Patent Description:
Industrial processes for the catalytic hydroformylation of higher olefins (i.e., those olefins having more than five carbons) face several challenges, including efficient catalyst recovery/recycle and the limited solubilities of the gaseous reactants (H<NUM> and CO) in the liquid reaction phase. See <NPL>). The commercial catalysts used in the lower olefin processes, mostly rhodium-based, are not applied in higher olefin hydroformylation because of their instability at the temperatures required for product separation/distillation. Hence, while the less expensive cobalt-based catalysts are used, harsher conditions (<NUM>-<NUM>, <NUM>-<NUM> MPa) are often employed to activate and stabilize the catalysts. In addition, the catalyst recovery typically involves significant quantities of solvents, acids, and bases in a series of many operating units. Thus, an engineered system is desired to realize process intensification at milder conditions with a highly active catalyst that requires a relatively simpler and environmentally friendlier catalyst recovery method. Similar issues and needs are encountered in carrying out other processes besides hydroformylation, for example, in hydrogenation, oxidation, and carbonylation.

Several approaches for catalyst recovery have been reported in literature. The first approach involves employing a "phase transition switch" whereby reactions are performed homogeneously, following which the catalysts are recovered from the product stream via phase transition triggered by a change in either the system temperature (see<NPL>); <NPL>)) or pressure (see <NPL>); <NPL>)).

The second approach involves biphasic media, such as water/organic (see<NPL>)), water/CO<NUM> (see <NPL>); <NPL>)), and room temperature ionic liquid/CO<NUM> (see <NPL>)), wherein the catalyst is sequestered in either the water or the ionic liquid phases whereas the product preferentially separates into the organic phase or the CO<NUM> phase.

The third approach involves immobilizing homogeneous rhodium ("Rh") catalysts on various supports to form a heterogenized catalyst that can be easily applied in fixed bed or slurry type reactors, i.e., the silicate MCM-<NUM> (see<NPL>)), zeolites (see <NPL>)), nanotubes (see <NPL>)), supported aqueous phase catalysis ("SAPC") (see<NPL>)), and polymers (see L<NPL>) and<NPL>)). However, such approaches approach still suffers from several drawbacks as follows that prevent it from being commercially viable: (a) metal leaching from the support; (b) reduced activity and selectivity compared to the homogeneous counterpart; (c) nonuniform structures of the resulting heterogeneous catalysts; (d) mass transfer limitations due to hindered diffusion; (e) low activity; and/or (f) high operating pressures and/or temperatures.

Previously, several research groups have developed polystyrene supports that facilitate the recycle of rhodium catalysts. <NPL>); <NPL>); <NPL>);<NPL>);<NPL>);<NPL>); <NPL>). However, the typical polymer supports suffer from serious limitations like insolubility, gel formation, tedious procedures to swell the polymer, and limited loading of the phosphorus ligand in the polymer backbone (e.g., <NUM> mmol/g). Many of these issues relate to the fact that polymers that are purchased commercially, or are prepared by conventional radical polymerization of styrene, have high molecular weight and/or broad molecular weight distribution. Thus, they have poor solubility properties. The slower kinetics of reactions catalyzed by gel-phase or solid-phase catalysts have important practical effects as well. For instance, the conjugate addition of arylboronic acids to enones suffers from competing hydrolysis of the costly boronic acids; the slower the catalyst is, the more hydrolysis occurs. Thus, when a heterogeneous polystyrene-supported catalyst is used for the conjugate addition, a <NUM>-<NUM>-fold excess of boronic acid is required.

The use of CO<NUM>-expanded liquids ("CXLs") as reaction media has received increased attention by the present inventors. CXLs are a continuum of compressible media generated when various amounts of dense phase carbon dioxide are added to an organic solvent. CXLs offer both reaction and environmental benefits. Near-critical carbon dioxide possesses highly tunable transport properties ranging from gas-like diffusivities to liquid-like viscosities. The presence of dense CO<NUM> imparts similar tunability to CXLs as well. The solubilities of many gaseous reagents (i.e., O<NUM>, H<NUM>) in CXLs are enhanced several-fold relative to the neat liquid phase (i.e., those without any CXLs). See<NPL>); <NPL>);<NPL>); <NPL>); <NPL>). Although most transition metal complexes are only sparingly soluble in supercritical CO<NUM> (scCO<NUM>), the presence of an appropriate amount of the organic liquid in CXLs ensures adequate solubilities of transition metal complexes in a CXL phase for performing homogeneous catalysis. Further, such solubilities are realized at pressures an order of magnitude lower than those required in scCO<NUM> medium for solubilizing Rh catalyst complexes with fluorinated ligands.

Recently, the present inventors reported the homogeneous catalytic hydroformylation of <NUM>-octene in CO<NUM>-expanded acetone with an unmodified rhodium catalyst. See <NPL>). At <NUM> and <NUM>, the turnover frequencies ("TOFs") in CO<NUM>-expanded acetone were up to four-fold greater than those obtained in either neat acetone (a polar solvent) or compressed CO<NUM>. The enhanced rates in CXLs were realized at significant solvent replacement (up to <NUM>% by volume) and at mild operating pressures (less than <NUM> MPa). Although the hydroformylation rates were enhanced, the regioselectivity towards linear and branched aldehydes (n/i ratio) remained unaffected by the change in either the acetone/CO<NUM> ratio or the temperature. In <CIT> an improved hydroformylation process was described. Altering the amount of the compressed gas in the liquid phase alters the chemoselectivity of the products. In addition, varying the content of the compressed gas in the liquid alters the regioselectivity of the products. The addition of the increasing amounts of the compressed gas surprisingly improves the ratio of linear to branched aldehydes during the hydroformylation process, and vice-versa. <CIT> discloses a catalyst system which is comprised of (a) palladium or a palladium compound and (b) a fluorinated alcohol is effective for polymerizing norbornene-functional monomers into polynorbornene-functional polymers. <CIT> discloses a palladium-catalysed carbon-carbon bond forming reaction in compressed carbon dioxide is provided wherein at least one of the reagents used in said reaction is bounded to a solid polymer support. <CIT> relates to processes for producing one or more substituted or unsubstituted hydroxyaldehydes, e.g., <NUM>-hydroxyhexanals, which comprise subjecting one or more substituted or unsubstituted alkadienes, e.g., butadiene, to hydrocarbonylation in the presence of a hydrocarbonylation catalyst, e.g., a metal-organophosphorus ligand complex catalyst, and hydroformylation in the presence of a hydroformylation catalyst, e.g., a metal-organophosphorus ligand complex catalyst, to produce one or more substituted or unsubstituted hydroxyaldehydes. <CIT> discloses a method for separating a noble metal catalyst from a crude reaction product of a noble metal-catalyzed hydroformylation reaction which comprises: (a) contacting the crude reaction product under perstraction conditions with a membrane capable of allowing a substantial portion of unreacted olefin feed and hydroformylation reaction product to pass therethrough as permeate while retaining a substantial portion of the catalyst as retentate; (b) removing the permeate by sweeping it away from the membrane by means of a sweep stream which is the same as the olefin feed used in the hydroformylation reaction; and (c) retaining the catalyst as retentate. <NPL> is a review article relating to transition metal catalysis using functionalized dendrimers. <CIT> relates to dendritic macromolecules and their use in metal-dendritic macroligand complex catalyzed processes, e.g., hydroformylation. The use of metal-dendritic macroligand complex catalysts in such processes facilitates the separation of desired product from catalyst, for example, by membrane filtration. <NPL> is a review article relating to soluble polymers as scaffolds for recoverable catalysts and reagents. <CIT> discloses a molecular weight-enlarged, homogeneously soluble ligand, useful in catalysts, particularly for the synthesis of enantiomerically enriched organic compounds. <CIT> relates to water-soluble chiral diphosphines that are useful as ligands in the synthesis of water-soluble complexes for asymmetric catalysis. <NPL> concerns homogenous catalysis in supercritical carbon dioxide with rhodium catalysts tethering fluoroacrylate polymer ligands. <NPL> discloses reactions of aldehydes with diethylzinc catalysed by polymer-supported ephedrine and camphor derivatives. <NPL> discloses soluble polymer-supported palladium catalysts for Heck, Sonogashira, and Suzuki Coupling reactions of aryl halides and the employment of nanofiltration for catalyst separation. In the present invention, soluble polymer-supported rhodium catalysts that have a narrow molecular weight distribution were prepared. These compounds can be readily recycled by precipitation and filtration. In addition to molecular weight control, it was important to design a polymer support that could bind Rh in a multidentate fashion. Such binding was expected to better site-isolate the rhodium catalysts as well as prevent leaching of rhodium from the polymer. Moreover, it was demonstrated that such catalysts can be employed using CXLs.

The present invention is as defined in the appended claims and directed to catalyst compositions and their methods of use. The catalyst composition comprises a polymer that is functionalized with a multidentate ligand for binding a transition metal containing compound. Thus the catalyst composition comprises polystyrene-co-<NUM>,<NUM>'-(<NUM>,<NUM>'-di-tert-butyl-<NUM>,<NUM>'-divinylbiphenyl-<NUM>,<NUM>' diyl)bis(oxy)didibenzo [<NUM>,<NUM>,<NUM>]dioxaphosphepine. This functionalized polymer forms a transition metal complex with rhodium as the said transition metal. The functionalized polymer has a number average molecular weight of about <NUM>,<NUM> to <NUM>,<NUM>/mol and a polydispersity index of about <NUM> to <NUM>. In another aspect, the functionalized polymer has a number average molecular weight of about <NUM>,<NUM>, <NUM>,<NUM>, <NUM>,<NUM>, <NUM>,<NUM>, <NUM>,<NUM>, <NUM>,<NUM>, <NUM>,<NUM>, <NUM>,<NUM>, <NUM>, <NUM>, <NUM>,<NUM>, <NUM>,<NUM>, <NUM>,<NUM>, <NUM>,<NUM>, <NUM>,<NUM>, <NUM>,<NUM>, <NUM>,<NUM>, <NUM>,<NUM>, <NUM>,<NUM>, <NUM>,<NUM>, <NUM>,<NUM>, <NUM>,<NUM>, <NUM>,<NUM>, <NUM>,<NUM>, <NUM>,<NUM>, <NUM>,<NUM>, <NUM>,<NUM>/mol, or some range therebetween. For example, the functionalized polymer may have a number average molecular weight selected from a range consisting o f about <NUM>,<NUM> to <NUM>,<NUM>/mol, <NUM>,<NUM> to <NUM>,<NUM>/mol, <NUM>,<NUM> to <NUM>,<NUM>/mol, and <NUM>,<NUM> to <NUM>,<NUM>/mol. In still another aspect, the polydispersity index is about <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, or some range therebetween. In another aspect, the catalyst composition has a transition metal complex which is covalently bound or chelated to said polystyrene at a ratio of about <NUM>:<NUM> to <NUM>:<NUM> mol:mol in terms of mole metal to mole of styrene monomer.

At least a portion of the reaction mixture is preferably in a liquid phase. Preferably the substrate and catalyst are in the liquid phase. The reactant may also be in the liquid phase (for example, oxidation of an oxidizable substrate using hydrogen peroxide). The substrate in the reaction mixture may include a ketone, aldehyde, enone, enal, olefin, alkyne, alcohol, oxidizable substrate, or mixtures thereof. The reactant may include a reactant gas selected from the group consisting of CO, O<NUM>, H<NUM>, or a H<NUM>/CO syngas.

In another aspect, a compressed gas is added to the reaction mixture. The compressed gas is preferably an inert gas, such as one selected from the group consisting of nitrogen, carbon dioxide, xenon, SF<NUM>, argon, or helium. It will be appreciated that the reactant may comprise a reactant gas which is also the compressed gas.

In still another aspect, a compressed gas is added to the reaction mixture to volumetrically expand the reaction mixture. The addition of the compressed gas also reduces the viscosity of the liquid phase of the reaction mixture. Thus, for example, the invention provides for an improved hydroformylation process comprising reacting an olefin with CO and H<NUM> in the presence of the inventive hydroformylation catalyst composition in a liquid that has been volumetrically expanded with a compressed gas, such as supercritical or subcritical carbon dioxide.

The compressed expanding gas is generally selected from the group consisting of carbon dioxide, N<NUM>O, xenon, and SF<NUM>, although for reasons of cost and ease of use, pressurized subcritical or supercritical carbon dioxide is usually the gas of choice. The expanding gas is present in the reaction mixture at a level below that which will cause the catalyst to precipitate; that is, the catalyst is usually the least soluble component of the reaction mixture, and for good results, it should remain uniformly solubilized in the reaction mixture. Therefore, the expanding gas is introduced at levels which will maintain uniform solubility of the inventive polymer-based catalyst composition with the molecular weight and narrow PDI as discussed herein. These levels of course vary depending upon the components of the reaction mixture, and especially the catalyst. It is therefore usually necessary to preliminarily determine the extent of expanding gas supplementation which can be accommodated with each individual reaction mixture. See Subramaniam, <CIT> and <CIT> titled "Catalytic oxidation of organic substrates by transition metal complexes in organic solvent media expanded by supercritical or subcritical carbon dioxide," and see Subramaniam, <CIT> titled "Tuning product selectivity in catalytic hydroformylation reactions with carbon dioxide expanded liquids,". The compressed gas typically has a volume fraction in the liquid phase between <NUM>% and <NUM>%. As discussed above, it will be appreciated that the reactant may comprise a reactant gas which is also the compressed gas used to volumetrically expand the liquid phase of the reaction mixture.

In another aspect, the catalyst composition comprising the polymer functionalized with a multidentate ligand of the present invention is recyclable. Thus, the present invention is also directed to a process for the separation of the catalyst composition from the reaction mixture. The process steps include forming a reaction mixture comprising a reactant, a substrate, an optional solvent, and the catalyst as described herein. The substrate and the catalyst composition are in a liquid phase. The liquid phase is then filtered through a filter to form a retentate composition and a permeate composition. The reaction and filtration steps may be performed either batchwise or continuously. Total losses of the transition metal are preferably less than <NUM>%, still more preferably less than <NUM>%, and are most preferably less than <NUM>%.

Thus, in one aspect, the present invention uses nanofiltration by (a) specifically designing and synthesizing bulky polymer-supported catalyst complexes of transition metals (such as Rh) such that the bulky complexes are substantially retained in the retentate composition and that the leakage of Rh and other metals along with the solvent that passes through the nanofiltration membrane into the permeate composition is lowered to tens of parts per billion (ppb); (b) using compressed gas-expanded liquids, such as CXLs, to lower the viscosity (compared to conventional non-expanded liquids) of the liquid phase being filtered and thereby improving the filtration rates; and (c) performing reactions continuously using the compressed gas-expanded liquids (e.g. CXLs) in the nanofiltration device/reactor to not only exploit the advantages of process intensification and improved selectivity afforded by CXLs but also simultaneously separate the products by the nanofiltration membrane while substantially retaining the catalyst composition in the retentate composition.

As an example, the present invention is directed to a catalyst composition comprising a soluble polymer-supported bidentate phosphite ligands with a narrow molecular weight distribution and PDI which binds to Rh-containing compounds. As a result, the precipitation of the heavier molecular weight fraction of the functionalized polymer in CXLs and the leakage of the lighter molecular weight fraction of the functionalized polymer (along with the bound Rh) through the membrane are simultaneously avoided. The precipitation and leakage cause losses of catalyst activity and metal, both of which are detrimental to process economics. Further, the use of a compressed gas such as CO<NUM> not only provides the pressure for nanofiltration but also lowers the viscosity of the solution by partly dissolving in the solution without causing precipitation of the complex.

The hydroformylation and other reactions using the catalyst composition of the present invention preferably occur at a pressure range selected from the group consisting of <NUM> to <NUM> MPa, <NUM> to <NUM> MPa, <NUM> to <NUM> MPa, and <NUM> to <NUM> MPa. The reactions using the catalyst composition of the present invention preferably take place at a temperature range selected from the group consisting of <NUM> to <NUM>, <NUM> to <NUM>, <NUM> to <NUM>, and <NUM>-<NUM>. The pressure and/or temperature may be constant or may vary through the reaction.

In still another aspect, the catalyst compositions of the present invention are particularly well adapted for use in hydroformylation reactions in which the inventive polymer-supported catalyst composition is recycled. Thus, the present invention is directed to a hydroformylation process comprising forming a reaction mixture comprising CO and H<NUM> as reactants, and in which the catalyst composition comprising the functionalized polymer is complexed with a transition metal and a olefin substrate are in the liquid phase. The liquid phase has preferably been volumetrically expanded with a compressed gas, such as compressed carbon dioxide, by adding a adding a compressed gas into the reaction mixture. The liquid phase is then passed through a filter to form a retentate composition and a permeate composition such that the retentate composition retains the catalyst composition and is recycled. The hydroformylation catalyst composition comprises a rhodium containing compound and a phosphorous-containing ligand in the polymer, i.e. the bis(phosphite) polystyrene defined in the appended claims. An organic solvent, such as acetone, toluene, tetrahydrofuran, or dichloromethane, may be added to the reaction mixture in the liquid phase. The process is preferably maintained at a temperature between <NUM> and <NUM> and a pressure less than <NUM> MPa. The reaction and filtration steps may be performed either batchwise or continuously.

As discussed herein, the catalyst compositions are recyclable using nanofiltration technologies. It is anticipated that the permeate composition has a concentration of the transition metal less than <NUM> ppb, preferably less than <NUM> ppb, and even less than <NUM> ppb. For example, for the exemplary catalyst composition described herein, rhodium retentate concentrations were about <NUM> ppm, while the rhodium permeate concentrations were under <NUM> ppb.

In still another aspect, the catalyst compositions of the present invention may used in oxidation reactions in which the metal catalyst composition is recycled. The compressed gas may comprise one selected from the oxygen, air, or a combination thereof. Hydrogen peroxide may also be used as an oxidant by providing the hydrogen peroxide in the liquid phase, along with the substrate. The reaction and filtration steps may be performed either batchwise or continuously.

In still another aspect, the catalyst compositions of the present invention are used in hydrogenation reactions in which the metal catalyst is recycled. The compressed gas comprises H<NUM>. The reaction and filtration steps may be performed either batchwise or continuously.

In still another aspect, the catalyst compositions of the present invention are used in a carbonylation reaction in which the metal catalyst is recycled. The compressed gas compressed gas comprises CO. The reaction and filtration steps may be performed either batchwise or continuously.

Additional aspects of the invention, together with the advantages and novel features appurtenant thereto, will be set forth in part in the description which follows, and in part will become apparent to those skilled in the art upon examination of the following, or may be learned from the practice of the invention. The objects and advantages of the invention may be realized and attained by means of the instrumentalities and combinations particularly pointed out in the appended claims.

As used herein, the term "carbon dioxide expanded liquids" or "CXLs" refer to a continuum of compressible media generated when a dense phase carbon dioxide is added to an organic liquid media. Pressurized subcritical or supercritical carbon dioxide is usually the gas of choice.

As used herein, the term "higher olefins" refers to olefins having more than five carbons in the chain.

As used herein, the term "internal" olefins are accordingly olefins whose double bond is, unlike alpha-olefins, not terminal but located in the interior of the olefin molecule.

As used herein, the term "turnover frequency" or "TOF" refers to a moles of substrate (e.g., <NUM>-octene) converted to all products per mole of catalyst per hour during fixed-time batch runs.

As used herein, the term "chemoselectivity" or "Sa" refers to the moles of aldehydes or the octene isomers formed relative to the moles of substrate (e.g., octene) converted during the hydroformylation process.

As used herein, the term "regioselectivity" or "n/i" refers to the ratio of linear to branched aldehydes in the product.

As use herein the term "polydispersity" or "polydispersity index" refers to the relationship between the weight average molecular weight of the polymer and the number average molecular weight of the polymer. Specifically, the polydispersity index is the ratio between weight average molecular weight and number average molecular weight.

The present invention is directed to catalyst compositions and their methods of use. The catalyst compositions comprise a polymer that is functionalized with a multidentate ligand for binding a transition metal containing compound as defined in the appended claims.

The functional groups may be attached to the polymer chain by copolymerization with one or more monomers (e.g. compound (<NUM>) in Example <NUM> and styrene as described herein). Alternatively, the functionalized polymer may be prepared by functionalizing the already formed polymer, for example as shown in <NPL>).

The present invention also relates to a process for the separation of a catalyst composition from a reaction mixture comprising a reactant, a substrate, and the catalyst composition as described herein. The reaction mixture is preferably a hydrogenation reaction mixture, a hydroformylation reaction mixture, an oxidation reaction mixture, or a carbonylation reaction mixture, or a combination thereof.

The hydroformylation is carried out in a homogeneous reaction system. The term "homogeneous reaction system" generally refers to a homogeneous solution comprised of gas-expanded solvent (e.g. CXLs), the catalyst composition as described herein, a syngas, and olefinically unsaturated comnound, and the reaction product. The amount of rhodium compound in the catalyst composition is not specially limited, but is optionally selected so that favorable results can be obtained with respect to catalyst activity and economy. In general, the concentration of rhodium in the reaction medium is between <NUM> and <NUM>,<NUM> ppm and more preferably between <NUM>-<NUM> ppm, calculated as the free metal.

The volume ratio of carbon monoxide to hydrogen in the synthesis gas is generally in the range from <NUM> to <NUM> and <NUM> to <NUM>, preferably between <NUM> to <NUM> to <NUM> to <NUM>, and most preferably <NUM>:<NUM> to <NUM>:<NUM>, in particular <NUM>:<NUM>. The synthesis gas is advantageously used in excess, for example in an amount up to three times the stoichiometric amount.

The olefin substrates in the present invention may be any organic compound having at least one ethylenically unsaturated functional group (i.e., a carbon-carbon double bond) and may be, for example, an aromatic, aliphatic, mixed aromatic-aliphatic (e.g., aralkyl), cyclic, branched or straight chain olefin. Preferred olefins are C<NUM> to C<NUM> olefins, and most preferred are "higher olefins" which refers to compounds containing more than <NUM> carbon atoms. More than one carbon-carbon double bond may be present in the olefin, and thus, dienes, trienes, and other polyunsaturated substrates thus may be used. The olefin may optionally contain substituents other than hydrocarbon substituents such as halide, carboxylic acid, ether, hydroxy, thiol, nitro, cyano, ketone, ester, anhydride, amino, and the like.

Exemplary olefins suitable in the process of the present invention include ethylene, propylene, butenes, butadiene, pentenes, isoprene, <NUM>-hexene, <NUM>-hexene, <NUM>-heptene, <NUM>-octene, diisobutylene, <NUM>-nonene, <NUM>-tetradecene, pentamyrcene, camphene, <NUM>-undecene, <NUM>-dodecene, <NUM>-tridecene, <NUM>-tetradecene, <NUM>-pentadecene, <NUM>-hexadecene, <NUM>-heptadecene decene, <NUM>-nonadecene, <NUM>-eicosene, the trimers and tetramers of propylene, polybutadiene, polyisoprene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, cyclododecatriene, dicyclopentadiene, methylenecyclopropane, methylenecyclopentane, methylenecyclohexane, vinylcyclohexane, vinyl cyclohexene, methallyl ketone, allyl chloride, allyl bromide, acrylic acid, methacrylic acid, crotonic acid, vinyl acetic acid, crotyl chloride, methallyl chloride, the dichlorobutenes, allyl alcohol, allyl carbonate, allyl acetate, alkyl acrylates and methacrylates, diallyl maleate, diallyl phthalate, unsaturated triglycerides such as soybean oil, and unsaturated fatty acids, such as oleic acid, linolenic acid, linoleic acid, erucic acid, palmitoleic acid, and ricinoleic acid and their esters (including mono-, di-, and triglyceride esters), and alkenyl aromatic compounds such as styrene, alpha-methyl styrene, beta-methyl styrene, divinyl benzene, <NUM>,<NUM>-dihydronaphthalene, indene, stilbene, cinnamyl alcohol, <NUM>-methyl-<NUM>-phenyl-<NUM>-propene, <NUM>-methyl-<NUM>-phenyl-<NUM>-propen-<NUM>-ol, cinnamyl acetate, cinnamyl bromide, cinnamyl chloride, <NUM>-stilbenemethanol, ar-methyl styrene, ar-ethyl styrene, ar-tert-butyl styrene, archlorostyrene, <NUM>,<NUM>-diphenylethylene, vinyl benzyl chloride, vinyl naphthalene, vinyl benzoic acid, ar-acetoxy styrene, ar-hydroxy styrene (i.e., vinyl phenol), <NUM>- or <NUM>-methyl indene, <NUM>,<NUM>,<NUM>-trimethylstyrene, <NUM>-phenyl-<NUM>-cyclohexene, <NUM>,<NUM>-diisopropenyl benzene, vinyl anthracene, vinyl anisole, and the like.

In an exemplary aspect, the olefin is a fatty compound, for example, mono- and polyunsaturated free fatty acids, fatty esters, triglyceride oils, or other fatty-derived materials. Suitable olefins are described in <CIT>.

Of these, linear higher olefins are most preferred. The olefin is preferably present in about <NUM> to <NUM> mol % of the reaction mixture. It will be appreciated to those skilled in the art that the olefin concentration (i.e., availability) in the liquid phase, where the reaction occurs, is most important, and for low boiling light olefins this is dictated by the operating pressure and temperature.

The structures of the comparative catalysts investigated are summarized in <CIT>. The identity of the specific catalyst composition of the claimed invention including that of the multitendate ligand emplöyed therein is, however, as defined in the claims. The rhodium concentration in the liquid reaction mixture is generally from <NUM> to <NUM> ppm by weight, preferably from <NUM> to <NUM> ppm by weight and particularly preferably from <NUM> to <NUM> ppm by weight.

The hydroformylation process within the separation process of the present invention can advantageously be carried out in the presence of solvents. In general, the polarity of the solvent will impact the regioselectivity, with non-polar solvents generally yielding higher n/i ratios. Adding a compressed gas such as CO<NUM> to the solvent allows for the continuous tunability of the polarity of the solvent system towards a more non-polar system. As solvents, preference is given to using the aldehydes which are formed in the hydroformylation of the respective olefins and also their higher-boiling downstream reaction products, i.e., the products of aldol condensation. Solvents which are likewise suitable are the olefins themselves, aromatics such as toluene and xylenes, hydrocarbons or mixtures of hydrocarbons, which can also serve for diluting the above-mentioned aldehydes and the downstream products of the aldehydes. Further possible solvents are esters of aliphatic carboxylic acids with alkanols, for example ethyl acetate or Texano®, ethers such as tert-butyl methyl ether and tetrahydrofuran. Is also possible to use non-polar solvents,e.g., alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, ketones such as acetone, and methyl ethyl ketone etc. "Ionic liquids" can also be used as solvents. These are liquid salts, for example, N,N'-dialkylimidazolium salts such as N-butyl-N'-methylimidazolium salts, tetraalkylammonium salts such as tetra-n-butylammonium salts, N-alkylpyridinium salts such as n-butylpyridinium salts, tetraalkylphosphonium salts such as trishexyl(tetradecyl)phosphonium salts, e.g., the tetrafluoroborates, acetates, tetrachloroaluminates, hexafluorophosphates, chlorides, and tosylates.

It is also anticipated that the catalyst compositions defined in the appended claims and the methods for retention and recycling of the catalyst compositions during either batch or continuous operation may be readily adapted to other reaction mixture systems in addition to hydroformylation systems, such as a hydrogenation reaction mixture, an oxidation reaction mixture, or a carbonylation reaction mixture, or a combination thereof. See generally, <NPL>). For example, <CIT> and <CIT> titled "Catalytic oxidation of organic substrates by transition metal complexes in organic solvent media expanded by supercritical or subcritical carbon dioxide,", disclose oxidation reaction mixtures broadly including an oxidizable substrate and an oxidation catalyst that are supplemented with a compressed gas such as carbon dioxide so as to volumetrically expand the reaction mixture, thereby facilitating and accelerating oxidation. Although the expansion gas could either be a compressible gaseous substrate or the oxidizing agent, typically a substrate or an oxidizing agent separate from the inert gas is employed. Thus, the compressed gas may be selected from the group consisting of oxygen, air, or a combination thereof as the oxidizing agent. Alternatively, the oxidizing agent (such as hydrogen peroxide) may be provided in the liquid phase. The reaction mixtures generally include an organic solvent system.

The present invention also involved methods to recycle the polymer-supported catalysts of the present invention using membrane filtration. The filter preferably has a molecular weight cut-off range selected from the group consisting of <NUM> to <NUM>/mol, <NUM> to <NUM>/mol, or <NUM> to <NUM>/mol based on <NUM>% rejection of the solute. Several membranes have been claimed to be capable of nanofiltration in organic solvent, known as solvent resistant nanofiltration (SRNF) membranes. Koch SelRO® membrane systems (USA) are solvent-stable, commercially available, and supplied in a wet form. Among of the most popularly examined membranes (MPF-<NUM>, MPF-<NUM> and MPF-<NUM>), MPF-<NUM> has been the most studied commercial SRNF membrane in many applications. STARMEM® from Membrane Extraction Technology (United Kingdom) and Solsep membranes from SolSep BV-Robust Membrane Technologies (The Netherlands) appeared in the market recently and have been successfully demonstrated in the literature for organic solvent nanofiltration. Another series of membranes, Desal-<NUM> and Desal-<NUM>-DK from GE Osmonics (USA) are designed for aqueous applications, but are also selective in SRNF. <NPL>) summarized more membrane information.

The membrane nanofiltration setups described in the literature can be categorized into two groups according to the flow direction relative to the membrane surface: dead-end filter (perpendicular) and cross-flow filter (parallel). Commercially available dead-end filtration cells include: a solvent-resistant stirred cell from Millipore (USA), MET cell from Membrane Extraction Technology Ltd. (UK) and HP4750 stirred cell from Sterlitech Corporation (USA). However, an alternative setup GE SepaTM CF II Med/High foulant allows for cross-flow filtration with any membrane. Cross-flow filtration set-ups are described in<NPL>) ; <NPL>);<NPL>);<NPL>).

The invention will be illustrated by the following non-limiting examples.

In this example, a well-characterized polymer having comparatively low molecular weight and a narrow molecular weight distribution (about <NUM> x <NUM><NUM> g/mol, polydispersity index = <NUM>) was prepared using the scheme below. Since the functional monomer (<NUM>) proved to be equally active toward polymerization as styrene, the PDI was expected to be similar to that reported for pure polystyrene. See <NPL>). Control of the molecular weight and distribution was achieved by adopting a living free radical polymerization technique that is mediated by the stable nitroxyl radical, TEMPO. Conducting the copolymerization of the functional monomer (<NUM>) and styrene (<NUM>:<NUM> ratio) at <NUM> produced a functional polymer whose ligand incorporation into the polystyrene backbone was estimated at <NUM>% from the <NUM>H NMR spectrum. Interestingly, end group analysis of the vinyl region of the <NUM>H NMR spectrum suggests that the polymer is not cross-linked under these conditions. In other words, a single alkene in the bis-alkene <NUM> undergoes polymerization. The resulting polymer was deprotected and the phosphite ligands introduced onto the polymer backbone. The result is a polymer supported Biphephos derivative that was denominated "JanaPhos" or compound PBB10. If incorporation of the phosphite into the polymer was perfect, one would expect a P-loading of <NUM> mmol/g and thus the ligand loading would be <NUM> mmol/g. Estimation of the P loading by 31P NMR spectroscopy shows that the P-loading is <NUM> mmol/g. This value was further confirmed by inductively coupled plasma optical emission spectrometry ("ICP-OES") analysis of the polymer, indicating that the polymer can support <NUM> mmol of rhodium per gram of polymer.

The synthesis of soluble polymer supported phosphite ligands is shown below in the scheme below:
<CHM>.

It will be appreciated that although compound PPB <NUM> (<NUM>) is shown with two polystyrene linkages, it is believed that the polystyrene is attached at only one of the aromatic groups shown as discussed herein.

Synthesis of <NUM>,<NUM>'-dimethoxy-<NUM>,<NUM>'-di-tert-butylbiphenyl-<NUM>,<NUM>'-diol (<NUM>): The compound <NUM> was prepared according to the reported procedure. See <NPL>). A solution of <NUM>-tert-butyl-<NUM>-hydroxyanisole (<NUM>, <NUM> mmol) in methanol (<NUM>) was prepared and a solution of KOH(<NUM>, <NUM> mmol) and K<NUM>Fe(CN)<NUM> (<NUM>, <NUM> mmol) in water (<NUM>) was added dropwise over one hour at room temperature. The mixture was stirred for two hours before the addition of <NUM> of water. The suspension was extracted with <NUM> of ethyl acetate twice. The aqueous solution was extracted with <NUM> of ether and the organic phases were combined and washed with <NUM> of saturated brine. The organic phase was dried over Na<NUM>SO<NUM>. Removal of the solvents under vacuum afforded a light brown solid. Washing with n-hexane resulted in an off-white powder; yield: <NUM> (<NUM>%).

<NUM>,<NUM>'-Dmethoxy-<NUM>,<NUM>'-di-tert-butylbiphenyl-<NUM>,<NUM>'-diol (<NUM>): Brownish solid, m. <NUM>-<NUM> ; <NUM>H NMR (<NUM>, CD<NUM>Cl<NUM>) δ ppm <NUM> (d, J = <NUM>, <NUM>), <NUM> (d, J = <NUM>, <NUM>), <NUM> (s, br, <NUM>), <NUM> (s, <NUM>), <NUM> (s, <NUM>); <NUM>C NMR (<NUM>, CDCl<NUM>) δ ppm <NUM> (2C), <NUM> (2C), <NUM> (2C), <NUM> (2C), <NUM> (2C), <NUM> (2C), <NUM> (2C), <NUM> (2C), <NUM> (6C); IR (CH<NUM>Cl<NUM>): v <NUM> (br), <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>-<NUM>; Calcd. HRMS for C<NUM>H<NUM>O<NUM> (M+), <NUM>; Found, <NUM>.

Synthesis of <NUM>,<NUM>'-di-tert-butylbiphenyl-<NUM>,<NUM>',<NUM>,<NUM>'-tetraol (<NUM>): To a stirring solution of <NUM> (<NUM>, <NUM> mmol) in CH<NUM>Cl<NUM> (<NUM>) borontribromide (<NUM>, <NUM> mmol, <NUM> in DCM) was added dropwise over <NUM> minutes at <NUM>. After addition the reaction mixture was taken to room temperature and stirred for <NUM> minutes. It was quenched by the addition of ice water and the white precipitate was dissolved by the addition of diethyl ether. It was taken in a separatory funnel and washed with <NUM>(N) HCl and brine, dried over anhydrous Na<NUM>SO<NUM>. Removal of the solvent under reduced pressure leaves a white chalky solid which is sufficiently pure for the next reaction. Yield (<NUM>, <NUM>%).

<NUM>,<NUM>'-di-tert-Butylbiphenyl-<NUM>,<NUM>',<NUM>,<NUM>'-tetraol (<NUM>): Colorless chalky solid, m. <NUM> ; <NUM>H NMR (<NUM>, DMSO-d6) δ ppm <NUM> (s, <NUM>), <NUM> (s, <NUM>), <NUM> (d, J = <NUM>, <NUM>), <NUM> (d, J = <NUM>, <NUM>), <NUM> (s, <NUM>); <NUM>C NMR (<NUM>, CDCl<NUM>) δ ppm <NUM> (2C), <NUM> (2C), <NUM> (2C), <NUM> (2C), <NUM> (2C), <NUM> (2C), <NUM> (2C), <NUM> (6C); IR (CH<NUM>Cl<NUM>): v <NUM> (br), <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>-<NUM> Calcd. HRMS for C<NUM>H<NUM>O<NUM> (M+<NUM>), <NUM>; Found, <NUM>.

Synthesis of <NUM>,<NUM>'-di-tert-butyl-<NUM>,<NUM>'-dihydroxybiphenyl-<NUM>,<NUM>'-diyl bis(trifluoromethanesulfonate) (<NUM>): Compound <NUM> (<NUM>, <NUM> mmol) was dissolved in <NUM> of dry dichloromethane. The solution was cooled to -<NUM> and pyridine (<NUM>, <NUM> mmol) was added dropwise to it. A dilute solution of triflic anhydride (<NUM>, <NUM> mmol) in dichloromethane (<NUM>) was added to it over a period of one hour. After addition the reaction mixture was taken to room temperature and stirred for <NUM> minutes. Then the reaction mixture was partitioned between Et<NUM>O, brine and <NUM> (N) HCl. The organic layer was washed with water, brine and dried over anhydrous Na<NUM>SO<NUM>. It was filtered and concentrated under vacuum. Purification by flash chromatography on silica gel provided the light brown gummy liquid, (<NUM>, <NUM>% yield).

<NUM>,<NUM>'-di-tert-butyl-<NUM>,<NUM>'-dihydroxybiphenyl-<NUM>,<NUM>'-diyl bis(trifluoromethanesulfonate) (<NUM>): Gummy liquid; <NUM>H NMR (<NUM>, CDCl<NUM>) δ ppm <NUM> (d, J = <NUM>, <NUM>), <NUM> (d, J = <NUM>, <NUM>), <NUM> (s, br, <NUM>), <NUM> (s, <NUM>); <NUM>C NMR (<NUM>, CDCl<NUM>) δ ppm <NUM> (2C), <NUM> (2C), <NUM> (2C), <NUM> (2C), <NUM> (2C), <NUM> (2C), <NUM>, <NUM>, <NUM>, <NUM>, <NUM> (2SO<NUM>CF<NUM>), <NUM> (2C), <NUM> (6C); IR (CH<NUM>Cl<NUM>): v <NUM> (br), <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>-<NUM>; Calcd. HRMS for C<NUM>H<NUM>F<NUM>O<NUM>S<NUM> (M+Na), <NUM>; Found, <NUM>.

Synthesis of <NUM>,<NUM>'-bis(tert-butoxycarbonyloxy)-<NUM>,<NUM>'-di-tert-butylbiphenyl-<NUM>,<NUM>'-diyl bis(trifluoromethanesulfonate) (<NUM>): To a stirring solution of <NUM> (<NUM>, <NUM> mmol) in CH<NUM>Cl<NUM> (<NUM>) was added di-tert-butyldicarbonate (<NUM>, <NUM> mmol) and <NUM>-dimethylaminopyridine (<NUM>, <NUM> mmol). The resulting solution was stirred overnight at <NUM> and then partitioned between Et<NUM>O, brine and <NUM> (N) HCl. The organic layer was washed twice with aqueous NaHCO<NUM>, once with brine, dried over anhydrous Na<NUM>SO<NUM>, filtered and concentrated under vacuum. Purification by flash chromatography on silica gel provided the colorless solid, which was recrystallized in hexane (<NUM>, <NUM>% yield).

<NUM>,<NUM>'-bis(tert-Butoxycarbonyloxy)-<NUM>,<NUM>'-di-tert-butylbiphenyl-<NUM>,<NUM>'-diyl bis (trifluoromethanesulfonate) (<NUM>): Colourless solid, m. <NUM>-<NUM>; <NUM>H NMR (<NUM>, CD<NUM>Cl<NUM>) δ ppm <NUM> (d, J = <NUM>, <NUM>), <NUM> (d, J = <NUM>, <NUM>), <NUM> (s, <NUM>), <NUM> (s, <NUM>); <NUM>C NMR (<NUM>, CDCl<NUM>) δ ppm <NUM> (2C), <NUM> (2C), <NUM> (2C), <NUM> (2C), <NUM> (2C), <NUM> (2C), <NUM> (2C), <NUM>, <NUM>, <NUM>, <NUM> (2SO<NUM>CF<NUM>), <NUM> (2C), <NUM> (2C), <NUM> (6C), <NUM> (6C); IR (CH<NUM>Cl<NUM>): v <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>-<NUM>; Calcd. HRMS for C<NUM>H<NUM>F<NUM>O<NUM>S<NUM> (M+Na), <NUM>; Found, <NUM>.

Synthesis of tert-butyl <NUM>,<NUM>'-di-tert-butyl-<NUM>,<NUM>'-divinylbiphenyl-<NUM>,<NUM>'-diyl dicarbonate (<NUM>): Compound <NUM> (<NUM>, <NUM> mmol) was dissolved in <NUM> of dry <NUM>,<NUM>-dioxane. Tri-n-butyl(vinyl)tin (<NUM>, <NUM> mmol), Pd(PPh<NUM>)<NUM> (<NUM>,. <NUM> mmol), lithium chloride (<NUM>, <NUM> mmol) and few crystals of <NUM>,<NUM>-di-tert-butyl-<NUM>-methylphenolwas added to it. The reaction mixture was refluxed at <NUM> for four hours. After the reaction is complete (TLC) it was cooled to room temperature. After removal of dioxane, the residues were dissolved in Et<NUM>O and then <NUM>% aqueous KF was added. The resulting solution was stirred at <NUM> for two hours. The solution was separated and followed by extraction with Et<NUM>O (<NUM> x <NUM>). The organic portions were combined and washed once with brine, dried over anhydrous Na<NUM>SO<NUM>. After removal of the solvent under reduced pressure crude material was obtained which was purified by column chromatography on silica gel with ethyl acetate:hexane (<NUM>:<NUM>). Colourless solid was obtained by recrystallization in MeOH (<NUM>, <NUM>% yield).

tert-Butyl <NUM>,<NUM>'-di-tert-butyl-<NUM>,<NUM>'-divinylbiphenyl-<NUM>,<NUM>'-diyl dicarbonate (<NUM>): Colorless solid, m. <NUM>; <NUM>H NMR (<NUM>, CDCl<NUM>) δ ppm <NUM> (s, <NUM>), <NUM> (s, <NUM>), <NUM> (dd, J<NUM> = <NUM>, J<NUM> = <NUM>, <NUM>), <NUM> (d, J = <NUM>, <NUM>), <NUM> (d, J = <NUM>, <NUM>), <NUM> (s, <NUM>), <NUM> (s, <NUM>); <NUM>C NMR (<NUM>, CDCl<NUM>) δ ppm <NUM> (2C), <NUM> (2C), <NUM> (2C), <NUM> (2C), <NUM> (2C), <NUM> (2C), <NUM> (2C), <NUM> (2C), <NUM> (2C), <NUM> (2C), <NUM> (2C), <NUM> (6C), <NUM> (6C); IR (CH<NUM>Cl<NUM>): v <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>-<NUM>; Calcd. HRMS for C<NUM>H<NUM>O<NUM> (M+<NUM>), <NUM>; Found, <NUM>.

Synthesis of poly[styrene-co-(<NUM>,<NUM>'-di-tert-butoxycarbonyloxy-<NUM>,<NUM>'-di-tert-butyl-<NUM>,<NUM>'-divinyl-<NUM>,<NUM>'-biphenyl)] (<NUM>): A mixture of <NUM> (<NUM>, <NUM> mmol) and styrene (<NUM>, <NUM> mmol) was taken in a schenck flask. TEMPO (<NUM>, <NUM> mmol) and benzoylperoxide, BPO (<NUM>, <NUM> mmol) were added to it and argon was bubbled through the mixture for half an hour prior to the heating. The mixture was then heated at <NUM> for four hours. It was cooled down to room temperature and poured slowly into a beaker containing MeOH (<NUM>) to give a white solid precipitation. Further purification was performed by repeating the dissolution-precipitation twice with toluene/MeOH. The final product was dried under reduced pressure to give white solid. (<NUM>, <NUM>% yield).

Poly[styrene-co-(<NUM>,<NUM>'-di-tert-butoxycarbonyloxy-<NUM>,<NUM>'-di-tert-butyl-<NUM>,<NUM>'-divinyl-<NUM>,<NUM>'-biphenyl)] (<NUM>): Threaded, white solid, <NUM>H NMR (<NUM>, CD<NUM>Cl<NUM>) δ ppm <NUM> (m, br, aromatic), <NUM> (m, br, aromatic), <NUM> (m, br, aromatic), <NUM> (m, C=CH, unreacted), <NUM> (m, C=CH, unreacted), <NUM> (m, br, CH-CH<NUM> polymer backbone), <NUM> (s, tert-butyl), <NUM> (s, tert- butoxy); <NUM>C NMR (<NUM>, CD<NUM>Cl<NUM>) δ ppm <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>; IR (CH<NUM>Cl<NUM>) v <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>-<NUM>.

Synthesis of polystyrene-co-(<NUM>,<NUM>'-di-tert-butyl-<NUM>,<NUM>'-divinylbiphenyl-<NUM>,<NUM>'-diol) (<NUM>): To a solution of copolymer <NUM> (<NUM>) in dry CH<NUM>Cl<NUM> (<NUM>) was added TFA (<NUM>). The mixture was stirred over <NUM> hours at <NUM> until IR and <NUM>H NMR showed Boc was removed completely. Upon cooling to <NUM>, the saturated aqueous NaHCO<NUM> was added until the solution was neutral. The organic layer was separated from the biphasic solution and the aqueous layer was extracted with CH<NUM>Cl<NUM> (<NUM> x <NUM>). The combined organic extracts were washed twice with brine, dried over Na<NUM>SO<NUM> The solvent was removed under reduced pressure to give pale-brown solid. Further purification was performed by repeating the dissolution-precipitation twice with toluene/MeOH. The final polymer was dried under vacuum overnight. (<NUM>% yield).

Polystyrene-co-(<NUM>,<NUM>'-di-tert-butyl-<NUM>,<NUM>'-divinylbiphenyl-<NUM>,<NUM>'-diol) (<NUM>): Threaded, white solid, <NUM>H NMR (<NUM>, CD<NUM>Cl<NUM>): δ ppm <NUM> (m, br, aromatic), <NUM> (m, br, aromatic), <NUM> (m, br, aromatic), <NUM> (m, br, CH-CH<NUM> polymer backbone), <NUM> (m, br, tert-butyl); <NUM>C NMR (<NUM>, CD<NUM>Cl<NUM>) δ <NUM>, <NUM>, <NUM>,<NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>; IR (CH<NUM>Cl<NUM>) v <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM><NUM>, <NUM>-<NUM>.

Synthesis of polystyrene-co-<NUM>,<NUM>'-(<NUM>,<NUM>'-di-tert-butyl-<NUM>,<NUM>'-divinylbiphenyl-<NUM>,<NUM>' diyl)bis(oxy)didibenzo [<NUM>,<NUM>,<NUM>]dioxaphosphepine (<NUM>): To a solution of copolymer <NUM> in CH<NUM>Cl<NUM> <NUM> equivalent of Et<NUM>N and <NUM> equivalent of <NUM>,<NUM>'-bisphenoxyphosphorous ch loride was added to the reaction vessel slowly at <NUM>. The reaction mixture was refluxed for <NUM> hours. Upon cooling to <NUM>, the solution was poured into dry MeOH to give white precipitates which was further purified by repeating dissolution-precipitation process three times with CH<NUM>Cl<NUM>/MeOH, toluene/MeOH and THF/MeOH. The final product was dried under vacuum for overnight (<NUM>% yield).

Polystyrene-co-<NUM>,<NUM>'-(<NUM>,<NUM>'-di-tert-butyl-<NUM>,<NUM>'-divinylbiphenyl-<NUM>,<NUM>' diyl)bis(oxy) didibenzo [<NUM>,<NUM>,<NUM>]dioxaphosphepine (<NUM>) or "JanaPhos": Threaded, white solid, <NUM>H NMR (<NUM>, CD<NUM>Cl<NUM>): δ ppm <NUM> (m, br, aromatic), <NUM> (m, br, aromatic), <NUM> (m, br, aromatic), <NUM> (m, br, CH-CH<NUM> polymer backbone), <NUM> (m, br, tert-butyl); <NUM>C NMR: δ (<NUM>, CD<NUM>Cl<NUM>) <NUM>, <NUM>, <NUM>,<NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>; <NUM>P NMR: δ ppm <NUM>; IR v (CH<NUM>Cl<NUM>) <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>-<NUM>.

The phosphorous content in the polymer backbone (<NUM>) was estimated by the <NUM>P NMR using triphenylphosphine as an internal standard. The phosphorous content is <NUM> mmol/g which has been further confirmed by ICP-OES analysis. Thus, ligand incorporation is <NUM> mmol/g of polymer.

For the following examples, the preparation of the polymer supported rhodium catalyst was performed in toluene <NUM> hours prior to the hydroformylation reaction. Polymer was dissolved in dry toluene (maximum solubility <NUM>/l) in an inert atmosphere and Rh(acac)(CO)<NUM> (Rh/P = <NUM>/<NUM>) was added to it and stirred for overnight. The solution turns into yellowish color. The binding of the Rh with the ligand was confirmed by the <NUM>P NMR. The change in NMR is shown in <FIG>.

This example concerns the use of the catalyst compositions made according to Example <NUM> in the catalytic hydroarylations of enones. The typical experimental procedure is straightforward and simple to operate. A mixture of enone (<NUM> mmol) and arylboronic acid (<NUM> eq. ) were placed in a round bottom flask and a toluene solution (<NUM>) containing Rh(acac)(CO)<NUM> and JanaPhos as prepared in Example <NUM> was added to it under an inert atmosphere. Finally, a solution of methanol and water (<NUM>:<NUM>, <NUM>) was added to it via syringe and the resulting reaction mixture was heated at <NUM>. It will be appreciated that reaction improvements have led to phosphorus loadings of <NUM> mmol/g in Example <NUM>; however the experiments reported in this example utilized polymer with lower (<NUM> mmol/g) phosphorus loading.

As can be seen from Table <NUM>, enals, aliphatic enones, chalcones, and cyclic enones all give high yields of hydroarylation products using the catalyst. Importantly, these high yields are obtained when using just <NUM> equivalents of boronic acid partners; prior reactions using polymer-supported rhodium catalysts require <NUM>-<NUM> fold excess of boronic acids. In fact, the recyclable catalyst performs as well as, or better than, typical small-molecule catalysts which typically utilize <NUM>-<NUM> equivalents of boronic acid.

<NUM>-Phenylpropanal (entry <NUM>, table <NUM>): Colorless liquid, <NUM>H NMR (<NUM>, CDCl<NUM>) δ ppm <NUM> (t, J = <NUM>, <NUM>), <NUM>- <NUM> (m, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM> (t, J = <NUM>, <NUM>), <NUM>-<NUM> (m, <NUM>); <NUM>C NMR (<NUM>, CDCl<NUM>) δ ppm <NUM>, <NUM>, <NUM> (2C), <NUM> (2C), <NUM>, <NUM>, <NUM>.

<NUM>-Phenylbutan-<NUM>-one (entry <NUM>, table <NUM>): Colorless liquid, <NUM>H NMR (<NUM>, CDCl<NUM>) δ ppm <NUM> (d, J = <NUM>, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM> (t, J = <NUM>, <NUM>), <NUM> (t, J= <NUM>, <NUM>), <NUM> (s, <NUM>); <NUM>C NMR (<NUM>, CDCl<NUM>) δ ppm <NUM>, <NUM>, <NUM> (2C), <NUM> (2C), <NUM>, <NUM>, <NUM>, <NUM>.

<NUM>-(<NUM>-Methoxyphenyl)-<NUM>,<NUM>-diphenylpropan-<NUM>-one (entry <NUM>, table <NUM>): Colorless solid, m. <NUM>; <NUM>H NMR (<NUM>, CDCl<NUM>) δ ppm <NUM> (d, J = <NUM>, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM>-<NUM>(m, <NUM>), <NUM> (d, J = <NUM>, <NUM>), <NUM> (t, J = <NUM>, <NUM>), <NUM> (s, <NUM>), <NUM> (d, J = <NUM>, <NUM>); <NUM>C NMR (<NUM>, CDCl<NUM>) δ ppm <NUM>, <NUM>, <NUM> (2C), <NUM> (2C), <NUM>, <NUM> (4C), <NUM> (4C), <NUM> (2C), <NUM> (2C), <NUM>, <NUM>, <NUM>.

<NUM>-Phenylcyclopentanone (entry <NUM>, table <NUM>)<NUM>: Colorless liquid, <NUM>H NMR (<NUM>, CDCl<NUM>) δ ppm <NUM> (t, J = <NUM>, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM>- <NUM> (m, <NUM>), <NUM> (dd, J= <NUM>, <NUM>), <NUM>- <NUM> (m, <NUM>),<NUM>- <NUM> (m, <NUM>); <NUM>C NMR (<NUM>, CDCl<NUM>) δ ppm <NUM>, <NUM>, <NUM> (2C), <NUM> (2C), <NUM>, <NUM>, <NUM>, <NUM>.

<NUM>-Phenylcyclohexanone (entry <NUM>, table <NUM>): Colorless liquid, <NUM>H NMR (<NUM>, CDCl<NUM>) δ ppm <NUM> (t, J = <NUM>, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM>- <NUM> (m, <NUM>), <NUM>- <NUM> (m, <NUM>), <NUM>- <NUM> (m, <NUM>), <NUM>- <NUM> (m, <NUM>); <NUM>C NMR (<NUM>, CDCl<NUM>) δ ppm <NUM>, <NUM>, <NUM> (2C), <NUM>, <NUM> (2C), <NUM>, <NUM>, <NUM>, <NUM>, <NUM>.

<NUM>-Phenylcycloheptanone (entry <NUM>, table <NUM>): Colorless liquid, <NUM>H NMR (<NUM>, CDCl<NUM>) δ ppm <NUM>- <NUM> (m, <NUM>), <NUM>- <NUM> (m, <NUM>), <NUM>- <NUM> (m, <NUM>), <NUM>- <NUM> (m, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM>- <NUM> (m, <NUM>), <NUM>- <NUM> (m, <NUM>); <NUM>C NMR (<NUM>, CDCl<NUM>) δ ppm <NUM>, <NUM>, <NUM> (2C), <NUM> (2C), <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>.

Next, the scope of boronic acids that can be utilized was briefly examined. More specifically, the general experimental procedure for the <NUM>,<NUM>-addition of arylboronic acids to enones will be described using <NUM>-cyclohexen-<NUM>-one and phenylboronic acid. A mixture of <NUM>-cyclohexen-<NUM>-one (<NUM>, <NUM> mmol) and phenylboronic acid (<NUM>, <NUM> mmol) was taken in a round bottom flask. A toluene solution (<NUM>) containing Rh(acac)(CO)<NUM> (<NUM>, <NUM> mmol) and JanaPhos (<NUM>, <NUM> mmol, Rh/P = <NUM>/<NUM>) was added to it in an inert atmosphere. A solution of methanol and water (<NUM>:<NUM>, <NUM>) was added to it via syringe. The reaction mixture was heated at <NUM> for <NUM> hours until the starting material was consumed as indicated by TLC. Then <NUM> methanol was added to it mixture and the catalyst was precipitated out as a white solid. It was filtered out by a Schlenk filter and underwent for the consecutive runs. The filtrate was evaporated under reduced pressure to obtain the crude product which was further purified by column chromatography (<NUM>% ethyl acetate in hexane) to obtain the pure product (<NUM>, <NUM>% yield).

Simple aryl and biaryl boronic acids all provided good yields of arylated products using a variety of enals and enones (Table <NUM>). Moreover, dibenzylidene acetone undergoes selective monoarylation, generating only <NUM>% of the double- addition product (Table <NUM>, entry <NUM>). Lastly, vinylboronic acids were suitable reaction partners, allowing access to gamma/delta-unsaturated ketones (Table <NUM>, entries <NUM> and <NUM>).

<NUM>-p-Tolylpentan-<NUM>-one (entry <NUM>, table <NUM>): Colorless liquid, <NUM>H NMR (<NUM>, CDCl<NUM>) δ ppm <NUM>-<NUM> (m, <NUM>), <NUM>. <NUM> (t, J = <NUM>, <NUM>), <NUM>. <NUM> (t, J = <NUM>, <NUM>), <NUM> (q, J= <NUM>, <NUM>), <NUM> (s, <NUM>), <NUM> (t, J = <NUM>, <NUM>); <NUM>C NMR (<NUM>, CDCl<NUM>) δ ppm <NUM>, <NUM>, <NUM>, <NUM> (2C), <NUM> (2C), <NUM>, <NUM>, <NUM>, <NUM>, <NUM>.

<NUM>-(Biphenyl-<NUM>-yl)pentan-<NUM>-one (entry <NUM>, table <NUM>): Colorless solid, m. <NUM>; <NUM>H NMR (<NUM>, CDCl<NUM>) δ ppm <NUM> (d, J = <NUM>, <NUM>), <NUM> (d, J = <NUM>, <NUM>), <NUM> (t, J = <NUM>, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM> (d, J = <NUM>, <NUM>), <NUM> (t, J = <NUM>, <NUM>), <NUM> (t, J = <NUM>, <NUM>), <NUM> (q, J = <NUM>, <NUM>), <NUM> (t, J= <NUM>, <NUM>); <NUM>C NMR (<NUM>, CDCl<NUM>) δ ppm <NUM>, <NUM>, <NUM>, <NUM>,<NUM>, <NUM> (2C), <NUM> (2C), <NUM> (2C), <NUM>, <NUM> (2C), <NUM>, <NUM>, <NUM>, <NUM>; IR (CH<NUM>Cl<NUM>): v <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>-<NUM>. HRMS for C<NUM>H<NUM>ONa (M+Na), <NUM>; Found, <NUM>.

<NUM>-(Biphenyl-<NUM>-yl)butanal (entry <NUM>, table <NUM>): Colorless liquid, <NUM>H NMR (<NUM>, CDCl<NUM>) δ ppm <NUM> (t, J = <NUM>, <NUM>), <NUM>- <NUM> (m, <NUM>), <NUM> (t, J = <NUM>, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM> (d, J = <NUM>, <NUM>); <NUM>C NMR (<NUM>, CDCl<NUM>) δ ppm <NUM>, <NUM>, <NUM>, <NUM>, <NUM> (2C), <NUM> (2C), <NUM> (3C), <NUM> (2C), <NUM>, <NUM>, <NUM>.

(E)-<NUM>,<NUM>-diphenyl-<NUM>-p-tolylpent-<NUM>-en-<NUM>-one (entry <NUM>, table <NUM>): Colorless solid, m. <NUM>; <NUM>H NMR (<NUM>, CDCl<NUM>) δ ppm <NUM>-<NUM> (m, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM>-<NUM>. <NUM> (m, <NUM>), <NUM> (d, J = <NUM>, <NUM>), <NUM> (d, J = <NUM>, <NUM>), <NUM> (d, J = <NUM>, <NUM>), <NUM> (d, J = <NUM>, <NUM>), <NUM> (s, <NUM>); <NUM>C NMR (<NUM>, CDCl<NUM>) δ ppm <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM> (2C), <NUM> (2C), <NUM> (2C), <NUM> (2C), <NUM> (2C), <NUM> (2C), <NUM>, <NUM>, <NUM>, <NUM>, <NUM>; IR (CH<NUM>Cl<NUM>): v <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>-<NUM>. HRMS for C<NUM>H<NUM>ONa (M+Na), <NUM>; Found, <NUM>.

<NUM>-(<NUM>-(Trifluoromethyl)phenyl)cyclohexanone (entry <NUM>, table <NUM>): Colorless liquid, <NUM>H NMR (<NUM>, CDCl<NUM>) δ ppm <NUM> (d, J = <NUM>, <NUM>), <NUM> (d, J = <NUM>, <NUM>), <NUM>- <NUM> (m, <NUM>), <NUM>- <NUM> (m, <NUM>), <NUM>- <NUM> (m, <NUM>), <NUM>- <NUM> (m, <NUM>), <NUM>- <NUM> (m, <NUM>); <NUM>C NMR (<NUM>, CDCl<NUM>) δ ppm <NUM>, <NUM>, <NUM>, <NUM> (4C) <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>.

<NUM>-(<NUM>-Acetylphenyl)cyclohexanone (entry <NUM>, table <NUM>): Colorless liquid, <NUM>H NMR (<NUM>, CDCl<NUM>) δ ppm <NUM> (d, J = <NUM>, <NUM>), <NUM> (d, J = <NUM>, <NUM>), <NUM>- <NUM> (m, <NUM>), <NUM> (s, <NUM>), <NUM>- <NUM> (m, <NUM>), <NUM>- <NUM> (m, <NUM>), <NUM>- <NUM> (m, <NUM>), <NUM>- <NUM> (m, <NUM>); <NUM>C NMR (<NUM>, CDCl<NUM>) δ ppm <NUM>, <NUM>, <NUM>, <NUM>, <NUM> (2C), <NUM> (2C), <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>.

(E)-<NUM>-Phenylhept-<NUM>-en-<NUM>-one (entry <NUM>, table <NUM>): Colorless liquid, <NUM>H NMR (<NUM>, CDCl<NUM>) δ ppm <NUM>- <NUM>(m, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM> (d, J = <NUM>, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM> (t, J = <NUM>, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM> (t, J = <NUM>, <NUM>); <NUM>C NMR (<NUM>, CDCl<NUM>) δ ppm <NUM>, <NUM>, <NUM>, <NUM>, <NUM> (2C), <NUM>, <NUM> (2C), <NUM>, <NUM>, <NUM>, <NUM>.

(E)-<NUM>-Phenylpent-<NUM>-enal (entry <NUM>, table <NUM>): Colorless liquid, <NUM>H NMR (<NUM>, CDCl<NUM>) δ ppm <NUM> (t, J= <NUM>, <NUM>), <NUM>-<NUM>(m, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM> (d, J = <NUM>, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM>- <NUM> (m, <NUM>); <NUM>C NMR (<NUM>, CDCl<NUM>) δ ppm <NUM>, <NUM>, <NUM>, <NUM> (2C), <NUM>, <NUM>, <NUM> (2C), <NUM>, <NUM>.

Lastly, to examine the utility of the catalyst on a somewhat larger scale, the reaction of cyclohexenone with phenylboronic acid was performed on a <NUM> mmol scale and the product <NUM>-phenyl cyclohexanone was isolated in identical yield (<NUM>%) to the small-scale reaction (Table <NUM>, entry <NUM>). Thus, the ligands described herein may have practical application in larger scale reactions.

The polymer-supported phosphite used in the hydroarylation reactions of Example <NUM> is quite soluble in tetrahydrofuran, dichloromethane, and toluene (e.g., <NUM>/ml in toluene), but is insoluble in methanol. Thus, it is recovered quantitatively by simple precipitation with excess methanol and filtration. Also, it is important to note that the MeOH/H<NUM>O cosolvent used in the hydroarylations was not enough to cause precipitation of the catalyst. In fact, the use of water as a cosolvent has a marked positive effect on the reaction yield; in the absence of protic cosolvent, the hydroarylation of cyclohexenone proceeds to only <NUM>% conversion after <NUM> hours.

In this example the reaction of cyclohexenone and phenylboric acid was investigated. The reusability of the catalytic system was also examined up to five consecutive hydroarylation runs (as described in Example <NUM>) and it was observed that filtration under air was associated with the gradual loss of catalytic activity with respect to yield of the product whereas filtration under schlenk system yielded no appreciable loss of catalytic activity for the subsequent runs. The results are shown in Table <NUM>.

In this example, membrane nano/ultra-filtration of designed polymer-bound Rh complex catalyst is demonstrated as an effective in situ catalyst recovery method for homogeneous hydroformylation reaction systems. Quantitative extents of recovery of the rhodium metal and phosphorus-based ligands were investigated in batch membrane filtration experiments with various soluble polymer bound rhodium complexes dissolved in toluene. ICP technique was explored for analyses of Rh and P in organic matrix.

The STARMEM® nano/ultra filtration membrane was distributed by Membrane Extraction Technology, UK and manufactured by W. Grace-Davison (USA). The membrane is made of highly cross-linked polyimide and asymmetric with the active side in contact with the solution to be filtered. This membrane rg has a diameter of <NUM> and an active surface area of <NUM><NUM>. The thickness of the active layer is less than <NUM> with a pore size less than <NUM> angstroms. The molecular weight cut-off (MWCO) of the membrane ranges from <NUM> to <NUM> Daltons, based on <NUM>% retention of the solute. This membrane is compatible with most of the conventional organic solvents, such as alkanes, aldehydes, alcohols, and aromatics. Its durable rating is up to one year with a maximum operating temperature of <NUM>.

The MET cell was purchased from Membrane Extraction Technology (MED) (London, UK) and made of <NUM> stainless steel. The flat paper-like membrane is placed at the bottom of the MET cell and supported by a porous sintered stainless steel disk, which provides mechanical strength to the membrane. Thus the membrane functions as a dead-end filter. The maximum working volume of the MET cell is <NUM> with a hold-up volume of <NUM>. Two inlets (one for feed and the other for pressurizing gas) enable continuous and air-free operation. The cell is equipped with Teflon-coated magnetic stirrer bar fixed on a metal bracket soldered to the top lid. The maximum pressure is <NUM> psi (<NUM> bars; <NUM> MPa). This is a dead-end mode filter with a flat membrane sheet.

<FIG> shows the schematic of the membrane filtration setup. The cell body is wrapped with a heating tape and insulation, and placed on a magnetic stirrer and hot plate (Barnstead Cimarec Stirrer with stirrer setting of <NUM>-<NUM> and stirrer speed range of <NUM>-<NUM> rpm) for mixing and heating. A thermocouple, interfaced with LabView® data acquisition, measures the solution temperature. The solvent or the substrate is pumped into the cell at a constant flowrate ranging from <NUM> to <NUM>/min. Both the feed reservoir and permeate receiver are blanketed with inert nitrogen gas. This setup is capable of either batchwise or continuous filtration under air-free condition. There are a variety of inert gases that can serve as pressurizing gases. Nitrogen was used in the current example. CO<NUM> will also be used in future studies to create CO<NUM>-expanded solvent media with lower viscosity. For performing homogeneous hydroformylation reactions with simultaneous filtration of the catalyst complex, either synthesis gas (CO/H<NUM> = <NUM>:<NUM> molar) or its mixture with CO<NUM> will be employed as the pressurizing gas. Following filtration, the cell pressure is released gradually via a regulating valve to avoid membrane doming caused by sudden pressure change. The permeate may be recycled back to the cell, with provisions for sample withdrawal for analysis purposes.

The homogeneous catalytic systems tested for filtration consist of the catalyst precursor Rh(acac)(CO)<NUM> (Rh-<NUM>) and various phosphorous ligands dissolved in toluene. Triphenylphosphine (TPPine) was used as the benchmark ligand with the lowest molecular weight. Biphephos and BiPhPhM bulky bidentate phosphite ligands were synthesized and supplied by the University of Kansas Department of Chemistry. The lettering protocol (a, b, and c) after the polymer supported ligands is used to designate different batches of polymer following the same synthesis procedure. The PDI for one PBB10 sample ws estimated to be <NUM>, but it is anticipated that the PDI should not vary significantly from batch to batch. Table <NUM> provides the structures of all the phosphorous ligands and their molecular weights. The shaded circles represent the polymer backbone. Table <NUM> shows the catalysts systems investigated.

Catalyst solutions were prepared by dissolving known amounts of Rh(acac)(CO)<NUM> (Rh-<NUM>) and other ligands in toluene and leaving the stirred solutions in a glove box overnight to allow Rh binding. The solutions were blanketed by an inert gas during mixing, binding, and transferring. The starting or feed solutions containing the catalyst complex or ligands are designated as F. The solution passing through the membrane is called the permeate (designated as P) and the solution rejected by the membrane is called the retentate (designated by letter R).

The unmodified rhodium catalyst, Rh(acac)(CO)<NUM>, designated as Rh-<NUM>, with a purity of <NUM>% and the ligand, triphenylphosphine (PPh<NUM>) with purity of <NUM>%, were obtained from Alfa Aesar. Anhydrous toluene in Sure/Seal™ at purity of <NUM>% was purchased from SigmaAldrich, Inc.

Inductively coupled plasma optical emission spectroscopy ("ICP-OES") was employed to quantify the rhodium and phosphorous concentrations in the starting catalyst solution, the retentate and the permeate. The ICP is an emission spectroscopic technique based on the principle that the intensity of the light emitted by excited ions is proportional to the respective elemental concentration in the analytical solution. The excitation energy is supplied by an electrical current produced by electromagnetic induction. The ICP is widely applied for elemental analyses in metallurgy, agriculture, biology, environment, and geological materials. In most cases, aqueous analysis is preferred after acid digesting the heterogeneous sample. In contrast, organic matrix analysis is rarely used due to the paucity of standards for organic matrix and their short shelf time. In this example, toluene was chosen as a solvent to accommodate phosphorous bound rhodium complexes, due to its strong solvation power for the catalyst complex and the hydroformylation reaction mixture.

The ICP instrument used in this work was a Jobin Yvon <NUM><NUM> with radial plasma view and monochromator optical system. The liquid sample solution is introduced by peristaltic pump and then sprayed and converted to aerosols by Meinhard concentric nebulizer. The aerosols are sorted by the cyclonic spray chamber and only droplets smaller than <NUM> reach the torch and plasma. It should be noted that only a small quantity of sample aerosols is allowed so as to keep the plasma from being extinguished. The radio frequency generator supplies energy for sustaining the plasma and produces a high-frequency electromagnetic field in the induction coil with output power of between <NUM> to <NUM> W at a frequency of <NUM>. Inside the high temperature plasma, the aerosols carried by argon gas are preheated to dryness and then excited by the ionized gas to high-energy atoms and ions. After passing the radiation zone, these particles release the energy in the form of photons at certain frequencies or wavelengths. Each element has its own characteristic emission lines. The principles of atomic emission, operating safety, matrix selection, and maintenance are detailed in the manufacturer-supplied manuals "User Manual Jobin-Yvon ICP Spectrometers" and "User Manual ICP V5 Software.

Calibration standards were made by dissolving Rh(acac)(CO)<NUM> and triphenylphosphine ("TPPine") in toluene. Toluene was also used to dilute the samples and calibration solutions to lower the viscosity of the sample solutions and reduce its influence on the results. The calibration graphs showed excellent linearity for both Rh and P spanning several orders of magnitude down to ppb level. For example, dissolved Rh can be detected quantitatively at concentrations as low as tens of ppb. Appendix III provides relevant details for ICP method development, calibration procedure, analysis protocols, and operation.

Prior to filtration, the membrane was conditioned by flushing pure toluene through it under nitrogen pressure of <NUM> MPa for one hour. The permeate from this conditioning run was disposed of because of contamination of the solvent with membrane lubricating preservative oil. Following the preconditioning step, the flushing was continued with fresh toluene that was continuously circulated back to the cell. This step was continued till the flux (mL toluene/min) through the membrane leveled out, signaling membrane equilibration. The equilibration step normally takes about three days. After these pretreatment steps, the membrane was ready for the nanofiltration studies of the solution containing dissolved catalyst complexes. Between each filtration run, the membrane was washed three times and soaked overnight in toluene.

During each filtration run, the permeate fluxes were periodically recorded to ensure constant rate throughout the filtration process thereby eliminating any variations due to physical damage to the membrane (i.e., cracking, clogging, and other defects on the membrane surface). Further, a blank filtration run with pure toluene was carried out before and after each filtration with the solution containing dissolved catalyst complex. Under identical gas pressures, lower fluxes were typically observed for the runs with dissolved compared to pure toluene. This is attributed to the increased viscosity of the catalyst solution containing dissolved polymer supports.

The permeate volume was measured in a <NUM> burette of which the ungraduated bottom part was calibrated as <NUM>. The accuracy of the burette is ± <NUM>. A stopwatch with an accuracy of ± <NUM> was used to record the time for collecting certain volumes of permeate. The transient permeate flux is represented by the average flux in a small period of time, in a form of <MAT>, where J is the membrane flux (L. m-<NUM> · hr-<NUM>), ΔV is the permeate volume (L), Δt is the period of time (hours) and A is active membrane surface area (m<NUM>), equal to <NUM><NUM> specified by the manufacturer. Another parameter characterizing the membrane flux is the membrane permeability, a normalized transient permeate flux to pressure ratio with a unit of L· tri-<NUM> · hr-<NUM>· bar-<NUM> (L · m-<NUM> · hr-<NUM> · (100kPa)-<NUM>).

To begin the batch filtration, the catalyst solution is transferred via air-tight syringe into the MET cell through the feed inlet with concurrent nitrogen purging at low pressure of a few psi. The typical volume of the initial solution is <NUM>. Then the cell is pressurized with nitrogen to the desired pressure (<NUM> MPa). The cell pressure is maintained constant by replenishing the dissolved gas that escapes through the membrane with fresh nitrogen from a source gas cylinder. The magnetic stirring rate is set at <NUM> out of <NUM> - <NUM>, and the <NUM> burette permeate receiver is purged with nitrogen. The filtration is commenced by opening the permeate valve and allowing the cell contents to be filtered through the membrane until half of the initial volume is collected as permeate. The permeate flux is calculated by timing the volumetric flow with the <NUM> burette placed in the effluent. After the desired amount of permeate is collected, the permeate check valve is shut off to stop filtration. The retentate and permeate streams are then sampled for Rh and P elemental analysis by ICP. The foregoing procedural steps were all done at room temperature (about <NUM>). Then the MET cell is transferred into a glove box and the retentate is collected after washing three times and overnight soaking. Before reusing the membrane, a visual check and flux measurement are made to ensure that the membrane is in good condition.

The metal pass-through was calculated as follows: <MAT>.

The three polymer supported ligands (PBB10a, PBB10b and PBB10c) as well as one bidentate ligand (BiPhPhM) were tested. The P-loading was <NUM>, <NUM>, and <NUM> mmol/g for the three batches investigated (PBB 10a, 10b, 10c, respectively), respectively. The catalyst solution contain rhodium and phosphorous at concentrations ranging from <NUM> - <NUM> ppm and <NUM> - <NUM> ppm respectively wit rh a molar P/Rh ratio of <NUM> to <NUM> as provided in the Table <NUM>.

All filtrations and flux measurements were run at room temperature (<NUM>). The permeate flux were measured before and after each filtration with pure toluene as blank run to check repeatability of the membrane flux so as to ensure the membrane in good condition. Table <NUM> provides membranes and nitrogen pressures used for each run.

<FIG> shows the permeate flux attained in various filtration runs performed with different solutions and different membranes. The white bars represent the blank filtration runs with pure toluene only while the hatched and dotted bars represent the first and second filtration runs respectively performed with solutions containing dissolved catalyst complexes. As expected, pure toluene with lower viscosity yields higher permeate fluxes compared to the catalyst solutions, at a constant gas pressure.

For each of the three polymer supported ligands PBB10a, PBB10b and PBB10c, two consecutive runs performed with the same membrane yielded nearly identical permeate fluxes confirming, the stability of the membrane. For the bidentate ligand (BiPhPhM), two repeated runs each were performed on two different membranes. These fluxes were reproducible as well.

<FIG> and <FIG> give the ICP-measured Rh and P concentrations in the permeate stream for each batch run. The metal pass-through was calculated as follows: <MAT>.

For the PBB10a ligand, the Rh concentrations in the permeate are approximately <NUM>µg/g (ppm) and <NUM>µg/g (ppm) in the first and second runs, respectively. The Rh pass-through estimates are approximately <NUM>% and <NUM>%, based on filtration of half of the initial solution volume. The rather high pass-through values are attributed to the larger pores in the higher MWCO membrane. They could also be due to either incomplete membrane equilibration and/or impurities in the polymer that degrade the membrane surface. For the PBB10b and PBP10a (not in accordance with the invention as claimed) ligands, the two first runs at constant membrane flux rates yield significantly low Rh pass-through values, on the order of a few tens of ppb. The second run yielded a somewhat higher rhodium concentrations in the permeate, albeit still at ppb levels. For the bidentate ligand (BiPhPhM) (not in accordance with the invention as claimed), Rh concentrations in the permeate are higher as expected, compared to those for the polymer supported ligands (PBB10b and PBP10a), which is attributed to the almost <NUM> fold smaller size of the non-polymer supported ligand and complex. <FIG> shows the same trends of P concentrations in permeate as Rh. Polymer supported ligands (PBB10b and PBP10a) yield the lowest P concentrations in the permeate and correspondingly lowest pass-through values, in the permeate.

This example deals with continuous membrane filtration coupled with hydroformylation reaction at elevated temperature and pressure to determine whether steady operation characterized by constant flux, stable substrate conversion and selectivity can be demonstrated for extended periods. The soluble polymer ligands that displayed the best retention properties during the batch and continuous filtration runs described in Example <NUM> were employed in the investigations under the conditions of hydroformylation.

For the continuous filtration, all the membrane and sample preparation procedures are the same as the batch runs described above. The main difference is that pure toluene is pumped continuously into the cell by means of an HPLC pump at a predetermined flow rate such that the liquid volume in the cell is maintained constant during filtration. A metering valve in the effluent stream is used to ensure that the feed and permeate flow rates are maintained constant. Permeate samples are withdrawn periodically for analysis. When running at elevated temperatures, the cell is preheated and the temperature of the cell contents is stabilized before filtration is commenced.

A substrate solution of toluene and <NUM>-octene (v/v = <NUM>:<NUM>) was prepared. After installing the membrane in the reactor, it was conditioned and equilibrated with anhydrous toluene under a nitrogen pressure of <NUM> MPa.

A <NUM> solution of Rh(acac)(CO)<NUM> and polymer bound ligand in toluene was injected via syringe into the MET cell under a nitrogen atmosphere. The mixture was stirred while repressurizing the system with syngas and raising the temperature to <NUM>. The feedstock pump was started at a flowrate of <NUM>-<NUM>/min, while simultaneously opening the permeate valve slowly and adjusting the permeate flow rate to the same value as that of the feed. The flowrate in this range ensures that the substrate has adequate residence time (at least <NUM> minutes) in the catalytic reactor. Every hour, a sample was taken from the permeate stream. One small portion of this sample was diluted with dichloromethane, and analyzed by gas chromatography Varian GC <NUM> (CP-Si15CB Chromapack® capillary column). The other portion of this sample was analyzed by ICP JY <NUM><NUM> for Rh and P analyses.

Each run was terminated by shutting down the syngas supply and closing the feed and permeate valves. However, reaction would still continue inside the membrane reactor until it reached equilibrium. This is signified by a drop in syngas pressure, sometimes down to zero when the substrate <NUM>-octene was in excess. Continuous operation is resumed by re-establishing syngas and feedstock flows, and by opening the permeate valve. The conversion versus time profile exhibited a rising profile during the start-up stage and then reached a steady state.

Two repeated filtration runs were performed using toluene-based solutions containing dissolved polymer supported ligand (PBB10c) with two fresh membranes (MWCO of <NUM> Daltons). The catalyst solutions contain Rh and P at concentrations ranging from <NUM>-<NUM> ppm with a molar P/Rh ratio of <NUM>.

The first continuous filtration run shown in <FIG> lasted for <NUM> hours. The permeate flux during the entire run remained constant at <NUM> m-<NUM> hr-<NUM>, which is approximately <NUM>% of the flux attained with pure toluene at identical cell pressures. The Rh and P concentrations in the effluent were high initially and decreased with time suggesting the removal of perhaps unbound Rh and P from the initial mixture and also from the fraction of the polymers that are lighter than the MWCO of the membrane. The Rh and P concentrations lined out at ppb levels (about <NUM> ppb) after several hours. Total losses of Rh and P during the line-out duration are <NUM>% and <NUM>% respectively, obtained by integrating the area under the empirically fitted concentration vs. time curves. This means that about <NUM>% of the Rh and P were retained in the cell. Assuming that the Rh and P leaching is substantially complete during the line-out period and remained at these values, the targeted rhodium recovery rate <NUM>% per pass is easily achieved beyond the line-out period.

<FIG> shows the permeate flux along with the Rh and P concentrations in the permeate versus time for the second continuous filtration run. This filtration run lasted for <NUM> hours in total, and was performed in three stages as follows. The first stage (the first <NUM> hours) represents a repeat of the first continuous run. After two weeks following this run, during which the cell contents were maintained in nitrogen atmosphere at a constant pressure, the filtration was resumed and continued for another <NUM> hours. Similar to the first run, the permeate flux remains constant. The Rhodium and phosphorous concentrations in permeate decreased down to <NUM> ppb and <NUM> ppb respectively after <NUM> hours of filtration. Total losses of Rh and P during the line-out period are <NUM>% and <NUM>% respectively obtained by integrating the area under the empirically fitted concentration versus time curves. The Rh and P losses are similar to those obtained during the line out phase of the first run.

In order to test the temperature effects, the filtration of the previous cell mixture (filtered for <NUM> hours at room temperature) was continued after two weeks, heating the cell to <NUM>. The higher Rh and P concentrations in the permeate following line-out is attributed to the approximately <NUM> times greater membrane flux, due partly to the lower mixture viscosity at higher temperature. However, the Rh concentration is still at tens of ppb levels.

The P concentration curve exhibits a spike at the beginning of each continued run. This is attributed to the flushing of the Rh and P that may have accumulated in the hold-up volume (under the membrane assembly) by slow diffusion across the membrane during the two weeks. When the filtration resumes, the accumulated Rh and P are first washed out before the profiles line out again at previously attained values (tens of ppb levels), as shown in <FIG>.

The continuous experiment for <NUM>-octene hydroformylation catalyzed by PBB 10d modified rhodium complex was carried out at temperature of <NUM> and under syngas pressure of <NUM> MPa. The solution was kept stirred at a setting that is equivalent to <NUM> rpm. The Rh and P concentrations in the initial solution are <NUM> ppm and <NUM> ppm, respectively. The molar P/Rh ratio is <NUM>.

As shown in <FIG>, the conversion slowly increases during the first <NUM> hours of the initial run and then remains at <NUM>% for the following <NUM> hours while the residence time is kept constant at <NUM> hours. The regioselectivity n/i ratio decreases from <NUM> for the first sample down to <NUM> at the end of the <NUM>-hour run. The selectivity towards aldehyde product reaches a steady value in the range of <NUM>-<NUM>%, with relatively less variation.

After sealing the reaction mixture for <NUM> days in the reactor at the same stirrer speed as the previous reaction, the continuous run was resumed at a higher syngas pressure (<NUM> MPa) for another <NUM> hours, with an average residence time of approximately <NUM> hours. The purpose of this run was to investigate the effect of syngas partial pressure on conversion and selectivity. As inferred from <FIG>, the reaction under <NUM> MPa syngas gives higher conversion (greater than <NUM>%) and higher selectivity to aldehydes (greater than <NUM>%), compared to the run under <NUM> MPa syngas. In contrast, the n/i ratio gradually decreases from <NUM> down to <NUM>.

The ICP analysis for the Rh and P concentrations in the permeate in the two consecutive continuous runs at different operating conditions is shown in <FIG>. The first continuous run at <NUM> MPa syngas gives Rh contents in permeate lower than <NUM> ppb during the <NUM>-hour run and P contents decreasing from <NUM> ppm to <NUM> ppb due to the pass-through of smaller size of polymer bound ligand.

The Rh and P levels from the second continuous run at <NUM> MPa syngas pressure are at low ppm levels. The reason for the increased pass-through is not clear at this time but it was observed that following the second continuous run, the retentate color (dark red) was completely different from that of the retentate for the batch runs (yellow). It is speculated that rhodium dimer was formed during the idle time between the two consecutive runs in the syngas starved environment and at the elevated temperature <NUM>. The rhodium dimer formation reported often occurs at low pressures of hydrogen and high rhodium concentrations. The color changes can be associated with the reactions as follows where the ligand is triphenylphosphine (PPh3):
<CHM>
The same type of reactions might also occur when polymer bound ligand is used. The binding between the resulting rhodium dimer and the polymer bound ligand PBB10 might be weak, thus causing high Rh leaching through the membrane due to the smaller size of the dimer than the PBB <NUM> rhodium complex.

While the first <NUM> hours of the continuous experiment yielded steady <NUM>-octene conversion and product selectivities, the actual values of these quantities are much lower than those attained during the batch experiments. It was suspected that this was due to a lack of vigorous mixing in the MET cell as received. That is, inadequate mixing would result in "syngas starvation" in the liquid phase which is known to adversely affect both conversion and product selectivity. To improve the mixing, the MET cell was fitted with a magnetically driven agitator that provided much better agitation of the liquid phase. The results are provided in the following second example.

In a related example, the continuous experiment for <NUM>-octene hydroformylation catalyzed by PBB 10d modified rhodium complex was carried out at temperature of <NUM> and under syngas pressure of <NUM> MPa. The solution was kept stirred with the new agitator at a setting that is equivalent to <NUM> rpm. The Rh and P concentrations in the initial solution are <NUM> ppm and <NUM> ppm, respectively. The molar P/Rh ratio is <NUM>.

As shown in <FIG>, the conversion slowly increases and reached a steady state after <NUM> hours around <NUM>%. The regioselectivity n/i ratio remained constant about <NUM> to <NUM>. The selectivity towards aldehyde product reaches a steady state value in the range of <NUM>% or above, and was typically greater than <NUM>%. The improved conversion and selectivity values prove that adequate mixing in the membrane reactor is important for achieving the desired conversion and selectivities.

The ICP analysis for the Rh and P concentrations is shown in <FIG>. Both concentrations reach a steady value in the permeate after <NUM> hours. The flow rate through the membrane was nearly constant throughout the <NUM> hour run suggesting that the membrane was not fouled. The Rh contents in permeate was lower than <NUM> ppb and were less than <NUM> ppb from <NUM> to <NUM> hours. The P content in the permeate decreasing from <NUM> ppm to <NUM> ppm due to the pass-through of smaller size of polymer bound ligand. The total losses of Rh and P during the <NUM> hour run were <NUM> wt% and <NUM> wt%.

In this example, the hydroformylation of <NUM>-octene was investigated using the catalyst composition of the present invention in which compressed carbon dioxide was utilized to volumetrically expand the liquid phase. In a stainless steel high-pressure reactor with thick-walled glass window and magnetic stirring bar, [Rh(acac)(CO)<NUM> (<NUM>, <NUM> mmol) and polymer (Rh/P = <NUM>/<NUM>) were dissolved in toluene (<NUM>) under inert atmosphere. The solution was stirred overnight at <NUM> and the solution turns to a yellowish color. After the addition of <NUM>-octene (<NUM>, <NUM> mmol) under an inert atmosphere, the reactor was charged with syngas (CO: H<NUM>, <NUM>:<NUM> v/v). The reactor was heated with a thermo-coil wrapped on it. After achieving <NUM> (takes about <NUM> minutes), the reaction mixture was flushed five times with syngas and maintained at a constant syngas pressure at <NUM> bar. After two hours, the reaction mixture was cooled to room temperature and depressurized by the slow release of syngas inside an efficient fume cupboard. Then the reaction mixture was collected and <NUM> times of methanol was added to it. The white catalyst precipitate was separated quantitatively by filtration and reused for the subsequent runs after washing and drying. The product was analyzed by GC and the linear/branched aldehydes ratio was determined from the integral values of <NUM>H NMR spectroscopy.

The same experiment was performed in CO<NUM>-expanded liquid system also. In that case, the reactor was pressurized with CO<NUM> (<NUM> bar) and left for one hour to attain equilibrium at <NUM>. The syngas pressure was <NUM> MPa (<NUM> bar) (total pressure <NUM> MPa (<NUM> bar)). The results are shown in Table <NUM>.

The dissolved polymer bound phosphite ligands discussed herein, used to facilitate better catalyst retention, could significantly increase the viscosities of hydroformylation reaction mixtures, especially at high concentration. When CO<NUM> is added into the organic solvent (toluene in this case), the organic solvent expands and the physical properties of the CO<NUM>-expanded solvent are altered with CO<NUM> pressure. This is generally described in <NPL>); <NPL>), and <CIT>.

Permeate flux is a key parameter for membrane filter throughput prediction, sizing and its capital cost estimation. In case that no significant concentration gradient is present in the porous membrane, the Hagen-Poiseuille equation was used to correlate solvent flux and viscosity for polyimide membranes. <MAT> where J is volume flux for solvent [m<NUM> m-<NUM> s-<NUM>], ΔP is the pressure drop across the membrane [Pa], η is solution viscosity [kg (m s)-<NUM>], ε is membrane porosity, rp is membrane pore radius [m], τ is tortuosity, l is membrane thickness [m]. See <NPL>). Solvent flux J increases with increasing pressure drop across the membrane and with decreasing viscosity. Obviously, viscosity is the only solution parameter that affects the solvent flux besides all other membrane parameters. The membrane pore size might change with the type of organic solvent used due to different swelling of membrane polymer. In addition, concentration polarization and non-ideality of solution are not considered herein.

The dissolution of CO<NUM> in organic solvents reduces the viscosities and increases the diffusivities of the organic solvents. Compared with other inert gases like nitrogen, CO<NUM> could not only serve as a pressurizing gas, but also as a reagent to tune the viscosities of the organic mixtures. Viscosity measurements of organic mixtures with various phosphorous ligands dissolved in toluene at different CO<NUM> pressures and temperatures will provide the evidence for the CO<NUM> tuning ability.

The viscosity measurements were performed in a ViscoPro <NUM> System <NUM> with SPL-<NUM> high pressure viscometer and Viscolab software, supplied by Cambridge Applied Systems (currently Cambridge Viscosity). The whole experimental setup consists of an air bath unit, feed pump, and CO<NUM> supply system. To obtain a uniform temperature environment, the air bath, which houses Jerguson view cell, circulation pump and viscometer, is controlled by a digital controller Yamato constant temperature oven DKN400. The Jerguson viewcell is rated to <NUM> MPa (<NUM> psi) and has a total sample volume of <NUM>. With the equipped Jerguson viewcell, cloud point and expansion data also were able to be collected. The circulation micropump is rated to <NUM> MPa (<NUM> psi), with a pressure head of <NUM> kPa (<NUM> psi) and maximum temperature of <NUM>. The feed pump (Eldex Laboratories Inc. <NUM> BBB -<NUM>) is used to pump the organic solvent into the system. CO<NUM> is pressurized by a syringe pump (ISCO Model 260D), which is insulated with a circulating water bath (Isotemp <NUM> Fisher Scientific) to keep the CO<NUM> at constant temperature. The system pressure is recorded by an in-situ p ressure transducer with a maximum pressure limit of <NUM> MPa (<NUM> psi) and a Heise digital pressure indicator.

The viscometer is a cylindrical cell with a piston inside it. Fluid is trapped in the annulus between piston and cylindrical cell wall. Two magnetic coils inside the sensor body vibrate the piston over a fixed distance, forcing the fluid to flow through the annular space between piston and chamber. The time required for the piston to complete a two-way cycle is directly related to the viscosity of the fluid. The viscometer sensor is capable of measuring viscosities from <NUM> to <NUM>,<NUM> cP with maximum operating pressure of <NUM>,<NUM> psi (<NUM> bar ; <NUM> MPa) and operating temperature ranging from -<NUM> to +<NUM>.

The viscometer is oriented at a <NUM>° angle so that any gas bubble trapped inside can be purged easily. According to manufacturer's specifications, the accuracy of the viscosity measurement is ± <NUM>% of the measured viscosity. The viscometer temperature is measured by a temperature sensor located at the bottom of the viscometer, with an accuracy of ± <NUM>. The raw viscosity data from the instrument reading were adjusted by temperature and pressure with a program provided by manufacture.

Prior to viscosity measurements, the volume expansion of organic mixtures with various phosphorous ligands dissolved in toluene was performed in Jerguson viewcell. CO<NUM> was gradually added to the mixture and after the temperature and pressure stabilized the volume of the mixture was recorded at each desired temperature and pressure until the highest CO<NUM> pressure is arrived at which the mixtures become cloudy. This highest CO<NUM> pressure is called cloud point pressure, which is the maximum CO<NUM> pressure that the organic mixtures can tolerate while remaining homogeneous. The cloud points are different for each specific mixture with different concentrations of phosphorous ligands. During the expansion and cloud point measurements, the viscometer was bypassed to prevent the piston from scratch by any particles formed when the cloud point is approached.

Of the systems that have been tested in this study shown in <FIG>, pure toluene and the mixture of toluene and BiPhPhM (not in accordance with the invention as claimed) ligand are miscible with CO<NUM> and do not display cloud points in the pressure and temperature ranges tested. Polymer supported ligands PBB10b, PBP10a (not in accordance with the invention as claimed) and PBB10c precipitate out at the highest CO<NUM> pressures shown in the figure. The cloud point pressure increases with increasing temperature. The cloud point measurements essentially provide the operating temperature and pressure ranges under which the polymer supported catalysts would remain in solution upon CO<NUM> addition and thereby facilitate homogeneous catalysis.

<FIG> shows the viscosities measured for the mixture of toluene and PBB10c at a concentration of <NUM>% by weight at four temperatures and five CO<NUM> pressures below the cloud point pressure. The viscosities decrease with increasing temperature at the same CO<NUM> pressure and with increasing CO<NUM> pressure at the same temperature. Viscosities decrease <NUM>% and <NUM>% respectively by adding CO<NUM> up to <NUM> MPa (<NUM> bars) at temperature <NUM> and <NUM>. Negligible change in viscosity was observed with temperature at CO<NUM> pressure of <NUM> MPa (<NUM> bars). CO<NUM> addition to the hydroformylation reaction mixture not only improves the linear aldehyde selectivity (demonstrated in <CIT>) but also decreases viscosity, thus providing an ability to tune the membrane flux. Another evidence that <NUM>-<NUM> times higher pure toluene flux was observed for CO<NUM> than nitrogen of the identical pressure <NUM> MPa (<NUM> bars) at the same temperature proved that CO<NUM> addition can facilitate solvent permeation. The relation of viscosity and CO<NUM> pressure at different temperature for the mixture toluene plus PBB10c at a concentration of <NUM>% by weight is plotted in <FIG>. Clearly, the viscosity drops when increasing CO<NUM> pressure at all temperatures. At lower temperature, the viscosity decreases more rapidly than that at higher temperature. This observation is consistent with the fact that at low temperature the mixture has higher volume expansion (higher CO<NUM> solubility) than at high temperature under the same CO<NUM> pressure.

The same trends were observed for the change in viscosities with temperature and CO<NUM> pressure in <FIG> and <FIG>, respectively, for a system containing higher concentrations of polymer bound ligands (<NUM>% by weight).

<FIG> shows the change in viscosity change with CO<NUM> pressure at <NUM> for different polymer concentrations. At the same temperature and CO<NUM> pressure, the viscosity increases with increasing polymer concentration. The degree of reduction in viscosity upon CO<NUM> addition is similar for both low and high polymer concentration mixtures.

Claim 1:
A catalyst composition comprising,
a polymer functionalized with a multidentate ligand for binding a transition metal containing compound to form a transition metal complex,
wherein said functionalized polymer has a number average molecular weight of about <NUM>,<NUM> to <NUM>,<NUM>/mol and a polydispersity index of about <NUM> to <NUM>, and a transition metal complexed to said multidentate ligand, wherein
the catalyst composition comprises polystyrene-co-<NUM>,<NUM>'-(<NUM>,<NUM>'-di-tert-butyl-<NUM>,<NUM>'-divinylbiphenyl-<NUM>,<NUM>' diyl)bis(oxy)didibenzo[<NUM>,<NUM>,<NUM>]dioxaphosphepine,
and
said transition metal is rhodium.