, hydrogenation, it should be noted that while selective hydro-genation of ethylenic unsaturation may be accomplished at the -i conditions ~ust recited conversion of the cyano groups to amine groups will, generally, begin to occur when the extent of hydro-~i genation of the ethylenic unsaturation reaches about 90~. In this regard, it should be noted that of the several variables available l for control of the extent of hydrogenation, temperature, catalyst .~! concentration and holding time generally have the greatest impact.
These variables may, then, be carefully controlled so as to avoid any significant conversion of the cyano groups to amine groups.
Hydrogenation of aromatic unsaturation, generally, will not occur .~ at the hydrogenation conditions contemplated for use in the process.~. of this invention. Some conversion of aromatic unsaturation may, s~ 25 however, occur at higher ethylenic unsaturation conversions.
~ While not wishing to be bound by any particular theory, it is `~ believed that when the palladium compound or compounds and the aluminum compound or compounds are combined, a reaction occurs to ' form a catalyst. The catalyst thus formed is stable and can be stored for relatively long periods prior to use.
After hydrogenation of the polymer has been completed, the polymer may be recovered as a crumb using methods well known in the . prior art. For example, the polymer may be recovered as a crumb by '`'! precipitation with a polar compound such as an alcohol. Alter-~ 35 natively, the solution may be contacted with steam or water and the ,, " .
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- - 1327~21 . - 12 -solvent then removed by an azeotropic distillation. Generally, , these recovery techniques will also effectively remove a significant portion of the catalyst.
The hydrogenated polymers produced by the method of this 5 invention can be used in any of the applications well known in the prior art for such hydrogenated polymers. For example, selectively hydrogenated copolymers comprising one or more conjugated diolefin monomer units and cyano groups will have improved weatherability and temperature resistance and may be used in seals, packing, tubes 10 and the like.
In one preferred embodiment of the present invention, a random copolymer comprising from about 55 wt% to about 85 wt% conjugated ' diolefin monomer units and from about 45 wt% to about 15 wt% ofunsaturated nitrile monomer units is selectively hydrogenated in .- 15 solution with a catalyst prepared by combining a palladium ~, carboxylate having from about 5 to about 30 carbon atoms and an'~, aluminum trialkyl wherein each alkyl group may be the same or different and has from 1 to about 5 carbon atoms. Preferably, a butadiene/acrylonitrile copolymer is hydrogenated in the presence 20 of a catalyst prepared by contacting a palladium 2-ethylhexanoate ~1 with triethyl aluminum. The palladium carboxylate and the aluminum ;~ trialkyl are preferably combined in amounts sufficient to provide an Al:Pd atomic ratio within the range from about 0.3 to about 0.9.
The catalyst is preferably prepared in a separate step using a 25 diether containing from about 4 to about 10 carbon atoms as -o~ solvent. Preferably 1,2-dimethyoxyethane is used as the solvent.
,~ In a further preferred embodiment, a random copolymer comprising from about 55 wt% to about 85 wt% conjugated diolefin monomer units and from about 45 wt% to about 15 wt% of unsaturated sJ 30 nitrile monomer units is selectively hydrogenated in solution with a catalyst prepared by combining a palladium carboxylate having from about 5 to about 30 carbon atoms and a blend of `~, alkylalumoxanes comprising at ieast one alumoxane having the . general formula (R-A10) and at least one alumoxane having the , 35 general formula R2A10-(R-Al-0)-nAlR2 wherein R is a methyl radical, ., .
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m is a number from about 3 to about 20 and n is a number from about 10 to about 20. Preferably, a butadiene/acrylonitrile copolymer is hydrogenated in the presence of a catalyst prepared by contacting a palladium 2-ethylhexanoate with a preferred blend of alkylalumoxanes. The palladium carbcxylate and the blend of alkylalumoxanes are preferably combined in amounts sufficient to provide an Al:Pd atomic ratio within the range from about 0.2:1 to about 10:1. The palladium carboxylate and the alkylalumoxane are preferably combined in amounts sufficient to provide an Al:Pd atomic ratio within the range from about 0.5:1 to about 2:1. The catalyst is preferably prepared in a separate step using an ether as a solvent. Most preferably, a diether containing from about 4 to about 10 carbon atoms such as 1,2-dimethoxyethane is used as the solvent for the catalyst preparation.
In both the preferred embodiments, the components used to prepare the catalyst are suitably contacted at a temperature within the range from about 25C to about ~0C and the contacting continued for a period of time within the range from about 15 to about 60 minutes. The hydrogenation is suitably accomplished at a temperature within the range from about 20C to about 100C at a total pressure within the range from about 50 psig to about 1,000 psig and at a hydrogen partial pressure within the range from 50 psig to about 950 psig. The hydrogenation is preferably accomplished in a ketone solvent, preferably an aliphatic ketone having from about 3 to about 10 carbon atoms, preferably a dialkyl ketone with each alkyl group being the same or different and containing from 1 to about 5 carbon atoms, a preferred ketone being methyl ethyl ketone.
The selective hydrogenation is suitably accomplished so as to convert tsaturate) at least about 85% of the ethylenic unsaturation intially contained in the polymer and such that no more than about 10% of the cyano groups are converted to amine groups. In the preferred embodiments, the polymer is preferably present in solution at a concentration within the range from about 2 to about 15 wt~ based upon combined polymer and solvent. The nominal . .
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' holding time at hydrogenation conditions is preferably within the range from about 30 to about 120 minutes. Preferably, sufficient catalyst will be added during the hydrogenation to provide from ~ about 0.2 to about 15 mmoles (gm moles) palladium per lb of ; 5 polymer, preferably from about 5 to about 15 mmoles ~gm moles) palladium per lb when using alumoxane(s).
Having thus broadly described the present invention and preferred embodiments thereof, it is believed that the invention , will become even more apparent by reference to the following -' 10 Examples. It will be appreciated, however, that the Examples are ~.~, presented solely for the purpose of illustration and should not be ,;-~ construed as lim$ting the invention.
~, Example 1 In this Example, a series of hydrogenation catalysts were .~ 15 prepared by combining a palladium salt of 2-ethyl-hexanoic acid and - triethyl aluminum at different Al:Pd atomic ratios. Also, for purposes of comparison, a catalyst, hereinafter referred to as . Catalyst No. 1, was prepared with palladium 2-ethylhexanoate without triethyl aluminum. This catalyst was, then, prepared ~ 20 simply by reducing the palladium salt of 2-ethylhexanoic ac~d with '~ hydrogen in the hydrogenation reactor and in the presence of the polymer. In the catalysts prepared in this Example, the Al:Pd atomic ratio ranged, then, from 0 to about 1.5. In preparing those catalysts wherein aluminum triethyl was used as a reducing agent, ~.. 25 the palladium salt and aluminum triethyl were combined in i' 1,2-dimethoxyethane, contacted at a temperature of 25C and then i allowed to exotherm for 30 minutes. The catalyst which was prepared without aluminum was prepared by contacting the palladium salt with hydrogen in methylethylketone and in the presence of the ~, 30 polymer at a temperature of 60C and at a hydrogen partial pressure ~ of about 895 psig. In preparing each of the catalysts, the : palladium salt was present in the solvent at a concentration of 40 mmoles/liter. After preparation, each of the catalysts prepared with triethyl aluminum were retained in the solvent and stored at a temperature of 25C until later used to selectively hydrogenate a .
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~' modified block copolymer. In all, nine catalysts were prepared in this Example. For convenience, these catalysts are hereinafter referred to as catalysts 1-9 and the relative Al:Pd atomic ratio ~: used in preparing each of the nine catalysts is summarizèd in the -' 5 following Table 1:
Table 1 :' `l Al:Pd ~ Catalyst No. Atomic Ratio 5~; 1 0 ~. 2 0.1 . . i 3 0.3 4 0.5 ~ 0.7 .~4 6 0.9 ," ~ 1 . 1 8 1.3 , 9 1.5 . .~
Example 2 ~ In this Example, each of the catalysts prepared in Example 1 ,j was used to selectively hydrogenate a butadiene-acrylonitrile rubber containing 80 wt~ butadiene and 20 wt% acrylonitrile. ~ach .`- 10 of the hydrogenations was accomplished in the presence of sufficient catalyst to provide about 8.5 mmoles Pd per lb of ~ polymer at 60C, at a total pressure of 900 psig and at a hydrogen -i partial pressure of about 895 psig. Each of the hydrogenations was 1 accomplished in a methylethyl ketone solvent and in each of the , hydrogenation runs the polymer was present at a concentration of 5 . wt% based on total polymer and solvent. During each hydrogenation run, a sample was withdrawn after 30 minutes, and at two hours and the extent of hydrogenation determined on each of these samples.
; The extent of hydrogenation was determined using an ozone titration 'i 20 to determine the relative amount of ethylenic unsaturation ;:
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HYDROGENATION PROCESS
This invention relates to a method for hydrogenating polymers containing ethylenic unsaturation. More particularly, this invention relates to a process for selectively hydrogenating ethylenic unsaturation contained in a polymer comprising ethylenic ' 5 unsaturation and one or more cyano groups.
Polymers containing both ethylenic unsaturation and cyano groups are, of course, well known in the prior art. Most frequently, such polymers are prepared by copolymerizing a poly-olefin, particularly a diolefin, and an ethylenically unsaturated i 10 nitrile such as acrylonitrile. Such polymers may also incorporate'j~3 other monomer units such as monomers which would incorporate .~ aromatic unsaturation into the polymer. Polymers prepared by -3 copolymerizing a con3ugated diolefin, particularly butadiene, with .:~ an ethylenically unsaturated nitrile, particularly acrylonitrile '-i 15 are, of course, well known in the prior art and such polymers have . been produced commercially for some time. Perhaps the most commonuse for such polymers is as a synthetic rubber but such polymers ~ are produced in a rather broad range of relative compositions over ,;'3 a broad range of molecular weights and have a wide range of end use .. ,l 20 applications. For example, such polymers are known to be useful in .~ fibers, packings, seals, tubes, membranes, sheaths and the like.
As is well known in the prior art, however, the polymer generally `1 cannot be used neat in many of these end use applications due to .~ poor oxygen and ozone resistance and to poor thermal stability.
It is, of course, known in the prior art to improve oxygen and . ozone resistance as well as thermal stability by selectively hydro-genating the polymer, thereby reducing the amount of ethylenic unsaturation contained therein. Earlier, heterogeneous catalysts . comprising a supported metal, such as taught in ~nited Kingdom Patents 2,011,911 and 2, 087,403, were used. Various metals or :
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, ., ~327~21 metal compounds, which may be used supported or unsupported, are also taught in U.S. Patent No. 3,700,637. These catalysts are not, ~ however, particularly active and many are not particularly : selective and, as a result, high degrees of ethylenic unsaturation ; 5 conversion frequently are not achievable without converting at least a portion of the cyano groups to amine groups. Later, mixed metal catalysts, particularly palladium in combination with one or more other metals, such as taught in U.S. Patent 4,337,329, have been used but these catalysts too are not particularly active and, again, many are not particularly selective. More recently, it has - been proposed to use a metal such as platinum, palladium, ruthenium ~j and the like supported on silica as taught in U.S. Patent 4,452,951 but these catalysts also frequently result in conversion of at least a portion of the cyano groups when a high degree of hydro-; 15 genation is achieved and the activity, particularly when Pd isi~ used, remains relatively low. Still more recently, it has beenproposed to use a catalyst prepared by combining a palladium carboxylate and a reducing agent such as hydrogen, as taught in U.S. Patent 4,510,293, but still conversion of the cyano groups to amine groups frequently occurs at high conversion. Moreover, this :l catalyst, particularly as prepared with hydrogen as the reducing agent, is not particularly active. Even more recently, it has been proposed to use various ruthenium compounds as taught in U.S.
Patent 4,631,315 and the use of various rhodium complexes is known ~,j 25 as taught in United Kingdom Patent 1,558,491 and U.S. Patent Nos. 3,700,637 and 4,647,627. At least certain of these latter ,ii . catalysts do facilitate particularly selective hydrogenation of such polymers but the catalyst metals are either rather expensive `' or in short supply. In light of these deficiencies, the need for ,,;
, 30 an improved catalyst composition comprising a metal or metals which ,, are at least reasonably available and which can be used to selectively hydrogenate polymers containing ethylenic unsaturation and one or more cyano groups which will permit relatively high , conversion ~saturation) of the ethylenic unsaturation in relatively ' ~
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short periods of time with reduced conversion of the cyano groups is believed to be readily apparent.
- It has now been discovered that the foregoing and other dis-advantages of the prior art processes for hydrogenating polymers ` 5 containing ethylenic unsaturation and cyano groups can be avoided, or at least reduced, with the process of this invention. This .~ invention therefore seeks to provide a process for selectively . hydrogenating a polymer comprising both ethylenic unsaturation and cyano groups. The invention also seeks to provide such a process which can yield a hydrogenated product having a significant portion of the ethylenic unsaturation converted (hydrogenated) with minimal conversion of cyano groups to amine groups. The invention also seeks to provide such a process which uses a catalyst prepared from materials which are readily available or easily obtained and a process wherein the selective hydrogenation may be accomplished ~ with relatively short contacting times.
:;-3 In accordance with the present invention, there is provided a i~ process for selectively hydrogenating a polymer comprising ~i ethylenic unsaturation and cyano groups comprising the steps of:
.. ~ 20 (a) contacting a polymer comprising ethylenic unsaturation and cyano groups with hydrogen in a first suitable solvent and in ~ the presence of a catalyst prepared by combining one or more ,i palladium compounds with one or more aluminum compounds in a second suitable solvent, which second suitable solvent may be the same or different from said first suitable solvent;
(b) maintaining the contact in step (a) for a sufficient period of time to permit conversion of at least a portion of the ethylenic unsaturation contained in said polymer; and (c) recovering an at least partially hydrogenated polymer.
In one form of the invention, the catalyst is prepared by - contacting one or more of certain palladium compounds with one or -1 more aluminum compounds selected from the group consisting of aluminum hydrides, aluminum alkyls and mixtures thereof. In an alternative preferred form of the invention, the catalyst is , , 35 prepared by contacting one or more palladium compounds with one or ::, '., . 1 ~ ,.
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: ` 1327~2~
more alkylalumoxanes in a suitable solvent. As a matter of convenience the one or more alkyl alumoxanes will frequently be referred to herein simply as alumoxanes.
The catalyst is prepared by com~ining the palladium compound .~ 5 or compounds and the aluminum compound or compounds in a suitable ' solvent. Hydrogenation of the polymer is suitably accomplished at ;: elevated temperatures and pressures and is also accomplished in a : suitable solvent.
The accompanying Figure is a graph showing the extent of ethylenic unsaturation conversion or hydrogenation at two different ;-~ nominal holding time periods as a function of the aluminum topalladium molar ratio used to prepare the hydrogenation catalyst.
~ As just indicated supra, the present invention relates to a i"~ process for selectively hydrogenating ethylenic unsaturation . 15 contained in a polymer comprising ethylenic unsaturation and one or more cyano groups. The hydrogenation is accomplished in the 3~ presence of a catalyst prepared by contacting one or more palladium .' compounds with one or more aluminum compounds in a suitable solvent.
.~ 20 In general, any polymer containing ethylenic unsaturation and . .i .~ one or more cyano groups may be hydrogenated with the method of ~ this invention. Polymers which may be hydrogenated, then, include , . .
addition polymers prepared by polymerizing one or more polyolefins, 'i particularly diolefins, which polymers also contain one or more :- 25 cyano groups. The cyano groups may be incorporated into the ,i polymer by copolymerizing one or more ethylenically unsaturated , ;!,, -` nitriles with the polyolefin or polyolefins. The cyano groups may ~, also be incorporated by grafting one or more ethylenically unsaturated nitriles onto a polymer containing ethylenic ~ 30 unsaturation. The cyano group may further be incorporated by :-1, reacting a polymer containing ethylenic unsaturation with a compound capable of adding a cyano group into the polymer. For example, one or more cyano groups may be introduced into a polymer containing metal atoms by reaction with Cl-C=N, as taught, for - 35 exa=p1e, in U.S. ~atent 3O. 3,13~,716. The poly=ers whlch =ay be , .1 , . . . , - :. .
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~ --` 1327421 .. hydrogenated with the process of this invention may also contain aromatic unsaturation. As is well known, aromatic unsaturation may be incorporated into a polymer by copolymerizing a monomer containing aromatic unsaturation such as a monoalkenyl aromatic hydrocarbon.
.~ As is well known in the prior art, polymers comprising poly-~ olefin monomer units as well as polymers containing both polyolefin ., monomer units and monoalkenyl aromatic hydrocarbon monomer units .i may be prepared by polymerizing the monomers in bulk, solution or.~ 10 emulsion. In general, any of the polymerization initiators or ~, catalysts known in the prior art may be used to effect the polymerization. Suitable catalysts, then, include free radical, ~, anionic snd cationic initiators or polymerization catalysts. As is i' well known however the anionic and cationic initiators are not acceptable for use in emuls$on polymerization. As is also well e known in the prior art, ethylenically unsaturated nitriles do not ' lend themselves to polymerization or copolymerization with anionic and cationic initiators. Polymers prepared by copolymerizing one . !
or more polyolefin monomers and one or more ethylenically i 20 unsaturated nitriles are, then, most generally, prepared with free -~ radical initiators or catalysts. Moreover, copolymers containing-, one or more ethylenically unsaturated nitrile monomer units are most frequently prepared using emulsion techniques. When the polymer to be hydrogenated with the method of the present invention .~ 25 is, then, a copolymer containing one or more ethylenically un-'~:'J, saturated nitriles, which copolymer is prepared by direct co-i"'~! polymerization, as opposed to grafting or modification, emulsion techniques will generally be used, as will a free radical -~ initiator. Such polymers may be random, tapered or block. When - 30 the polymer to be hydrogenated, on the other hand, is a graft or~l modified copolymer the base polymer containing ethylenic un-''J saturation may first be prepared using any of the known techniques ;.~ and an ethylenically unsaturated nitrile then grafted thereon using a free radical initiator or the cyano group incorporated via direct ;, 35 or indirect reaction between a base polymer containing ethylenic ' . .
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unsaturation or ethylenic and aromatic unsaturation and a compound capable of adding a cyano group into the polymer. Again, the base ; polymer, when not a homopolymer, may be random, tapered or block.
While the method of the present invention may be used to selectively hydrogenate any polymer containing ethylenic , ..
unsaturation and one or more cyano groups and, optionally, aromatic ~; unsaturation, the method of this invention will be used most frequently to selectively hydrogenate copolymers of one or more ~l conjugated diolefins and one or more ethylenically unsaturated `'~t1 10 nitriles; copolymers of one or more monoalkenyl aromatic hydro-', l ' carbon monomers, one or more conjugated diolefins and one or more .l ethylenically unsaturated nitriles; graft copolymers wherein one or more ethylenically unsaturated nitriles are grafted onto a base ~ polymer of one or more conjugated diolefins or a base copolymer of :~ 15 one or more monoalkenyl aromatic hydrocarbon monomers and one or more conjugated diolefins; modified copolymers of one or more conjugated diolefins and modified copolymers of one or more mono-alkenyl aromatic hydrocarbon monomers and one or more conjugated .; diolefins; said polymers being modified by reacting the polymer or a derivative thereof with a compound capable of adding a cyano . group into the polymer. Each of these polymers may be prepared ~ using methods well known in the prior art. In general, the *'~ molecular weight and relative composition of the polymers hydro-,i genated with the method of this invention are not critical. It is, ~ 25 however, important that the polymer be soluble in a suitable -.i solvent for effecting the hydrogenation and this requirement could limit the maximum useful polymer molecular weight or the . composition thereof with any given solvent.
In general, any of the palladium compounds known to be useful 3o in the preparation of catalysts for the hydrogenation of ethylenic unsaturation can be used separately or in combination to prepare the catalyst of this invention. Suitable compounds, then, include ; palladium carboxylates having the formula (RC00) Pd, where R is a ,l hydrocarbyl radical having from l to about 50 carbon atoms, ~ 35 preferably from about 5 to 30 carbon atoms, and n is a number ,, ....
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satisfying the valence of the Pd; palladium chelates containing from about 3 to about 50 carbon atoms, preferably from about 3 to about 20 carbon atoms; alkoxides having the formula (RCO)nPd wherein R is a hydrocarbon radical having from 1 to about 50 carbon ~- 5 atoms, preferably about 5 to about 30 carbon atoms, and n is a number satisfying the valence of the Pd; salts of sulfur-containing !...... , acids having the general formula Pd(S0x) and partial esters . thereof; and palladium salts of aliphatic and aromatic sulfonic .~ acids having the general formula Pd~R'S03) wherein R' is an13 aliphatic or aromatic radical having from 1 to about 20 carbon atoms and n is a number satisfying the valence of Pd. The carboxylates useful in preparing the catalyst of this invention `.` include palladium salts of hydrocarbon aliphatic acids, hydrocarbon ` cycloaliphatic acids and hydrocarbon aromatic acids. Examples of hydrocarbon aliphatic acids include hexanoic acid, ethylhexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, dodecanoic acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, rhodinic acid and the like. Examples of hydrocarbon aromatic acids include benzoic acid and alkyl-substituted aromatic acids in which the alkyl substitution has from - 1 to about 20 carbon atoms. Examples of cycloaliphatic acids . include naphthenic acid, cyclohexylcarboxylic acid, abietic-type resin acids and the like. Suitable chelating agents which may be combined with various palladium compounds thereby yielding a palladium chelate compound useful in the preparation of the -' catalyst of this invention include ~-ketones, ~-hydroxycarboxylic acids, ~-hydroxy carboxylic acids, ~-hydroxycarbonyl compounds and the like. Examples of ~-ketones which may be used include - acetylacetone, 1,3-hexanedione, 3,5-nonadione, methylacetoacetate, - 30 ethylacetoacetate and the like. Examples of ~-hydroxycarboxylic acid which may be used include lactic acid, glycolic acid, ~-hydroxyphenylacetic acid, o-hydroxy-o-phenylacetic acid, u-hydroxycyclohexylacetic acid and the like. Examples of ~-hydroxycarboxylic acids include salicylic acid, alkyl-substituted ' 35 salicyclic acids and the like. Examples of ~-hydroxylcarbonyl :~' '.i ,~
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compounds that may be used include salicylaldehyde, o-hydrsxy-acetophenone and the like. The metal alkoxides which are useful in preparing catalysts of this invention include palladium alkoxides of hydrocarbon aliphatic alcohols, hydrocarbon cycloaliphatic alcohols and hydrocarbon aromatic alcohols.
Examples of hydrocarbon aliphatic alcohols include hexanol, ,.
i ethylhexanol, heptanol, octanol, nonanol, decanol, dodecanol and ;~, the like. The palladium metal salts of sulfur-containing acids ` and partial esters thereof include palladium salts of sulfonic . . .
' 10 acid, sulfuric acid, sulphurous acid, partial esters thereof and the like. Of the aliphatic and aromatic acids salts, salts of ;,"
~- aromatic sulfonic acids such as benzene sulfonic acid, p-toluene . ..
' sulfonic acid and the like are particularly useful.
In general, any one or more of the aluminum compounds known to be useful in preparing a hydrogenation catalyst may be ,; used to prepare the hydrogenation catalyst used in the method of - this invention. Suitable aluminum compounds, then, include those aluminum compounds having the general formula: Al(R)3; wherein . each R may be the same or a different radical selected from H and hydrocarbyl radicals having from 1 to about 20 carbon atoms.
Preferably, each R will be an alkyl radical having from 1 to about 5 carbon atoms.
A further preferred group of suitable aluminum compounds are the alkylalumoxane compounds known to be useful in the preparation of olefin polymerization catalysts as taught, for ~-~ example, in U.S. ~atent No. 4,665,208, may be used separately or ' in combination in preparing the hydrogenation catalyst of this ~ .
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invention. Alumoxane compounds useful in preparing the catalyst of this invention may be cyclic or linear. Cyclic alumoxanes may be represented by the general formula (R-Al-O)m while linear alumoxanes may be represented by the general formula R2AlO-(R-Al-O)-nAlR2. In both of the general formulae each R and/or each R2 will be the same or a different alkyl group having from 1 to about 8 carbon atoms, preferably from 1 to about 5 carbon . .
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: 1327~L21 , 9 .~ atoms, such as, for example, methyl, ethyl, propyl, butyl and pentyl; m is an integer from about 3 to about 40 and n is an integer from about 1 to about 40. In a preferred embodiment of the present invention, the one or more alkylalumoxanes will be a blend ~` 5 of cyclic and linear alumoxanes wherein each R will be methyl, m will be a number from about 3 to about 20 and n will be a number ^ from about 10 to about 20. As is well known alumoxanes may be prepared by reacting an aluminum alkyl with water. Generally, the ; resulting product will be a mixture of both linear and cyclic compounds.
As is well known, contacting of the aluminum alkyl and water ; may be accomplished in several ways. For example, the aluminum . alkyl may first be dissolved in a suitable solvent such as toluene i~ or an aliphatic hydrocarbon and the solution then contacted with a similar solvent containing relatively minor amounts of moisture.
; Alternatively, an aluminum alkyl may be contacted with a hydrated salt such as hydrated copper sulfate or ferrous sulfate. Uhen this method is used, a hydrated ferrous sulfate is frequently used.
, According to this method, a dilute solution of aluminum alkyl in a suitable solvent such as toluene is contacted with hydrated ferrous sulfate. In general, about 1 mole of hydrated ferrous sulfate will be contacted with from about 6 to about 7 moles of the aluminum trialkyl. ~hen aluminum trimethyl is the aluminum alkyl actually used, methane will be evolved as conversion of the aluminum alkyl to an alumoxane occurs.
In general, the hydrogenation catalyst useful in the hydro-, .
genation process of this invention will be prepared by combining the palladium compound or compounds and the aluminum co~pound or compounds in a suitable solvent or diluent. In general, the palladium and aluminum compounds will be combined so as to provide an Al:Pd atomic ratio within the range from about 0.1:1 to about `~ 1.5:1, although when alumoxanes are used the range can suitably be up to about 20:1. In general, the contacting will be accomplished at a temperature within the range from about 20 to about 100C in an inert or reducing atmosphere. In general, any solvent or ,~ , . .. . ..
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`~` 1327~21 - 10 - ' diluent that does not react with either the palladium or aluminum compounds used to prepare the catalyst may be used during the preparation of said catalyst. It will, of course, frequently be most convenient to prepare the catalyst in the same solvent in which the polymer is dissolved and in which the subsequent hydro-genation will occur and such solvents may be used to prepare the catalyst used in the method of this invention. Suitable solvents for the polymers which may be hydrogenated with the process of this ii invention are discussed infra. Catalysts prepared in an ether solvent are, however, significantly more active than catalysts prepared in hydrocarbon. The use of an ether solvent in preparing the catalyst is, therefore, preferred. In general, any linear or cyclic ether having from two to about 20 carbon atoms and from l to about 3 oxygen atoms may be used. Diethers having from about 4 to about lO carbon atoms are particularly effective and are preferred.
In general, the palladium and aluminum compounds used to prepare the hydrogenation catalyst may be, and preferably will be, combined in a separate vessel but each of the components could be separately introduced into the hydrogenation reaction vessel so long as the temperature at which these components are contacted is within the range heretofore specified. In general, contacting times within the range from about l to about 120 minutes will be sufficient to effect reduction of the palladium compound or compounds or other-wise produce an active catalyst.
In general, the hydrogenation will be accomplished with the polymer in solution. In general, any of the solvents known in the prior art to be useful for dissolving copolymers containing one or more conjugated diolefins, optionally one or more alkenyl aromatic hydrocarbons, and one or more cyano groups may be used to effect the hydrogenation in the process of this invention. Suitable solvents, then, include linear and cyclic ethers such as diethyl ether, tetrahydrofuran, and the like; halogenated, particularly chlorinated, aromatic hydrocarbons such as chlorobenzene, dichloro-benzene, methylchlorobenzene and the like; aliphatic and cyclic ketones such as acetone, methylethyl ketone, diethyl ketone, ,1 '';
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: butanone, pentanone, cyclopentanone, cyclohexanone and the like.
i,i In general, the hydrogenation will be accomplished at a temperature within the range from about 20C to about 175C at a total pressure .-~ within the range from about 50 psig to about 1,000 psig and at a ,i 5 hydrogen partial pressure within the range from about 50 psig to about 950 psig. In general, the catalyst or the components thereof will be added during hydrogenation in a concentration sufficient to .1 provide from about 0.4 to about 40 mmoles (gm moles) of palladium per lb. oi polymer. In general, contacting at hydrogenation ~ 10 conditions will be continued for a nominal holding time within the .-: range from about 10 to about 360 minutes. With respect to the .; .
`, hydrogenation, it should be noted that while selective hydro-genation of ethylenic unsaturation may be accomplished at the -i conditions ~ust recited conversion of the cyano groups to amine groups will, generally, begin to occur when the extent of hydro-~i genation of the ethylenic unsaturation reaches about 90~. In this regard, it should be noted that of the several variables available l for control of the extent of hydrogenation, temperature, catalyst .~! concentration and holding time generally have the greatest impact.
These variables may, then, be carefully controlled so as to avoid any significant conversion of the cyano groups to amine groups.
Hydrogenation of aromatic unsaturation, generally, will not occur .~ at the hydrogenation conditions contemplated for use in the process.~. of this invention. Some conversion of aromatic unsaturation may, s~ 25 however, occur at higher ethylenic unsaturation conversions.
~ While not wishing to be bound by any particular theory, it is `~ believed that when the palladium compound or compounds and the aluminum compound or compounds are combined, a reaction occurs to ' form a catalyst. The catalyst thus formed is stable and can be stored for relatively long periods prior to use.
After hydrogenation of the polymer has been completed, the polymer may be recovered as a crumb using methods well known in the . prior art. For example, the polymer may be recovered as a crumb by '`'! precipitation with a polar compound such as an alcohol. Alter-~ 35 natively, the solution may be contacted with steam or water and the ,, " .
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- - 1327~21 . - 12 -solvent then removed by an azeotropic distillation. Generally, , these recovery techniques will also effectively remove a significant portion of the catalyst.
The hydrogenated polymers produced by the method of this 5 invention can be used in any of the applications well known in the prior art for such hydrogenated polymers. For example, selectively hydrogenated copolymers comprising one or more conjugated diolefin monomer units and cyano groups will have improved weatherability and temperature resistance and may be used in seals, packing, tubes 10 and the like.
In one preferred embodiment of the present invention, a random copolymer comprising from about 55 wt% to about 85 wt% conjugated ' diolefin monomer units and from about 45 wt% to about 15 wt% ofunsaturated nitrile monomer units is selectively hydrogenated in .- 15 solution with a catalyst prepared by combining a palladium ~, carboxylate having from about 5 to about 30 carbon atoms and an'~, aluminum trialkyl wherein each alkyl group may be the same or different and has from 1 to about 5 carbon atoms. Preferably, a butadiene/acrylonitrile copolymer is hydrogenated in the presence 20 of a catalyst prepared by contacting a palladium 2-ethylhexanoate ~1 with triethyl aluminum. The palladium carboxylate and the aluminum ;~ trialkyl are preferably combined in amounts sufficient to provide an Al:Pd atomic ratio within the range from about 0.3 to about 0.9.
The catalyst is preferably prepared in a separate step using a 25 diether containing from about 4 to about 10 carbon atoms as -o~ solvent. Preferably 1,2-dimethyoxyethane is used as the solvent.
,~ In a further preferred embodiment, a random copolymer comprising from about 55 wt% to about 85 wt% conjugated diolefin monomer units and from about 45 wt% to about 15 wt% of unsaturated sJ 30 nitrile monomer units is selectively hydrogenated in solution with a catalyst prepared by combining a palladium carboxylate having from about 5 to about 30 carbon atoms and a blend of `~, alkylalumoxanes comprising at ieast one alumoxane having the . general formula (R-A10) and at least one alumoxane having the , 35 general formula R2A10-(R-Al-0)-nAlR2 wherein R is a methyl radical, ., .
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m is a number from about 3 to about 20 and n is a number from about 10 to about 20. Preferably, a butadiene/acrylonitrile copolymer is hydrogenated in the presence of a catalyst prepared by contacting a palladium 2-ethylhexanoate with a preferred blend of alkylalumoxanes. The palladium carbcxylate and the blend of alkylalumoxanes are preferably combined in amounts sufficient to provide an Al:Pd atomic ratio within the range from about 0.2:1 to about 10:1. The palladium carboxylate and the alkylalumoxane are preferably combined in amounts sufficient to provide an Al:Pd atomic ratio within the range from about 0.5:1 to about 2:1. The catalyst is preferably prepared in a separate step using an ether as a solvent. Most preferably, a diether containing from about 4 to about 10 carbon atoms such as 1,2-dimethoxyethane is used as the solvent for the catalyst preparation.
In both the preferred embodiments, the components used to prepare the catalyst are suitably contacted at a temperature within the range from about 25C to about ~0C and the contacting continued for a period of time within the range from about 15 to about 60 minutes. The hydrogenation is suitably accomplished at a temperature within the range from about 20C to about 100C at a total pressure within the range from about 50 psig to about 1,000 psig and at a hydrogen partial pressure within the range from 50 psig to about 950 psig. The hydrogenation is preferably accomplished in a ketone solvent, preferably an aliphatic ketone having from about 3 to about 10 carbon atoms, preferably a dialkyl ketone with each alkyl group being the same or different and containing from 1 to about 5 carbon atoms, a preferred ketone being methyl ethyl ketone.
The selective hydrogenation is suitably accomplished so as to convert tsaturate) at least about 85% of the ethylenic unsaturation intially contained in the polymer and such that no more than about 10% of the cyano groups are converted to amine groups. In the preferred embodiments, the polymer is preferably present in solution at a concentration within the range from about 2 to about 15 wt~ based upon combined polymer and solvent. The nominal . .
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' holding time at hydrogenation conditions is preferably within the range from about 30 to about 120 minutes. Preferably, sufficient catalyst will be added during the hydrogenation to provide from ~ about 0.2 to about 15 mmoles (gm moles) palladium per lb of ; 5 polymer, preferably from about 5 to about 15 mmoles ~gm moles) palladium per lb when using alumoxane(s).
Having thus broadly described the present invention and preferred embodiments thereof, it is believed that the invention , will become even more apparent by reference to the following -' 10 Examples. It will be appreciated, however, that the Examples are ~.~, presented solely for the purpose of illustration and should not be ,;-~ construed as lim$ting the invention.
~, Example 1 In this Example, a series of hydrogenation catalysts were .~ 15 prepared by combining a palladium salt of 2-ethyl-hexanoic acid and - triethyl aluminum at different Al:Pd atomic ratios. Also, for purposes of comparison, a catalyst, hereinafter referred to as . Catalyst No. 1, was prepared with palladium 2-ethylhexanoate without triethyl aluminum. This catalyst was, then, prepared ~ 20 simply by reducing the palladium salt of 2-ethylhexanoic ac~d with '~ hydrogen in the hydrogenation reactor and in the presence of the polymer. In the catalysts prepared in this Example, the Al:Pd atomic ratio ranged, then, from 0 to about 1.5. In preparing those catalysts wherein aluminum triethyl was used as a reducing agent, ~.. 25 the palladium salt and aluminum triethyl were combined in i' 1,2-dimethoxyethane, contacted at a temperature of 25C and then i allowed to exotherm for 30 minutes. The catalyst which was prepared without aluminum was prepared by contacting the palladium salt with hydrogen in methylethylketone and in the presence of the ~, 30 polymer at a temperature of 60C and at a hydrogen partial pressure ~ of about 895 psig. In preparing each of the catalysts, the : palladium salt was present in the solvent at a concentration of 40 mmoles/liter. After preparation, each of the catalysts prepared with triethyl aluminum were retained in the solvent and stored at a temperature of 25C until later used to selectively hydrogenate a .
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~' modified block copolymer. In all, nine catalysts were prepared in this Example. For convenience, these catalysts are hereinafter referred to as catalysts 1-9 and the relative Al:Pd atomic ratio ~: used in preparing each of the nine catalysts is summarizèd in the -' 5 following Table 1:
Table 1 :' `l Al:Pd ~ Catalyst No. Atomic Ratio 5~; 1 0 ~. 2 0.1 . . i 3 0.3 4 0.5 ~ 0.7 .~4 6 0.9 ," ~ 1 . 1 8 1.3 , 9 1.5 . .~
Example 2 ~ In this Example, each of the catalysts prepared in Example 1 ,j was used to selectively hydrogenate a butadiene-acrylonitrile rubber containing 80 wt~ butadiene and 20 wt% acrylonitrile. ~ach .`- 10 of the hydrogenations was accomplished in the presence of sufficient catalyst to provide about 8.5 mmoles Pd per lb of ~ polymer at 60C, at a total pressure of 900 psig and at a hydrogen -i partial pressure of about 895 psig. Each of the hydrogenations was 1 accomplished in a methylethyl ketone solvent and in each of the , hydrogenation runs the polymer was present at a concentration of 5 . wt% based on total polymer and solvent. During each hydrogenation run, a sample was withdrawn after 30 minutes, and at two hours and the extent of hydrogenation determined on each of these samples.
; The extent of hydrogenation was determined using an ozone titration 'i 20 to determine the relative amount of ethylenic unsaturation ;:
. . ~ !
'.`:~i ~ .
''.~
'~, ., .
f !: ' ' '': . ' : ; .
2 7 ~
-~ - 16 -: .
remaining in the polymer. The extent of hydrogenation realized with each of the catalysts at both 30 minutes and two hours is - plotted in the attached Figure and is summarized in the following, Table 2:
"r'~ Table 2 , .
s~ CatalystAl:Pd Extent -C-C-conv. after .~' No. Atomic Ratio 30 min. 120 min.
~ 2 0.1 58 80 .,, 3 0.3 64 90 ,~i 4 0.5 64 88 0.7 66 88 -~ 6 0.9 68 87 - 7 1.1 67 82 .`1 8 1.3 62 75 : 9 1.5 30 38 As will be apparent from the data summarized in the preceding Table ~,'? 2 and from the Figure, best performance was realized with those ~, catalysts prepared with an Al:Pd atomic ratio from about 0.3 to ' about 0.9. That this is the case is particularly apparent from the curve in the Figure obtained with data taken after a nominal ~ 10 holding time of two hours.
.! Example 3 In this Example, a hydrogenation catalyst, hereinafter l referred to as Catalyst No. 10, was prepared by combining a '':'!' palladium salt of 2-ethyl-hexanoic acid and a methyl alumoxane at , 15 an Al:Pd atomic ratio of 0.7:1. Also, for purposes of comparison, ,i a catalyst, hereinafter referred to as Catalyst No. 11, was .-, prepared by combining a palladium 2-ethylhexanoate identical to - ~ that previously used with triethyl aluminum at an Al:Pd atomic ratio of 0.7:1. In preparing these catalysts, the palladium-2-~- 20 ethylhexanoate and the aluminum compounds were combined in an .'; ' :, ~':,`,, , ,. , . . :
,........................ . . . . . . .
2742i . - 17 -ether, viz., 1,2-dimethoxyethane, contacted at a temperature of 25C and then allowed to exotherm for 30 minutes. In preparingeach of the catalysts, the palladium-2-ethylhexanoate was present ~` in the solvent at a concentration of 40 mmoles/liter. After preparation, each of the catalysts prepared were retained in the .i solvent and stored at a temperature of 25C until later used to~: selectively hydrogenate a butadiene-acrylonitrile copolymer as summarized in Example 4.
~ Example 4 " 10 In this Example, the catalysts prepared in Example 3 were used `~, to selectively hydrogenate a butadiene-acrylonitrile rubber containing 80 wt% butadiene and 20 wt% acrylonitrile. Each of the hydrogenations was accomplished in the presence of sufficient ` catalyst to provide about 8.5 mmoles Pd per lb of polymer at 60C, at a total pressure of 900 psig and at a hydrogen partial pressure of about 895 psig. Each of the hydrogenations was accomplished in ` a methylethyl ketone solvent and in each of the hydrogenation runs .~ the poly~er was present at a concentration of 5 wt% based on total polymer and solvent. During each hydrogenation run, a sample was withdrawn after 30 minutes, 60 minutes and at two hours and the extent of hydrogenation determined on each of these samples. The extent of hydrogenation was determined using an ozone titration to determine the relative amount of ethylenic unsaturation remaining ,~ in the polymer. The extent of hydrogenation realized with each of i~ 25 the catalysts at 30 minutes, 60 minutes and two hours is summarized ' in the following Table 3:
. .
, :;
, Table 3 ;,..
. ..
- Extent -C~C-conv. after ` Catalyst No. 30 min. 60 min.120 min.
-'1 , ,,,~ .
.l 10 84 89 90 ' 11 6~ 86 89 ....
....
.
,., ,,,~, : .
, .~. .
, .,............................................ .
.~
1327~21 , .
As will be apparent from the data summarized in the preceding Table, Catalyst No. lO was even more active than Catalyst No. 11 ~ for the entire time tested (2 hrs.).
.~, Example 5 In this Example, two additional catalysts identical to those ~` prepared in Example 3, except that the amount of aluminum compound used to prepare the same was increased to an amount sufficient to i<~ provide an Al:Pd atomic ratio of 1.5:1, were prepared. The .i reactants used to prepare the catalysts and the method used there-for were identical to those summarized in Example 3. For convenience, the catalyst prepared with the alkylalumoxane is hereinafter referred to as Catalyst No. 12 while the catalyst ~-i prepared with triethyl aluminum is hereinafter referred to as Catalyst No. 13. After preparation, the catalysts were retained in the solvent and stored at 25C. until used to hydrogenate a polymer ~ identical to that hydrogenated in Example 4 as s = arized in .j Example 6 below.
~ Example 6 ;l In this Example, the catalysts prepared in Example 5, ,, Catalysts Nos. 12 and 13, were used to hydrogenate a polymer identical to that hydrogenated in Example 4 and the same hydro-genation conditions as were used in Example 4 were used in this ~` Example. During each of the hydrogenation runs, samples were withdrawn at 30, 60 and 120 minutes and the extent of hydrogenation then determined in the same manner as was used in Example 4. The . results obtained in these runs are summarized in the following Table 4:
, . ..
Table 4 ' ~ -C C- hydro~enated after Catalyst No. 30 min. 60 min. 120 min.
. .
, . ' ., ~,, .;.~ . , '. ' , .
.. ,-. .
~: - 1 9 -; As will be apparent from the data suD~marized in the preceding Table, the catalyst prepared with the aluminoxane, Catalyst No. 12, remained particularly effective at this Al:Pd atomic ratio while the catalyst prepared with triethyl aluminum, Catalyst ~o. 13, was significantly less effective.
,. .
i:`
~, ~
., ç~ ~
, ., , .
- . . /
.,, ~
."~.
.~.
,,,~, ..3 ., .
::"
,, ' :' . ., i,, .
..~, i, ~. .
,,.,~ .
r, '.
i 7 .~:
..~?
, ' , . ., , ., , .,, .. ,~ .
'~.; ~
-~ - 16 -: .
remaining in the polymer. The extent of hydrogenation realized with each of the catalysts at both 30 minutes and two hours is - plotted in the attached Figure and is summarized in the following, Table 2:
"r'~ Table 2 , .
s~ CatalystAl:Pd Extent -C-C-conv. after .~' No. Atomic Ratio 30 min. 120 min.
~ 2 0.1 58 80 .,, 3 0.3 64 90 ,~i 4 0.5 64 88 0.7 66 88 -~ 6 0.9 68 87 - 7 1.1 67 82 .`1 8 1.3 62 75 : 9 1.5 30 38 As will be apparent from the data summarized in the preceding Table ~,'? 2 and from the Figure, best performance was realized with those ~, catalysts prepared with an Al:Pd atomic ratio from about 0.3 to ' about 0.9. That this is the case is particularly apparent from the curve in the Figure obtained with data taken after a nominal ~ 10 holding time of two hours.
.! Example 3 In this Example, a hydrogenation catalyst, hereinafter l referred to as Catalyst No. 10, was prepared by combining a '':'!' palladium salt of 2-ethyl-hexanoic acid and a methyl alumoxane at , 15 an Al:Pd atomic ratio of 0.7:1. Also, for purposes of comparison, ,i a catalyst, hereinafter referred to as Catalyst No. 11, was .-, prepared by combining a palladium 2-ethylhexanoate identical to - ~ that previously used with triethyl aluminum at an Al:Pd atomic ratio of 0.7:1. In preparing these catalysts, the palladium-2-~- 20 ethylhexanoate and the aluminum compounds were combined in an .'; ' :, ~':,`,, , ,. , . . :
,........................ . . . . . . .
2742i . - 17 -ether, viz., 1,2-dimethoxyethane, contacted at a temperature of 25C and then allowed to exotherm for 30 minutes. In preparingeach of the catalysts, the palladium-2-ethylhexanoate was present ~` in the solvent at a concentration of 40 mmoles/liter. After preparation, each of the catalysts prepared were retained in the .i solvent and stored at a temperature of 25C until later used to~: selectively hydrogenate a butadiene-acrylonitrile copolymer as summarized in Example 4.
~ Example 4 " 10 In this Example, the catalysts prepared in Example 3 were used `~, to selectively hydrogenate a butadiene-acrylonitrile rubber containing 80 wt% butadiene and 20 wt% acrylonitrile. Each of the hydrogenations was accomplished in the presence of sufficient ` catalyst to provide about 8.5 mmoles Pd per lb of polymer at 60C, at a total pressure of 900 psig and at a hydrogen partial pressure of about 895 psig. Each of the hydrogenations was accomplished in ` a methylethyl ketone solvent and in each of the hydrogenation runs .~ the poly~er was present at a concentration of 5 wt% based on total polymer and solvent. During each hydrogenation run, a sample was withdrawn after 30 minutes, 60 minutes and at two hours and the extent of hydrogenation determined on each of these samples. The extent of hydrogenation was determined using an ozone titration to determine the relative amount of ethylenic unsaturation remaining ,~ in the polymer. The extent of hydrogenation realized with each of i~ 25 the catalysts at 30 minutes, 60 minutes and two hours is summarized ' in the following Table 3:
. .
, :;
, Table 3 ;,..
. ..
- Extent -C~C-conv. after ` Catalyst No. 30 min. 60 min.120 min.
-'1 , ,,,~ .
.l 10 84 89 90 ' 11 6~ 86 89 ....
....
.
,., ,,,~, : .
, .~. .
, .,............................................ .
.~
1327~21 , .
As will be apparent from the data summarized in the preceding Table, Catalyst No. lO was even more active than Catalyst No. 11 ~ for the entire time tested (2 hrs.).
.~, Example 5 In this Example, two additional catalysts identical to those ~` prepared in Example 3, except that the amount of aluminum compound used to prepare the same was increased to an amount sufficient to i<~ provide an Al:Pd atomic ratio of 1.5:1, were prepared. The .i reactants used to prepare the catalysts and the method used there-for were identical to those summarized in Example 3. For convenience, the catalyst prepared with the alkylalumoxane is hereinafter referred to as Catalyst No. 12 while the catalyst ~-i prepared with triethyl aluminum is hereinafter referred to as Catalyst No. 13. After preparation, the catalysts were retained in the solvent and stored at 25C. until used to hydrogenate a polymer ~ identical to that hydrogenated in Example 4 as s = arized in .j Example 6 below.
~ Example 6 ;l In this Example, the catalysts prepared in Example 5, ,, Catalysts Nos. 12 and 13, were used to hydrogenate a polymer identical to that hydrogenated in Example 4 and the same hydro-genation conditions as were used in Example 4 were used in this ~` Example. During each of the hydrogenation runs, samples were withdrawn at 30, 60 and 120 minutes and the extent of hydrogenation then determined in the same manner as was used in Example 4. The . results obtained in these runs are summarized in the following Table 4:
, . ..
Table 4 ' ~ -C C- hydro~enated after Catalyst No. 30 min. 60 min. 120 min.
. .
, . ' ., ~,, .;.~ . , '. ' , .
.. ,-. .
~: - 1 9 -; As will be apparent from the data suD~marized in the preceding Table, the catalyst prepared with the aluminoxane, Catalyst No. 12, remained particularly effective at this Al:Pd atomic ratio while the catalyst prepared with triethyl aluminum, Catalyst ~o. 13, was significantly less effective.
,. .
i:`
~, ~
., ç~ ~
, ., , .
- . . /
.,, ~
."~.
.~.
,,,~, ..3 ., .
::"
,, ' :' . ., i,, .
..~, i, ~. .
,,.,~ .
r, '.
i 7 .~:
..~?
, ' , . ., , ., , .,, .. ,~ .
'~.; ~
Claims (22)
1. A process for selectively hydrogenating a polymer comprising ethylenic unsaturation and cyano groups comprising the steps of:
(a) contacting a polymer comprising ethylenic unsaturation and cyano groups with hydrogen in a first suitable solvent and in the presence of a catalyst prepared by combining one or more palladium compounds with one or more aluminum compounds in a second suitable solvent, which second suitable solvent may be the same or different from said first suitable solvent;
(b) maintaining the contact in step (a) for a sufficient period of time to permit conversion of at least a portion of the ethylenic unsaturation contained in said polymer; and (c) recovering an at least partially hydrogenated polymer.
(a) contacting a polymer comprising ethylenic unsaturation and cyano groups with hydrogen in a first suitable solvent and in the presence of a catalyst prepared by combining one or more palladium compounds with one or more aluminum compounds in a second suitable solvent, which second suitable solvent may be the same or different from said first suitable solvent;
(b) maintaining the contact in step (a) for a sufficient period of time to permit conversion of at least a portion of the ethylenic unsaturation contained in said polymer; and (c) recovering an at least partially hydrogenated polymer.
2. The process of claim 1 wherein the contacting in step (a) is accomplished at a temperature within the range from about 20 to about 175°C at a total pressure within the range from about 50 to about 1,000 psig and a hydrogen partial pressure within the range from about 50 to about 950 psig.
3. The process of claim 1 or 2 wherein the contacting in step (a) is continued for a nominal holding time within the range from about 10 to about 360 minutes.
4. The process of claim 1 or 2 wherein said one or more palladium compounds is a palladium carboxylate containing from 1 to about 50 carbon atoms.
5. The process of claim 4 wherein said palladium carboxylate contains from about 5 to about 30 carbon atoms.
6. The process of claim 5 wherein said palladium carboxylate is palladium 2-ethylhexanoate.
7. The process of claim 1, 2, 5 or 6 wherein said one or more palladium compounds and said one or more aluminum compounds are combined in an ether having from about 2 to about 20 carbon atoms.
8. The process of claim 7 wherein said ether is a diether having from about 4 to about 10 carbon atoms.
9. The process of claim 8 wherein said ether is 1,2-dimethoxyethane.
10. The process of claim 1, 2, 5, 6, 8 or 9 wherein said first suitable solvent is a ketone having from 3 to about 10 carbon atoms.
11. The process of claim 10 wherein said ketone is methyl ethyl ketone.
12. The process of claim 1, 2, 5, 6, 8, 9 or 11 wherein said hydrogenation is accomplished so as to convert (saturate) at least about 85% of the ethylenic unsaturation initially contained in the polymer while converting less than about 5% of the cyano groups to amine groups.
13. The process of claim 1, 2, 5, 6, 8, 9 or 11 wherein said one or more aluminum compounds are selected from aluminum hydrides, aluminum alkyls and mixtures thereof.
14. The process of claim 13 wherein said catalyst is prepared by combining the one or more palladium compounds and the one or more aluminum compounds in a ratio sufficient to provide an Al:Pd atomic ratio within the range from about 0.1:1 to about 1.5:1.
15. The process of claim 14 wherein said Al:Pd atomic ratio is within the range from about 0.3:1 to about 0.9:1.
16. The process of claim 1, 2, 5, 6, 8, 9 or 11 wherein said one or more aluminum compounds are one or more alkylalumoxanes.
17. The process of claim 16 wherein said catalyst is prepared by combining the one or more palladium compounds and the one or more alkylalumoxanes in a ratio sufficient to provide an Al:Pd atomic ratio within the range from about 0.2:1 to about 10:1.
18. The process of claim 17 wherein said Al:Pd atomic ratio is within the range from about 0.5:1 to about 2.0:1.
19. The process of claim 16 wherein said one or more alkylalumoxanes is a blend comprising at least one alkylalumoxane having the general formula (R-Al-O)m and at least one alkyl-alumoxane having the general formula R2A10-(R-Al-0)-nAlR2 where-in each R and R2 is the same or different alkyl radical having from 1 to about 5 carbon atoms, m is a number from about 5 to about 20 and n is a number from about 10 to about 20.
20. The process of claim 19 wherein said R is a methyl radical.
21. The process of claim 19 wherein said R is an ethyl radical.
22. A polymer which has been at least partially hydrogenated by the process of claim 1, 2, 5, 6, 8, 9, 11, 14, 15, 17, 18, 19, 20 or 21.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/256,537 US4892928A (en) | 1988-10-12 | 1988-10-12 | Hydrogenation process |
| US256,537 | 1988-10-12 | ||
| US269,034 | 1988-11-09 | ||
| US07/269,034 US4876314A (en) | 1988-11-09 | 1988-11-09 | Hydrogenation process |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1327421C true CA1327421C (en) | 1994-03-01 |
Family
ID=26945439
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000615412A Expired - Fee Related CA1327421C (en) | 1988-10-12 | 1989-09-29 | Hydrogenation process |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP2792686B2 (en) |
| BR (1) | BR8905155A (en) |
| CA (1) | CA1327421C (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4593374B2 (en) * | 2005-06-07 | 2010-12-08 | エヌ・イーケムキャット株式会社 | Method for producing Pd colloidal solution |
| JP4956956B2 (en) * | 2005-10-12 | 2012-06-20 | Ｊｓｒ株式会社 | Hydrogenation catalyst and method for producing hydrogenated polymer |
-
1989
- 1989-09-29 CA CA000615412A patent/CA1327421C/en not_active Expired - Fee Related
- 1989-10-11 BR BR8905155A patent/BR8905155A/en not_active IP Right Cessation
- 1989-10-12 JP JP26604989A patent/JP2792686B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2792686B2 (en) | 1998-09-03 |
| BR8905155A (en) | 1990-05-15 |
| JPH02196803A (en) | 1990-08-03 |
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