WO2012013697A2 - Hydrogenation of diene-based polymers - Google Patents
Hydrogenation of diene-based polymers Download PDFInfo
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- UWYPIMMDVRGQSS-UHFFFAOYSA-N Nc(cc1)ccc1NC(c1cc(C(O)=O)cc(C(O)=O)c1)=O Chemical compound Nc(cc1)ccc1NC(c1cc(C(O)=O)cc(C(O)=O)c1)=O UWYPIMMDVRGQSS-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/02—Hydrogenation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F36/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F36/04—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F36/06—Butadiene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/02—Carriers therefor
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/04—Reduction, e.g. hydrogenation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/002—Dendritic macromolecules
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/002—Dendritic macromolecules
- C08G83/003—Dendrimers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/002—Dendritic macromolecules
- C08G83/005—Hyperbranched macromolecules
Definitions
- This invention relates to a process for the hydrogenation of diene based copolymers in the presence of catalysts supported on specific carrier materials.
- nitrile rubbers by emulsion polymerization of (meth)acrylonitrile with conjugated dienes, for example butadiene, and optionally, small amounts of other comonomers are widely known, for example, from DE 658 172.
- conjugated dienes for example butadiene
- other comonomers are widely known, for example, from DE 658 172.
- One type of such other co-monomers are , ⁇ -unsaturated carboxylic acids and the resulting terpolymers are often abbreviated as "XNBR".
- XNBR terpolymers
- the polymer may be hydrogenated as such, however, that good results are in particular obtained if the polymer is used in the form of a solution.
- US-A-4,452,951 the hydrogenation of acrylonitrile/butadiene copolymers using a hydrogenation catalyst supported on silicon dioxide having a specific surface area of not more than 600 m 2 /g and an average pore diameter of from 80 to 1,000 A is described.
- the carrier materials proposed so far for the heterogeneous hydrogenation catalysts used for hydrogenating diene based polymers often suffer from having low mechanical strength which in consequence results in the disadvantage, that they cannot be successfully used several times, since, owing to the mechanical stress a fine grain portion occurs, which either renders the hydrogenation product impure or results in a working-up step substantially more difficult.
- HB polymers Hyper-branched polymers
- HB polymers are highly branched macromolecules with a three-dimensional architecture which pursuant to Prog. Polym. Sci. 29 (2004) 183-275 belong to the class of dendritic polymers.
- HB polymers have attracted increasing attention owing to their interesting properties and greater availability as compared with other types of dendrimers. In Prog. Polym. Sci.
- HB polymers have potential applications in coatings, as additives, for drug and gene delivery, as macromolecular building blocks, for nanotechnology and supramolecular science.
- HB polymers have potential applications in coatings, as additives, for drug and gene delivery, as macromolecular building blocks, for nanotechnology and supramolecular science.
- Adv. Synth. Catal., 345 (2003), 333 (Mecking et al.) it is described to use hybrids of palladium nanoparticles with highly branched amphiphilic polyglycerol as a catalyst for the hydrogenation of cyclohexene.
- the reaction was performed in a continuously operated membrane reactor and the reaction mixture was continuously drawn from the reactor via the membrane.
- hydroformylation of 1-hexene may be performed with rhodium colloids stabilized by poly(ethylene imine)amides with a hyper-branched polyamine core and a lipophilic periphery.
- the object of the present invention was to provide a new and improved hydrogenation process using a heterogeneous catalyst allowing the selective hydrogenation of a diene-based polymer with a high degree of hydrogenation within short reaction times at low reaction pressures and mild temperatures. It was a further object to find a catalyst disposing of sufficient mechanical strenght which may be easily recovered and often re-used in such hydrogenation of diene-based polymers.
- the present invention provides a process for hydrogenating carbon-carbon double bonds in a polymer containing repeating units based on dienes which process comprises subjecting such polymer to hydrogenation in the presence of a group Vllib metal containing catalyst supported on a carrier material comprising at least one hyper-branched polymer.
- the process of the present invention allows a selective hydrogenation of the carbon-carbon double bonds which are present in repeating units of polymers based on diene monomers. This means that, for example, the double bonds in aromatic or naphthenic groups are not hydrogenated and double or triple bonds between carbon and hetero atoms such as nitrogen or oxygen and in particular nitrile groups are also not affected.
- the feature of using a group Vlllb meta! containing catalyst supported on a hyper-branched polymer is important for the successful performance of the process pursuant to the present invention in order to obtain a very high degree of hydrogenation at a reaction pressure and temperature being substantially lower than known from prior art for other processes. Furtheron the rate of hydrogenation is high and the crosslinking problem occurring in other processes known from prior art is overcome.
- the polymer to be hydrogenated by the process pursuant to the present invention comprises repeating units of at least one diene, preferably at least one conjugated diene.
- the conjugated diene can be of any nature, in one embodiment (C 4 -Ce) conjugated dienes are used.
- C 4 -Ce conjugated dienes Preference is given to 1,3-butadiene, isoprene, 1-methylbutadiene, 2,3-dimethylbutadiene, piperylene, chloroprene, or mixtures thereof. Particular preference is given to 1,3-butadiene and isoprene or mixtures thereof. Especial preference is given to 1,3-butadiene.
- diene-based polymers having carbon-carbon double bonds can be used which comprise repeating units of not only at least one conjugated diene as monomer (a), but additionally of at least one further copolymerizable monomer (b), preferably of two further copolymerizable monomers (b).
- Suitable monomers (b) are olefins, such as ethylene or propylene.
- suitable monomers (b) are vinylaromatic monomers, such as styrene, o-, m- or p-methyl styrene, vinylnaphthalene, vinylpyridine, o-chiorostyrene or vinyltoluenes, vinylesters of aliphatic or branched C Ci8 monocarboxylic acids, such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl valerate, vinyl hexanoate, vinyl 2-ethylhexanoate, vinyl decanoate, vinyl laurate and vinyl stearate.
- One preferred polymer to be hydrogenated in the present process is a copolymer of 1,3-butadiene and styrene or alpha-methylstyrene. Said copolymers may have a random or block type structure.
- Suitable other copolymerizable monomers (b) are ⁇ , ⁇ -unsaturated nitriles. It is possible to use any known ⁇ , ⁇ -unsaturated nitrile, preferably a (C 3 -C 5 ) , ⁇ -unsaturated nitrile such as acrylonitrile, methacrylonitrile, ethacrylonitrile or mixtures thereof. Particular preference is given to acrylonitrile.
- One further preferred polymer to be used in the present invention is a copolymer having repeating units of at least one conjugated diene and at least one , ⁇ -unsaturated nitrile which are also abbreviated "nitrile rubbers" or "NBR" for short. Even more preferably a copolymer having repeating units based on 1,3- butadiene and acrylonitrile can be hydrogenated according to the novel process.
- copolymerizable monomers (b) it is possible to make use, for example, of fluorine-containing vinylmonomers, preferably fluoroethyl vinyl ether, fluoropropyl vinyl ether, o-fluoromethylstyrene, vinyl pentafluorobenzoate, difluoroethylene and tetrafluoroethylene, or else copolymerizable anti-ageing monomers, preferably N-(4-anilinophenyl)acrylamide, N-(4-anilinophenyl)methacrylamide, N-(4- anilinophenyl)cinnamides, N-(4-anilinophenyl)crotonamide, N-phenyl-4-(3-vinylbenzyloxy)aniIine and N-phenyl-4-(4-vinylbenzyloxy)aniline, and also non-conjugated dienes, such as 4-cyanocyclohexene and 4-vinylcyclo
- copolymerizable termonomers containing carboxyl groups, examples being ⁇ , ⁇ -unsaturated monocarboxylic acids, their esters, their amides, , ⁇ -unsaturated dicarboxylic acids, their monoesters, their diesters, or their corresponding anhydrides and amides.
- a nitrile rubber is used as diene-based polymer which comprises repeating units based on at least one conjugated diene, more preferably (C 4 -C 6 ) conjugated dienes, even more preferably selected from the group consisting of 1,3-butadiene, isoprene, 1-methylbutadiene, 2,3-dimethylbutadiene, piperylene, chloroprene, and mixtures thereof, at least one , ⁇ -unsaturated nitriles, more preferably a (C 3 - C ; ) ⁇ , ⁇ -unsaturated nitrile, even more preferably selected from the group consisting of acrylonitrile, methacryionitrile, ethacrylonitrile and mixtures thereof, and optionally one or more further copolymerizable monomers, preferably selected from the group consisting of ⁇ , ⁇ -unsattirated monocarboxylic acids, their esters, their amides, ⁇ , ⁇ -unsaturated die
- ⁇ , ⁇ -unsaturated monocarboxylic acids it is possible with preference to use acrylic acid and methacryiic acid.
- esters of the ⁇ , ⁇ -unsaturated monocarboxylic acids preferably their alkyl esters and alkoxyalkyl esters.
- the alkyl esters especially Ci-Cig alkyl esters, of the ⁇ , ⁇ - unsaturated monocarboxylic acids
- alkoxyalkyl esters of the ⁇ , ⁇ -unsaturated monocarboxylic acids more preferably alkoxyalkyl esters of acrylic acid or of methacryiic acid, more particular C 2 -Ct2 alkoxyalkyl esters of acrylic acid or of methacryiic acid, very preferably methoxymethyl acrylate, methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate and methoxyethyl (meth)acrylate.
- Use may also be made of mixtures of alkyl esters, such as those mentioned above, for example, with alkoxyalkyl esters, in the form of those mentioned above, for example.
- cyanoalkyl acrylate and cyanoalkyl methacrylates in which the C atom number of the cyanoalkyl group is 2-12, preferably a-cyanoethyl acrylate, ⁇ -cyanoethyl acrylate and cyanobutyl methacrylate.
- Use may also be made of hydroxyalkyl acrylates and hydroxyalkyl methacrylate in which the C atom number of the hydroxyalkyl groups is 1-12, preferably 2-hydroxyethyI acrylate, 2- hydroxyethyl methacrylate and 3-hydroxypropyl acrylate; use may also be made of fluorine-substituted benzyl-group-containing acrylates or methacrylates, preferably fluorobenzyl acrylate, and fluorobenzyl methacrylate. Use may also be made of acrylates and methacrylates containing fiuoroalkyl groups, preferably trifluoroethyl acrylate and tetrafluoropropyi methacrylate. Use may also be made of ⁇ , ⁇ - unsaturated carboxylic esters containing amino groups, such as dimethylaminomethyl acrylate and diethylaminoethyl acrylate.
- ⁇ -unsaturated dicarboxylic acids preferably maleic acid, fumaric acid, crotonic acid, itaconic acid, citraconic acid and mesaconic acid.
- Use may be made, furthermore, of , ⁇ -unsaturated dicarboxylic anhydrides, preferably maleic anhydride, itaconic anhydride, citraconic anhydride and mesaconic anhydride.
- ⁇ , ⁇ -unsaturated dicarboxylic monoesters or diesters may be, for example, alkyl esters, preferably C r C 10 alkyl, more particularly ethyl, n-propyl, isopropyi, n-butyl, tert-butyl, n-pentyi or n-hexyl esters, alkoxyalkyl esters, preferably C 2 -Ci 2 alkoxyalkyl, more preferably C3-Q- alkoxyalkyl, hydroxyalkyl, preferably C r Ci 2 hydroxyalkyl, more preferably C 2 -Cg hydroxyalkyl, cycloalkyl esters, preferably C 5 -Ci 2 cycloalkyl, more preferably C 6 -C ]2 cycloalkyl, alkylcycloalky
- alkyl esters of ⁇ , ⁇ -unsaturated monocarboxylic acids are methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylaie, t-butyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, 2-propylheptyl acrylate and lauryl (meth)acrylate. More particularly, n-butyl acrylate is used.
- alkoxyalkyl esters of the ⁇ , ⁇ -unsaturated monocarboxylic acids are methoxy ethyl (meth)acrylate, ethoxyethyl (meth)acry!ate and methoxyethyl (meth)acrylate. More particularly, methoxyethyl acrylate is used.
- Particularly preferred hydroxyalkyl esters of the ⁇ , ⁇ -unsaturated monocarboxylic acids are hydroxyeihyl (meth)acrylate, hydroxypropyl (meth)acrylate and hydroxybuty! (meth)acrylate.
- Other esters of the ⁇ , ⁇ -unsaturated monocarboxylic acids that are used are additionally, for example, polyethylene glycol (meth)acryl te, polypropylene glycol (meth)acrylate, glycidyl (meth)acrylate, epoxy (meth)acrylate, N-(2-hydroxyethyI)acryIamides, N-(2-hydroxymethyl)acrylamides and urethane (meth)acrylate.
- maleic acid monoalkyl esters preferably monomethyi maleate, monoethyl maleate, monopropyl maleate and mono-n-butyl maleate;
- maleic acid monocycloalkyl esters preferably monocyclopenty! maleate, monocyclohexyl maleate and monocycioheptyl maleate;
- maleic acid monoalkyl cycioalkyl esters preferably monomethyi cyclopentyl maieate and monoethyl cyclohexyl maleate;
- maleic acid monoaryl esters preferably monophenyl maleate
- maleic acid monobenzyl esters preferably monobenzyl maleate
- fumaric acid monoalkyl esters preferably monomethyi fumarate, monoethyl fumarate, monopropyl fumarate and mono-n-butyl fumarate;
- fumaric acid monocycloalkyl esters preferably monocyclopentyl fumarate, monocyclohexyl fumarate and monocycioheptyl fumarate;
- fumaric acid monoalkyl cycioalkyl esters preferably monomethyi cyclopentyl fumarate and monoethyl cyclohexyl fumarate;
- fumaric acid monoaryl esters preferably monophenyl fumarate
- citraconic acid monoalkyl esters preferably monomethyi citraconate, monoethyl citraconate, monopropyl citraconate and mono-n-butyl citraconate;
- citraconic acid monocycloalkyl esters preferably monocyclopentyl citraconate, monocyclohexyl citraconate and monocycioheptyl citraconate;
- citraconic acid monoalkyl cycioalkyl esters preferably monomethyi cyclopentyl citraconate and monoethyl cyclohexyl citraconate;
- citraconic acid monoaryl esters preferably monophenyl citraconate
- citraconic acid monobenzyl esters preferably monobenzyl citraconate
- itaconic acid monoalkyl esters preferably monomethyi itaconate, monoethyl itaconate, monopropyl itaconate and mono-n-butyl itaconate;
- itaconic acid monocycloalkyl esters preferably monocyclopentyl itaconate, monocyclohexyl itaconate and monocycioheptyl itaconate;
- ⁇ itaconic acid monobenzyl esters preferably monobenzyl itaconate.
- ester groups may also be chemically different groups.
- a copolymer having repeating units of at least one conjugated diene, at least one ⁇ , ⁇ -unsaturated nitriles and one or more further copolymerisable monomers is subjected to hydrogenation.
- the proportions of conjugated diene(s) and ⁇ , ⁇ -unsaturated nitrile(s) in the NBR polymers may vary within wide ranges.
- the proportion of or the sum of the conjugated dienes is typically in the range from 40 to 90% preferably in the range from 50 to 85%, by weight, based on the overall polymer.
- the proportion of or the sum of the , ⁇ - unsaturated nitriles is typically 10 to 60%, preferably 15 to 50%, by weight, based on the overall polymer.
- the proportions of the monomers add up in each case to 100% by weight.
- the additional monomers may be present in amounts of 0% to 40% by weight, based on the overall polymer.
- corresponding proportions of the conjugated diene or dienes and/or of the ⁇ , ⁇ -unsaturated nitrile or nitriles are replaced by the proportions of the additional monomers, with the proportions of all the monomers adding up in each case to 100% by weight.
- nitrile rubbers may be hydrogenated which typically have a Mooney viscosity (ML (1+4) at 100°C) in the range of from 5 to 140, preferably 5 to 130, more preferably 10 to 100, even more preferably 20 to 100, and particularly preferred from 25 to 100.
- the weight average molecular weight M w lies in the range of from 5,000 - 500,000, preferably in the range of from 20,000 - 500,000, more preferably in the range 25,000 - 400,000.
- the determination of the Mooney viscosity is carried out in accordance with ASTM standard D 1646.
- the hydrogenated nitrile rubbers obtained after hydrogenating the aforementioned nitrile rubbers typically have a Mooney viscosity (ML (1+4) at 100°C) in the range of from 5 to 200, preferably 5 to 160, more preferably 5 to 140, even more preferably 20 to 140, and particularly preferred from 25 to 140.
- the weight average molecular weight M w lies in the range of from 30,000 to 400,000, preferably in the range of from 30,000 to 350,000, more preferably in the range of from 35,000 to 300,000.
- nitrile rubbers may be hydrogenated which have a very low viscosity:
- Such nitrile rubber have a weight average molecular weight M w of 60,000 g/mol or less, preferably 5,000 to 55,000 gm/mol, more preferably 10,000 to 50,000 g/mol, more preferably 12,000 to 50,000 g/mol and a polydispersity (Mw Mn) of at maximum 2.5, preferably at maximum 2.4, more preferably at maximum 2.3, even more preferably at maximum 2.2 and most preferably at maximum 2.0.
- the hydrogenated nitrile rubbers obtained after hydrogenating the aforementioned nitrile rubbers with very low viscosity typically have a viscosity of at maximum 20,000 Pa*s measured at 100°C and a shear rate of 1/s, preferably at maximum 10,000 Pa*s, more preferably at maximum 5,000 Pa*s and most preferably at maximum 1,000 Pa*s.
- the weight average molecular weight M w of such hydrogenated nitrile rubbers typically amounts to at maximum 60,000 g mol, preferably 10,000 to 50,000 g mol, more preferably 12,000 to 50,000 g/mol and a polydispersity (Mw/Mn) of at maximum 2.5, preferably at maximum 2.4, more preferably at maximum 2.3, even more preferably at maximum 2.2 and most preferably at maximum 2.0.
- nitrile rubbers by polymerization of the abovementioned monomers is adequately known to those skilled in the art and is comprehensively described in the polymer literature. Usually the polymerization is performed in emulsion: However, a solution based polymerization is also possible, as disclosed in a recent European patent application not yet published. It is also possible to subject such nitrile rubbers (prior to hydro genation) to a metathesis reaction in the presence of a metal complex- metathesis catalyst in order to decrease the molecular weight and viscosity thereof.
- Such cross-metathesis reaction which can optionally be performed in the additional presence of a low molecular weight olefine (the so called "co-olefine") is widely known in the art and subject of numerous patents and patent applications like e.g. WO- A-2002/100941 or WO-A-2002/100905.
- Nitrile rubbers which can be used for the purposes of the invention are also commercially available, e.g. as products from the product range of the trade names Perbunan ® and Krynac ® from Lanxesstechnik GmbH.
- a polymer other than a nitrile rubber which contains repeating units of one or more dienes, preferably conjugated dienes, and one or more other copolymerizable monomers as defined above, like e.g. styrene or o-methylstyrene
- the proportion of the dienes, preferably conjugated diene(s) is usually from 15 to less than 100% b.w. and the proportion of or of the sum of the copolymerizable monomer(s) is from greater than 0 to 85 % b.w. with the proportion of all monomers in each case adding up to 100%.
- the proportion of styrene and/or o-methyl styrene is preferably from 15 to 60% b.w., while the remainder to 100% b.w. is represented by the conjugated diene(s).
- the carbon-carbon double bonds containing polymer (other than NBR) to be used in the present invention may be prepared by any method known to those skilled in the art, such as emulsion polymerization, solution polymerization or bulk polymerization.
- the carbon-carbon double bond containing polymer useful in the present invention is prepared in an aqueous emulsion polymerization process.
- the hydrogenation catalyst to be used in the process of the present invention is a Group Vlllb metal containing catalyst supported on a carrier material comprising at least one hyper-branched polymer.
- Group Vlllb metal means a metal of Group Vlllb of the Periodic Table of Elements. Suitable metals of Group Vlllb of the Periodic Table of Elements are Ru, Rh, Pd, Fe, Co, Ni, Os, Ir, and Pt. Preferably a Palladium containing catalyst deposited on a carrier material comprising at least one hyper-branched pofymer is used for the hydrogenation.
- Hyper-branched polymers (“HB polymers” for short) are highly branched macromolecules with a three- dimensional architecture and pursuant to Prog. Polym. Sci. 29 (2004) 183-275 they belong to the class of dendritic polymers. Hyperbranched polymers are typically synthesized pursuant to the following two major methods also described in detail in Prog. Polym. Sci. 29 (2004) 183-275:
- DMM double-monomer methodology
- single monomer methodology includes at least four specific approaches: (1) polycondensation of AB n monomers; (2) self-condensing vinyl polymerisation (“SCVP”);” (3) self-condensing ring-opening polymerization (“SCROP”) and (4) proton-transfer polymerization (“PTP”).
- SCVP self-condensing vinyl polymerisation
- SCROP self-condensing ring-opening polymerization
- PTP proton-transfer polymerization
- AB n monomers (1) in particular AB 2 monomers allows the synthesis of HB po!yphenylenes, polyethers, polyesters, polyamides, polycarbonates and pol(etherketone)s.
- AB n monomers HB polyurethanes, polycarbosilanes, polymides and poly(acetophenone)s may also be obtained.
- SCROP (3) allows the synthesis of HB polyamtnes, polyethers, and polyesters.
- PTP (4) allows the synthesis of HB polyesters with epoxy or hydroxyl end groups as well as HB polysiloxanes.
- hyper-branched polymers can be favourably used in the process according to the invention: Hyper-branched aliphatic and aromatic polyamides, polyethyleneimines, functionalized polyethyleneimines, polyureas, polyols, polyglycidoles, polyethers, polythiols, polythioethers.
- the hyper-branched polymer used as carrier material represents a hyper-branched aliphatic or aromatic polyamide.
- Such hyper-branched aliphatic or aromatic polyamides can be obtained by S M as well as DMM.
- DMM hyper-branched aliphatic or aromatic polyamides can be obtained by poiycondensation of difunctional monomers ("A 2 " for short) with monomers being trifunctional or higher than trifunctional (“B 3 " for short).
- the hyper-branched aliphatic or aromatic polyamide can be prepared by poiycondensation of an aliphatic or aromatic diamine ("A 2 ") with an acid having at least three carboxyl groups ('3 ⁇ 4" for short) or in the alternative by poiycondensation of a dicarboxylic acid (“A 2 ") with an amine having at least three amino groups (“B 3 ”)-
- the principle method of preparing HB aromatic polyamides using the A 2 +B 3 approach was reported in Macromolecules, 1999, 32, 2061 (Mitsutoshi Jikei et al.).
- Preferred hyper-branched aromatic polyamides can be synthesized by poiycondensation of p- phenylenediamine (for short “PD” as A 2 monomer) and/or 4,4'-oxyphenylene diamine (for short “ODA” as A 2 monomer) and trimesic acid (for short “TMA” as B 3 monomer).
- the resulting hyper-branched aromatic polyamides are hereinafter denoted as "pPDT” for short and possess the principle structure as hereinafter shown schematically for PD as diamine.
- pPDT can be successfully used as the polymeric carrier to produce active Pd-containing pPDT supported catalysts, which can hydrogenate NBR to high
- Scheme 1(a) shows the same poiycondensation in some more detail with regard to the resulting HB pPDT.
- the advantage of such DMM method to prepare HB aromatic polyamides is the use of commercially available reactants for the easy preparation thereof.
- To obtain the HB pPDT with suitable structure for synthesizing the Pd/pPDT catalyst it is advisable to optimize polymerization conditions (temperature, reagent amount and concentrations, ratio of functional groups in the reaction system, reaction time, etc), it is also recommendable to adequately handle the HB pPDT during the finishing process and the metal salt loading process.
- the performance of the hydrogenation can be optimized by influencing the pore size of the hyper- branched polymer used as catalyst support: It is recommendable to use HB polymer particles with pore sizes larger than the size of tangled NBR molecules present in the solution to be hydrogenated.
- the hyper-branched polymer used as carrier material represents a hyper-branched aliphatic polyamide like poly(amido amine) (for short "HB PAMAM”) as schematically shown in Scheme 3 which are obtainable by I) adding four molecules of methylacrylate to ethylene diamine, 2) amidation of the terminal carboxymethyl groups with excess ethylene diamine and 3) repeating the addition of methylacrylate and amidation with excess ethylene diamine various times to prepare the hyper-branched structure.
- H PAMAM hyper-branched aliphatic polyamide like poly(amido amine)
- HB polymers are polyethylenimine, functionalized polyethylenimines and polyureas with principle structures as shown in Scheme 4(a) to (c).
- HB Polyethyieneimines are obtainable by cationic ring-openinng polymerisation of aziridine or cationic polymerisation of ethyleneimine
- HB functionized polyethyieneimines are typcially obtainable by converting HB polyethyieneimines with desired functional izing agents as e.g. carboxylic acids (see Scheme 4(b) with hexane carboxylic acid as functionalizing agent).
- HP Polyureas are obtainable by polyaddition of isocyanates with amines according to the A 2 +B3 approach by either using diisocyanates and triamines or diamines with triisocyanates.
- HB polymers are HB polyesters like e.g. poly glycerol es which are obtainable by polycondensation of glycerol and carboxyiic acids with at least two carboxy groups per molecule like e.g. phihaiic acid.
- glycerol may be polycondensed with the respective carboxyiic acid anhydrides which in-situ form carboxyiic acids with two carboxy groups like e.g. phtha!ic anhydride.
- the following A 2 and B 3 monomer pairs may be used in the DMM synthesis of HB polymers viable to be used in the process according to the present invention:
- the following monomers may be used either in the SMM process in case of AB n monomers or in the DMM process using appropriate monomer pairs to prepare HB polymers viable to be used in the process according to the present invention.
- the preparation of the supported catalyst is typically performed in a three step procedure comprising (i) the synthesis of the carrier material as outlined above,
- the reaction conditions for preparing hyper-branched polymers can be taken from literature.
- the synthesis of hyper-branched polyamides e.g. starting from aromatic diamines and an acid having at least three carboxyl groups like e.g. trimesic acid is described in Applied Catalysis, A: General, 1999, 177(2), 219 (Shirai, et a!.).
- the metals of Group VIHb of the Periodic Table of Elements can be deposited on the carrier by any ordinary supporting method. For example, these metals can be deposited in the elemental state on the earner.
- the carrier may be contacted with a solution of a halide, oxide, hydroxide, acid chloride, sulfate, or carbonate of such metals.
- an organic solvent or water may be employed to dissolve the metal compound.
- Palladium is used as Group VIHb metal.
- a broad variety of palladium compounds may then be used for impregnation e.g.
- salts, complex saits or complexes such as PdCl 2 , Pd(OAc) 2 , palladium fluoride, palladium hydroxide, palladium nitrate, palladium sulfate, palladium oxide, dichlorocyclooctadienepaliadium, dichioronorbornadiene-paliadium, tetrakisacetonitrilepalladium tetrafluoroborate, tetrakisbenzonitrilepalladium ditetrafluoroborate, dichlorobisacetonitrilepalladium, dichlorobisethylene-diaminepalladium, bisacetylacetonatopalladium, tristriphenhylphosphine- acetonitrilepalladium tetrafluoroborate, dichlorobistriethylphosphinepalladium, dichlorobis-(dimethyl sulfide)palladium, dibenzoylsulfidepalla
- the hyper-branched polymer is not impregnated with the metal in the elemental state but with a metal compound as outlined above in solution the impregnated group VIHb metal containing compound is then subsequently subjected to a reduction to provide the desired catalyst
- the group VIHb metal containing compound After the impregnation process the group VIHb metal containing compound must be activated if the loading has not been performed with the group Viiib metal in the elemental state.
- Such catalyst activation is typically achieved by a reduction which can be performed according to three different methods.
- the first two methods comprise a reduction prior to performing the hydrogenation, i.e. prior to any contact with the diene-based polymer to be hydrogenated either by using hydrogen or a viable reduction agent other than hydrogen, like e.g. NaBH 4 .
- the third method comprises the reduction in-situ when performing the hydrogenation.
- the catalyst activation may be performed as follows:
- the Pd-containing pPDT catalysts is mixed with an adequate amount of an organic solvent, preferably acetone, under adequate temperature and pressure. Temperature may typically vary in the range of from 20 to 150°C, pressure is typically chosen in the range of from 0,1 MPa to 20 MPa; after reduction, the catalyst is typically collected by filtration and then used for hydrogenation;
- an organic solvent preferably acetone
- the Pd-containing/pPDT catalyst is mixed into an aqueous solution of NaBH 4 under adequate temperature and pressure.
- Temperature may typically vary in the range of from 20 to 100°C; the concentration of the aqueous solution of NaBFLjmay typically vary in the range of from 0,01 M to 10 M; after reduction, the particles may be washed to efficiently remove the excess of the reducing agent and dried at adequate temperatures, optionally under reduced pressure, and then can be used for hydrogenation;
- the reduction time can be chosen by any artisan in a range of from several minutes to hours depending on the pressure and temperature.
- the amount of Group Vlllb metal deposited on the carrier material comprising at least one hyper- branched polymer is usually 0.001 to 30 % by weight (calculated as metal, i.e. after activation), preferably 0.05 to 10 % by weight, more preferably 0, 1 to 5 % by weight based on 100% of the carrier material. If the amount of Group Vlllb metal is too small, i.e. smaller than the above mentioned lowest value, the supported catalyst must be used in a great quantity in the reaction. Consequently, the viscosity of the reaction system might become too high, so that is is difficult to stir. Hence, the catalyst might not be effectively used.
- the weight ratio of the weight ratio of the Group Vlllb metal containing catalyst deposited on the carrier material comprising at least one hyper-branched polymer (calculated as Group Vlllb metal) to the diene- based polymer is in the range of from 0.002 to 0.5, preferably 0.004 to 0.2; more preferably 0.07 to 0.15 and most preferably of 0.01 to 0.1.
- the process of the present invention is generally carried out at a temperature in the range of from 0 °C to 150°C, preferably in the range of from 5°C to 100 °C, more preferably in the range of from 10°C to 90 °C, even more preferably in the range of from 15 °C to 70 °C and in particular in the range of from 20°C to 60°C. This means that the process may be carried out at mild conditions.
- the hydrogenation process of the present invention is preferably carried out with hydrogen gas at a pressure of from 0, 1 to 20 MPa, preferably of from 0,25 to 16 MPa, and more preferably of from 1 to 12 MPa.
- said hydrogen gas is essentially pure.
- the hydrogenation temperature in the range of from 0 °C to 150°C, preferably in the range of from 5°C to 100 °C, more preferably in the range of from 10°C to 90 °C, even more preferably in the range of from 15 °C to 70 °C and in particular in the range of from 20°C to 60°C and the hydrogenation pressure is in the range of from 0.1 to 20 MPa, preferably of from 0.25 to 16 MPa, and more preferably of from 1 to 12 MPa.
- said hydrogen gas is essentially pure.
- organic solvent shall be inert under the reaction conditions of the reduction and/or hydrogenation and should not disadvantageous ⁇ influence the catalyst.
- Suitable solvents encompass ketones, such as acetone, methyl ethyl ketone, methyl isopropyl ketone, diisopropyl ketone, 2- or 3-pentanone, cyclohexanone, preferably acetone and methyl ethyl ketone, ethers, such as tetrahydrofuran, dioxan, anisole or ethylene glycol monomethyl ether, preferably tetrahydrofuran and anisole, and aromatic hydrocarbons, such as benzene, toluene or xylene.
- ketones such as acetone, methyl ethyl ketone, methyl isopropyl ketone, diisopropyl ketone, 2- or 3-pentanone, cyclohexanone, preferably acetone and methyl ethyl ketone
- the concentration of the diene-based polymer, preferably the NBR, in the reaction mixture is up 25 % by weight, preferably up to 20% by weight, more preferably up to 18% by weight and most preferably up to 15% by weight based on the reaction mixture.
- the solution of the diene based polymer is contacted with the Group VIII metal containing catalyst deposited on a carrier material containing at least one hyper- branched polymer.
- a suited reactor can be charged with the needed amount of the Group VHIb metal containing catalyst supported on at least one hyper-branched polymer and the desired amount of diene based polymer dissolved in an organic solvent. Then the reactor is sealed and the reaction system assembled for the hydrogenation.
- reaction mixture is then typically purged by bubbling nitrogen gas. After that the reaction system is heated to the desired reaction temperature, preferably under stirring with high speed agitation. Then hydrogen gas is introduced into the reaction until the designed pressure is reached. Hydrogenation pressure and reaction temperature are mostly maintained constant throughout the reaction period. After the required reaction time, the reactor is cooled down, the hydrogen pressure released, and the solution containing the hydrogenated polymer together with the heterogeneous catalyst poured out into a flask.
- the catalyst can be easily and completely removed from the hydrogenation mixture by simple filtration, recovered and used for further hydrogenation steps again.
- One relevant feature for this easy and complete removal is the high mechanical strength of the catalyst.
- the polymer can be isolated from the remaining reaction mixture by typical methods well-known to the artisan.
- Degree of hydrogenation :
- the hydrogenation may be performed with reaction times in the range of 0,5 to 10 hours, it is surprising that even when choosing very short reaction times in the range of from 0.5 to 2 hours hydrogenation degrees of more than 98% may be performed depending the other hydrogenation parameters chosen.
- Room temperature means 22 °C +/- 2°C
- NMP N-methylpyrrolidinone
- PD means p-phenylene diamine
- TMA trimesic acid
- the synthesis was performed in accordance with the procedure described in Applied Catalysis, A: General, 1999, 177(2), 219.
- a 250 mL three-necked flask was charged with 7.5 mL of pyridine and 80 mL of NMP at room temperature, and then 1.08g (10 mmol) of PD and 2.10g (10 mmol) of TMA were added into the solvent medium; after PD and TMA were totally dissolved, 7.82 mL (30 mmol) of iriphenyl phosphate was added to the solution, and then the mixture was heated to 80°C for one and half hour followed by pouring the hot solution into 500 mL of methanol containing 10 mL of 12 N aqueous HC1. The precipitated product was collected by filtration.
- the obtained pPDT polymer particles were stirred in a solution (an aqueous solution or an organic solvent) containing a Pd metal salt at room temperature for 48 hours.
- a Mettler HR83 moisture analyzer was used to heat a sample of the catalyst to 150°C and hold for 5 minutes to check the weight loss, and then the solid content of the catalyst was calculated based on this measurement. After this solid content measurement, the samples of the prepared Pd/pPDT catalysts were analyzed by inductively coupled plasma atomic emission spectroscopy (ICP) in order to determine the Pd metal content of the dried Pd pPDT. The measured Pd metal content can be seen in different tables in later parts of this report.
- ICP inductively coupled plasma atomic emission spectroscopy
- Reduction by NaBH 4 in advance - Pd/pPDT catalyst was mixed into an aqueous solution of NaBH 4 (0.1M) at 50°C for 2 hours; after the reduction, the particles were washed extensively to remove the excess of the reducing agent and dried at 60°C under vacuum for 24 hours before being used for hydrogenation;
- the hyper-branched polymer support i.e. the pPDT material
- TEM measurements were performed with a Philips high resolution transmission electron miscroscope.
- the polymer/Pd powders were suspended in 2-propanol and a drop of the resultant mixture was deposited on a carbon grid at room temperature.
- the obtained TEM micrographs show the view of 200K amplifications. All Pd metallic particles found in the TEM pictures have a diameter less than 10 nm.
- the pPDT material itself was found to be soluble in NMP, DMSO and DMF, and not dissolvable in methanol, ethanol, acetone, MEK, MCB, THF, CHC1 3 or CCI 4 .
- the Pd/pPDT was no longer soluble in any of the above solvents. This is due to gel formation promoted by the supported Pd metal.
- rynac ® 3345F available from Lanxess Germany GmbH, was the NBR grade used for all hydrogenation experiments having an acrylonitrile content of 33 % b.w. and a Mooney viscosity (ML (1+4) at 100°C) of 45.
- the reactor was cooled down, the hydrogen pressure was released, and then the polymer solution with the catalyst was poured out into a flask.
- the catalyst was easily removed from the hydrogenation mixture by simple filtration. The recovered catalyst could be used for hydrogenation again.
- Tab!e 1 shows the results achieved in hydrogenation experiments 1 to 7 with Pd/pPDT catalysts.
- NBR can be selectively hydrogenated using the Pd pPDT catalysts.
- the conversion could reach 98% within half an hour at 60°C under 3.45 MPa (500 psi) of hydrogen pressure, while it took longer reaction time to reach high conversion when the temperature was down to 25°C or the hydrogen pressure was lowered to 0.35 MPa (50 psi).
- Examples 8 and 9 prove the recyclability of the supported catalysts.
- the Pd/pPDT catalyst was separated by simple filtration followed by extensive washing using acetone. The recycled Pd/pPDT catalyst was then reused for a new hydrogenation reaction.
- the hydrogenation results using fresh and recycled Pd/pPDT catalysts are summarized in Table 2.
- Examples 10 to 13 using Pd/pPDT catalysis show the influence of the Pd/NBR ratio on the hydrogenation.
- Pd(OAc) 2 was used to impregnate the pPDT and the reduction of the palladium (II) was performed in-situ when hydrogenating NBR with 3 ⁇ 4.
- Table 3 Effect of Pd NBR ratio on NBR hydrogenation
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Abstract
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KR1020137005042A KR101589353B1 (en) | 2010-07-28 | 2011-07-27 | Hydrogenation of diene-based polymers |
JP2013521122A JP5819961B2 (en) | 2010-07-28 | 2011-07-27 | Hydrogenation of diene-based polymers |
EP11743992.7A EP2598537B1 (en) | 2010-07-28 | 2011-07-27 | Hydrogenation of diene-based polymers |
BR112013002027A BR112013002027A2 (en) | 2010-07-28 | 2011-07-27 | process for selective hydrogenation of carbon-carbon double bonds in diene-based polymer |
CN201180045539.3A CN103347903B (en) | 2010-07-28 | 2011-07-27 | Based on the hydrogenation of the polymkeric substance of diene |
US13/812,240 US9371403B2 (en) | 2010-07-28 | 2011-07-27 | Hydrogenation of diene-based polymers |
CA2806424A CA2806424A1 (en) | 2010-07-28 | 2011-07-27 | Hydrogenation of diene-based polymers |
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KR101968221B1 (en) * | 2015-09-25 | 2019-04-11 | 주식회사 엘지화학 | Carbon black dispersed solution and method for preparing the same |
KR101615865B1 (en) | 2015-11-05 | 2016-04-27 | 정용호 | Management System for working in place and Drive Method of the Same |
CN108778502B (en) * | 2016-03-31 | 2022-01-04 | 日本瑞翁株式会社 | Metal-supported catalyst and method for producing hydrogenated conjugated diene polymer |
CN106046382B (en) * | 2016-05-25 | 2018-10-09 | 暨南大学 | It is a kind of to load nitric oxide production cationic polymer and its preparation method and application |
CN109569694B (en) * | 2019-01-17 | 2021-08-31 | 福州大学 | Preparation method of nitrile rubber selective hydrogenation supported catalyst and hydrogenation process thereof |
WO2021066300A1 (en) | 2019-09-30 | 2021-04-08 | 주식회사 엘지화학 | Catalyst for hydrogenation reaction and method for producing same |
CN111393664B (en) * | 2020-04-14 | 2021-11-02 | 天津大学 | Bimetallic MOF material, preparation method thereof and application thereof in hydrogenation reaction |
CN116410350A (en) * | 2023-02-16 | 2023-07-11 | 大连理工大学 | Method for preparing hydrogenated nitrile rubber by selectively hydrogenating nitrile rubber |
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EP1760093B1 (en) * | 2005-08-30 | 2011-12-21 | LANXESS Deutschland GmbH | Use of catalysts for the metathesis degradation of nitrile rubber |
DE102006008521A1 (en) | 2006-02-22 | 2007-08-23 | Lanxess Deutschland Gmbh | Use of a specified ruthenium or osmium catalyst in the metathesis of nitrile rubbers results in improvements in activity and in gel prevention |
DE102006040569A1 (en) | 2006-08-30 | 2008-03-06 | Lanxess Deutschland Gmbh | Process for the metathesis degradation of nitrile rubbers |
EP2075262A1 (en) * | 2007-12-17 | 2009-07-01 | Lanxess Inc. | Hydrogenation of diene-based polymers |
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2011
- 2011-07-27 JP JP2013521122A patent/JP5819961B2/en not_active Expired - Fee Related
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