WO1997016401A1 - Melanges reactionnels contenant des diols d'hydrocarbures substitues et procedes de preparation - Google Patents

Melanges reactionnels contenant des diols d'hydrocarbures substitues et procedes de preparation Download PDF

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Publication number
WO1997016401A1
WO1997016401A1 PCT/US1996/017885 US9617885W WO9716401A1 WO 1997016401 A1 WO1997016401 A1 WO 1997016401A1 US 9617885 W US9617885 W US 9617885W WO 9716401 A1 WO9716401 A1 WO 9716401A1
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substituted
reaction mixture
carbon atoms
propanediol
ethyl
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PCT/US1996/017885
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English (en)
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David Marston Lincoln
Charles Guthrie Moyers, Jr.
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Union Carbide Chemicals & Plastics Technology Corporation
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Priority to AU77238/96A priority Critical patent/AU7723896A/en
Publication of WO1997016401A1 publication Critical patent/WO1997016401A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
    • C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • C08G18/3209—Aliphatic aldehyde condensates and hydrogenation products thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C08G63/183—Terephthalic acids
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/582—Recycling of unreacted starting or intermediate materials

Definitions

  • This invention relates to processes for the preparation of reaction mixtures containing substituted hydrocarbon diols, e.g., substituted 1,3-propanediols, as principal products of reaction and to reaction mixtures containing the substituted hydrocarbon diols as principal products of reaction.
  • substituted hydrocarbon diols and derivatives thereof are useful alone or in the production of intermediates, and have utility in coatings, adhesives, inks, fibers, pharmaceutical intermediates, sealants, stereolithography, as well as in other end uses.
  • Hydrocarbon diols in general are well known in industry and many are important articles of commerce. It is well known that one or more hydrocarbon diols such as ethylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol and 1,6-hexanediol are used as ingredients for the preparation of polyesters, as short chain extenders for polyurethanes, as antifreeze agents, as humectants, as emollients, as well as for other end uses.
  • hydrocarbon diols such as ethylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol and 1,6-hexanediol are used as ingredients for the preparation of polyesters, as short chain extenders for polyurethanes, as antifreeze agents, as humectants, as emollients, as well as for other end uses.
  • This invention relates in part to a process for producing a batchwise or continuously generated reaction mixture comprising, based on 100 percent of the weight of the reaction mixture and exclusive of any water present:
  • R'l is a substituted hydrocarbon residue having 5 or more carbon atoms in which the primary hydroxyl groups are separated by 3 or more carbon atoms linearly arranged and in which at least one of said carbon atoms linearly arranged is a disubstituted carbon atom or at least 2 of said carbon atoms linearly arranged are monosubstituted carbon atoms;
  • a substituted hydrocarbon diol to ester-diol weight ratio of greater than about 4 which process comprises subjecting a first reaction mixture comprising a substituted hydroxyaldehyde to hydrogenation in the presence of a hydrogenation catalyst to produce said batchwise or continuously generated reaction mixture.
  • This invention also relates in part to a process for producing a batchwise or continuously generated reaction mixture comprising, based on 100 percent ofthe weight of the reaction mixture and exclusive of any water present:
  • R' ⁇ is a substituted hydrocarbon residue having 5 or more carbon atoms in which the primary hydroxyl groups are separated by 3 or more carbon atoms linearly arranged and in which at least one of said carbon atoms linearly arranged is a disubstituted carbon atom or at least 2 of said carbon atoms linearly arranged are monosubstituted carbon atoms;
  • a substituted hydrocarbon diol to ester-diol weight ratio of greater than about 4 which process comprises: (1) subjecting a first reaction mixture comprising a substituted first aldehyde and a substituted or unsubstituted second aldehyde to aldol condensation in the presence of an aldol condensation catalyst to produce a second reaction mixture comprising a substituted hydroxyaldehyde; and (2) subjecting said second reaction mixture to hydrogenation in the presence of a hydrogenation catalyst to produce said batchwise or continuously generated reaction mixture.
  • This invention further relates in part to a process for producing a batchwise or continuously generated reaction mixture comprising, based on 100 percent of the weight of the reaction mixture and exclusive of any water present:
  • 'l is a substituted hydrocarbon residue having 5 or more carbon atoms in which the primary hydroxyl groups are separated by 3 or more carbon atoms linearly arranged and in which at least one of said carbon atoms linearly arranged is a disubstituted carbon atom or at least 2 of said carbon atoms linearly arranged are monosubstituted carbon atoms;
  • a substituted hydrocarbon diol to ester-diol weight ratio of greater than about 4 which process comprises: (1) reacting an olefinically unsaturated compound with carbon monoxide and hydrogen in the presence of a metal-ligand complex catalyst to produce a first reaction mixture comprising a substituted first aldehyde; (2) subjecting said first reaction mixture and a substituted or unsubstituted second aldehyde to aldol condensation in the presence of an aldol condensation catalyst to produce a second reaction mixture comprising a substituted hydroxyaldehyde; and (3) subjecting said second reaction mixture to hydrogenation in the presence of a hydrogenation catalyst to produce said batchwise or continuously generated reaction mixture.
  • This invention yet further relates in part to a process for producing a batchwise or continuously generated reaction mixture comprising, based on 100 percent of the weight of the reaction mixture and exclusive of any water present:
  • R'2 and R'3 are the same or different and are linear or branched alkyl having from 1 to 4 carbon atoms;
  • This invention also relates in part to a process for producing a batchwise or continuously generated reaction mixture comprising, based on 100 percent of the weight of the reaction mixture and exclusive of any water present:
  • R'2 and R' ⁇ are the same or different and are linear or branched alkyl having from 1 to 4 carbon atoms;
  • This invention further relates in part to a process for producing a batchwise or continuously generated reaction mixture comprising, based on 100 percent of the weight of the reaction mixture and exclusive of any water present:
  • R'2 and R'3 are the same or different and are linear or branched alkyl having from 1 to 4 carbon atoms;
  • This invention yet further relates in part to a process for preparing substituted hydrocarbon diols represented by the formula:
  • R'l is a substituted hydrocarbon residue having 5 or more carbon atoms in which the primary hydroxyl groups are separated by 3 or more carbon atoms linearly arranged and in which at least one of said carbon atoms linearly arranged is a disubstituted carbon atom or at least 2 of said carbon atoms linearly arranged are monosubstituted carbon atoms, which process comprises subjecting a first reaction mixture comprising a substituted hydroxyaldehyde to hydrogenation in the presence of a hydrogenation catalyst to produce a second reaction mixture comprising said substituted hydrocarbon diol.
  • This invention also relates in part to a process for preparing substituted hydrocarbon diols represented by the formula:
  • R'l is a substituted hydrocarbon residue having 5 or more carbon atoms in which the primary hydroxyl groups are separated by 3 or more carbon atoms linearly arranged and in which at least one of said carbon atoms linearly arranged is a disubstituted carbon atom or at least 2 of said carbon atoms linearly arranged are monosubstituted carbon atoms, which process comprises: (1) subjecting a first reaction mixture comprising a substituted first aldehyde and a substituted or unsubstituted second aldehyde to aldol condensation in the presence of an aldol condensation catalyst to produce a second reaction mixture comprising a substituted hydroxyaldehyde; and (2) subjecting said second reaction mixture to hydrogenation in the presence of a hydrogenation catalyst to produce a third reaction mixture comprising said substituted hydrocarbon diol.
  • This invention further relates in part to a process for preparing substituted hydrocarbon diols represented by the formula:
  • R'l is a substituted hydrocarbon residue having 5 or more carbon atoms in which the primary hydroxyl groups are separated by 3 or more carbon atoms linearly arranged and in which at least one of said carbon atoms linearly arranged is a disubstituted carbon atom or at least 2 of said carbon atoms linearly arranged are monosubstituted carbon atoms, which process comprises: (1) reacting an olefinically unsaturated compound with carbon monoxide and hydrogen in the presence of a metal-ligand complex catalyst to produce a first reaction mixture comprising a substituted first aldehyde; (2) subjecting said first reaction mixture and a substituted or unsubstituted second aldehyde to aldol condensation in the presence of an aldol condensation catalyst to produce a second reaction mixture comprising a substituted hydroxyaldehyde; and (3) subjecting said second reaction mixture to hydrogenation in the presence of a hydrogenation catalyst to produce a third reaction mixture comprising said substituted hydrocarbon diol.
  • This invention yet further relates in part to a process for preparing substituted 1,3-propanediols represented by the formula: R' 2 I HOCH 2 — C-CH 2 OH
  • '2 and R'3 are the same or different and are linear or branched alkyl having from 1 to 4 carbon atoms, which process comprises subjecting a first reaction mixture comprising a substituted 3-hydroxypropanal to hydrogenation in the presence of a hydrogenation catalyst to produce a second reaction mixture comprising said substituted 1,3-propanediol.
  • This invention also relates in part to a process for preparing substituted 1,3-propanediols represented by the formula:
  • R'2 and R'3 are the same or different and are linear or branched alkyl having from 1 to 4 carbon atoms, which process comprises: (1) subjecting a first reaction mixture comprising a substituted first aldehyde and a substituted or unsubstituted second aldehyde to aldol condensation in the presence of an aldol condensation catalyst to produce a second reaction mixture comprising a substituted 3-hydroxypropanal; and (2) subjecting said second reaction mixture to hydrogenation in the presence of a hydrogenation catalyst to produce a third reaction mixture comprising said substituted 1,3-propanediol.
  • This invention further relates in part to a process for preparing substituted 1,3-propanediols represented by the formula: R' 2
  • R'2 and R'3 are the same or different and are linear or branched alkyl having from 1 to 4 carbon atoms, which process comprises: (1) reacting an olefinically unsaturated compound with carbon monoxide and hydrogen in the presence of a metal-ligand complex catalyst to produce a first reaction mixture comprising a substituted first aldehyde; (2) subjecting said first reaction mixture and a substituted or unsubstituted second aldehyde to aldol condensation in the presence of an aldol condensation catalyst to produce a second reaction mixture comprising a substituted 3-hydroxypropanal; and (3) subjecting said second reaction mixture to hydrogenation in the presence of a hydrogenation catalyst to produce a third reaction mixture comprising said substituted 1,3-propanediol.
  • This invention relates in part to a batchwise or continuously generated reaction mixture comprising, based on 100 percent of the weight of the reaction mixture and exclusive of any water present:
  • R'l is a substituted hydrocarbon residue having 5 or more carbon atoms in which the primary hydroxyl groups are separated by 3 or more carbon atoms linearly arranged and in which at least one of said carbon atoms linearly arranged is a disubstituted carbon atom or at least 2 of said carbon atoms linearly arranged are monosubstituted carbon atoms;
  • This invention also relates in part to a batchwise or continuously generated reaction mixture comprising, based on 100 percent of the weight of the reaction mixture and exclusive of any water present:
  • R'2 and R'3 are the same or different and are linear or branched alkyl having from 1 to 4 carbon atoms;
  • This invention further relates in part to a reaction mixture comprising a substituted hydrocarbon diol represented by the formula:
  • '* is a substituted hydrocarbon residue having 5 or more carbon atoms in which the primary hydroxyl groups are separated by 3 or more carbon atoms linearly arranged and in which at least one of said carbon atoms linearly arranged is a disubstituted carbon atom or at least 2 of said carbon atoms linearly arranged are monosubstituted carbon atoms, in which said reaction mixture is prepared by a process comprising subjecting a first reaction mixture comprising a substituted hydroxyaldehyde to hydrogenation in the presence of a hydrogenation catalyst to produce said reaction mixture comprising said substituted hydrocarbon diol.
  • This invention yet further relates in part to a reaction mixture comprising a substituted hydrocarbon diol represented by the formula:
  • R'l is a substituted hydrocarbon residue having 5 or more carbon atoms in which the primary hydroxyl groups are separated by 3 or more carbon atoms linearly arranged and in which at least one of said carbon atoms linearly arranged is a disubstituted carbon atom or at least 2 of said carbon atoms linearly arranged are monosubstituted carbon atoms, in which said reaction mixture is prepared by a process comprising: (1) subjecting a first reaction mixture comprising a substituted first aldehyde and a substituted or unsubstituted second aldehyde to aldol condensation in the presence of an aldol condensation catalyst to produce a second reaction mixture comprising a substituted hydroxyaldehyde; and (2) subjecting said second reaction mixture to hydrogenation in the presence of a hydrogenation catalyst to produce said reaction mixture comprising said substituted hydrocarbon diol.
  • This invention yet further relates in part to a reaction mixture comprising a substituted hydrocarbon diol represented by the formula:
  • R'l is a substituted hydrocarbon residue having 5 or more carbon atoms in which the primary hydroxyl groups are separated by 3 or more carbon atoms linearly arranged and in which at least one of said carbon atoms linearly arranged is a disubstituted carbon atom or at least 2 of said carbon atoms linearly arranged are monosubstituted carbon atoms, in which said reaction mixture is prepared by a process comprising: (1) reacting an olefinically unsaturated compound with carbon monoxide and hydrogen in the presence of a metal-ligand complex catalyst to produce a first reaction mixture comprising a substituted first aldehyde; (2) subjecting said first reaction mixture and a substituted or unsubstituted second aldehyde to aldol condensation in the presence of an aldol condensation catalyst to produce a second reaction mixture comprising a substituted hydroxyaldehyde; and (3) subjecting said second reaction mixture to hydrogenation in the presence of a hydrogenation catalyst to produce said reaction mixture comprising said reaction
  • R'2 and R'3 are the same or different and are linear or branched alkyl having from 1 to 4 carbon atoms, in which said reaction mixture is prepared by a process comprising subjecting a first reaction mixture comprising a substituted 3-hydroxypropanal to hydrogenation in the presence of a hydrogenation catalyst to produce said reaction mixture comprising said substituted 1,3-propanediol.
  • This invention further relates in part to a reaction mixture comprising a substituted 1,3-propanediol represented by the formula:
  • R'2 and R'3 are the same or different and are linear or branched alkyl having from 1 to 4 carbon atoms, in which said reaction mixture is prepared by a process comprising: (1) subjecting a first reaction mixture comprising a substituted first aldehyde and a substituted or unsubstituted second aldehyde to aldol condensation in the presence of an aldol condensation catalyst to produce a second reaction mixture comprising a substituted 3-hydroxypropanal; and (2) subjecting said second reaction mixture to hydrogenation in the presence of a hydrogenation catalyst to produce said reaction mixture comprising said substituted 1,3-propanediol.
  • This invention further relates in part to a reaction mixture comprising a substituted 1,3-propanediol represented by the formula:
  • R'2 and R'3 are the same or different and are linear or branched alkyl having from 1 to 4 carbon atoms, in which said reaction mixture is prepared by a process comprising: (1) reacting an olefinically unsaturated compound with carbon monoxide and hydrogen in the presence of a metal-ligand complex catalyst to produce a first reaction mixture comprising a substituted first aldehyde; (2) subjecting said first reaction mixture and a substituted or unsubstituted second aldehyde to aldol condensation in the presence of an aldol condensation catalyst to produce a second reaction mixture comprising a substituted 3-hydroxypropanal; and (3) subjecting said second reaction mixture to hydrogenation in the presence of a hydrogenation catalyst to produce said reaction mixture comprising said substituted 1,3-propanediol.
  • the processes of this invention are distinctive insofar as they achieve the generation of high selectivities of hydrocarbon diols in a manner which can be suitably employed in a commercial process for the manufacture of hydrocarbon diols.
  • the processes of this invention allow for the production of hydrocarbon diols in relatively high yields without generating large amounts of byproducts, e.g., ester-diol.
  • the hydroformylation reaction may be asymmetric or non-asymmetric, the preferred processes being non-asymmetric, and may be conducted in any continuous or semi-continuous fashion and may involve any catalyst liquid and/or gas recycle operation desired.
  • the particular hydroformylation process for producing such aldehydes from an olefinic unsaturated compound, as well as the reaction conditions and ingredients of the hydroformylation process are not critical features of this invention.
  • hydroformylation is contemplated to include, but not limited to, all permissible asymmetric and non-asymmetric hydroformylation processes which involve converting one or more substituted or unsubstituted olefinic compounds or a reaction mixture comprising one or more substituted or unsubstituted olefinic compounds to one or more substituted or unsubstituted aldehydes or a reaction mixture comprising one or more substituted or unsubstituted aldehydes.
  • Illustrative metal-organophosphorus ligand complex catalyzed hydroformylation processes include such processes as described, for example, in U.S. Patent Nos. 4,148,830; 4,593,127; 4,769,498; 4,717,775; 4,774,361; 4,885,401; 5,264,616; 5,288,918; 5,360,938; 5,364,950; and 5,491,266; the disclosures of which are incorporated herein by reference. Accordingly, the hydroformylation processing techniques of this invention may correspond to any known processing techniques. Preferred processes are those involving catalyst liquid recycle hydroformylation processes.
  • such catalyst liquid recycle hydroformylation processes involve the production of aldehydes by reacting an olefinic unsaturated compound with carbon monoxide and hydrogen in the presence of a metal-organophosphorus ligand complex catalyst in a liquid medium that also contains an organic solvent for the catalyst and ligand.
  • a metal-organophosphorus ligand complex catalyst in a liquid medium that also contains an organic solvent for the catalyst and ligand.
  • free organophosphorus ligand is also present in the liquid hydroformylation reaction medium.
  • free organophosphorus ligand is meant organophosphorus ligand that is not complexed with (tied to or bound to) the metal, e.g., metal atom, of the complex catalyst.
  • the recycle procedure generally involves withdrawing a portion of the liquid reaction medium containing the catalyst and aldehyde product from the hydroformylation reactor (i.e., reaction zone), either continuously or intermittently, and recovering the aldehyde product therefrom by use of a composite membrane such as disclosed in U.S. Patent No. 5,430,194 and copending U.S. Patent Application Serial No.
  • Condensation of the volatilized materials, and separation and further recovery thereof, for example, by further distillation, can be carried out in any conventional manner, the crude aldehyde product can be passed on for further purification and isomer separation, if desired, and any recovered reactants, e.g., olefinic starting material and syn gas, can be recycled in any desired manner to the hydroformylation zone (reactor).
  • any recovered reactants e.g., olefinic starting material and syn gas
  • the recovered metal catalyst containing raf ⁇ inate of such membrane separation or recovered non-volatilized metal catalyst containing residue of such vaporization separation can be recycled, to the hydroformylation zone (reactor) in any conventional manner desired.
  • the hydroformylation reaction mixtures employable herein includes any organic solution derived from any corresponding hydroformylation process that contains at least some amount of four different main ingredients or components, i.e., the aldehyde product, a metal-organophosphorus ligand complex catalyst, free organophosphorus ligand and an organic solubilizing agent for said catalyst and said free ligand, said ingredients corresponding to those employed and/or produced by the hydroformylation process from whence the hydroformylation reaction mixture starting material may be derived.
  • the hydroformylation reaction mixture compositions employable herein can and normally will contain minor amounts of additional ingredients such as those which have either been deliberately employed in the hydroformylation process or formed in situ during said process.
  • Illustrative metal-organophosphorus ligand complex catalysts employable in such hydroformylation reactions encompassed by this invention are known in the art and include those disclosed in the above mentioned patents. In general such catalysts may be preformed or formed in situ as described in such references and consist essentially of metal in complex combination with an organophosphorus ligand. It is believed that carbon monoxide is also present and complexed with the metal in the active species. The active species may also contain hydrogen directly bonded to the metal.
  • the catalyst useful in the hydroformylation reaction includes a metal-organophosphorus ligand complex catalyst which can be optically active or non-optically active.
  • the permissible metals which make up the metal-organophosphorus ligand complexes include Group 8, 9 and 10 metals selected from rhodium (Rh), cobalt (Co), iridium (Ir), ruthenium (Ru), iron (Fe), nickel (Ni), palladium (Pd), platinum (Pt), osmium (Os) and mixtures thereof, with the preferred metals being rhodium, cobalt, iridium and ruthenium, more preferably rhodium, cobalt and ruthenium, especially rhodium.
  • permissible metals include Group 11 metals selected from copper (Cu), silver (Ag), gold (Au) and mixtures thereof, and also Group 6 metals selected from chromium (Cr), molybdenum (Mo), tungsten (W) and mixtures thereof. Mixtures of metals from Groups 6, 8, 9, 10 and 11 may also be used in this invention.
  • the permissible organophosphorus ligands which make up the metal-organophosphorus ligand complexes include organophosphines, e.g., triorganophosphines, and organophosphites, e.g., mono-, di-, tri- and polyorganophosphites.
  • organophosphorus ligands include, for example, organophosphonites, organophosphinites, organophosphorus amides and the like. Mixtures of such ligands may be employed if desired in the metal-ligand complex catalyst and/or free ligand and such mixtures may be the same or different.
  • This invention is not intended to be limited in any manner by the permissible organophosphorus ligands or mixtures thereof. It is to be noted that the successful practice of this invention does not depend and is not predicated on the exact structure of the metal-ligand complex species, which may be present in their mononuclear, dinuclear and or higher nuclearity forms. Indeed, the exact structure is not known. Although it is not intended herein to be bound to any theory or mechanistic discourse, it appears that the catalytic species may in its simplest form consist essentially of the metal in complex combination with the ligand and carbon monoxide when used.
  • complex means a coordination compound formed by the union of one or more electronically rich molecules or atoms capable of independent existence with one or more electronically poor molecules or atoms, each of which is also capable of independent existence.
  • the organophosphorus hgands employable herein may possess one or more phosphorus donor atoms, each having one available or unshared pair of electrons which are each capable of forming a coordinate covalent bond independently or possibly in concert (e.g., via chelation) with the metal.
  • Carbon monoxide (which is also properly classified as a ligand) can also be present and complexed with the metal.
  • the ultimate composition ofthe complex catalyst may also contain an additional ligand, for example, hydrogen or an anion satisfying the coordination sites or nuclear charge ofthe metal.
  • the complex species are preferably free of any additional organic ligand or anion that might poison the catalyst and have an undue adverse effect on catalyst performance. It is preferred in the metal-organophosphorus ligand complex catalyzed hydroformylation reactions that the active catalysts be free of halogen and sulfur directly bonded to the metal, although such may not be absolutely necessary.
  • Preferred metal-ligand complex catalysts include rhodium-organophosphine ligand complex catalysts and rhodium-organophosphite ligand complex catalysts.
  • the catalytic species may comprise a complex catalyst mixture, in their monomeric, dimeric or higher nuclearity forms, which are preferably characterized by at least one organophosphorus-containing molecule complexed per one molecule of metal, e.g., rhodium.
  • the catalytic species of the preferred catalyst employed in the hydroformylation reaction may be complexed with carbon monoxide and hydrogen in addition to the organophosphorus ligands in view of the carbon monoxide and hydrogen gas employed by the hydroformylation reaction.
  • organophosphines and organophosphites that may serve as the ligand of the metal-organophosphorus ligand complex catalyst and/or free ligand of the hydroformylation reaction may be of the achiral (optically inactive) or chiral (optically active) type and are well known in the art. Achiral organophosphorus ligands are preferred.
  • organophosphines that may serve as the ligand of the metal-organophosphine complex catalyst and/or free organophosphine ligand of the hydroformylation reaction mixture starting materials are triorganophosphines, trialkylphosphines, alkyldiarylphosphines, dialkylarylphosphines, dicycloalkylarylphosphines, cycloalkyldiarylphosphines, triaralkylphosphines, tricycloalkylphosphines, and triarylphosphines, alkyl and/or aryl biphosphines and bisphosphine mono oxides, as well as ionic triorganophosphines containing at least one ionic moiety selected from the salts of sulfonic acid, of carboxylic acid, of phosphonic acid and of quaternary ammonium compounds, and the like.
  • any of the hydrocarbon radicals of such tertiary non-ionic and ionic organophosphines may be substituted if desired, with any suitable substituent that does not unduly adversely affect the desired result of the hydroformylation reaction.
  • the organophosphine ligands employable in the hydroformylation reaction and/or methods for their preparation are known in the art.
  • Illustrative triorganophosphine ligands may be represented by the formula:
  • each R ⁇ is the same or different and is a substituted or unsubstituted monovalent hydrocarbon radical, e.g., an alkyl or aryl radical
  • Suitable hydrocarbon radicals may contain from 1 to 24 carbon atoms or greater, the most preferred hydrocarbon radical being phenyl, ⁇ CQH.5 — ).
  • Illustrative substituent groups that may be present on the aryl radicals include, e.g., alkyl radicals, alkoxy radicals, silyl radicals such as — Si(R2)3; amino radicals such as — N(R2)2; acyl radicals such as — C(O)R2; carboxy radicals such as — C(O)OR2; acyloxy radicals such as — OC(O)R2; amido radicals such as — C(O)N(R2)2 and — N(R2)C(O)R 2 ; ionic radicals such as — SO3M wherein M represents inorganic or organic cation; sulfonyl radicals such as — SO2R ; ether radicals such as — OR ; sulfinyl radicals such as — SOR2; sulfenyl radicals such as — SR as well as halogen, nitro, cyano, trifluoromethyl and
  • Illustrative alkyl radicals include, e.g., methyl, ethyl, propyl, butyl and the like.
  • Illustrative aryl radicals include, e.g., phenyl, naphthyl, diphenyl, fluorophenyl, difluorophenyl, benzoyloxyphenyl, carboethoxyphenyl, acetylphenyl, ethoxyphenyl, phenoxyphenyl, hydroxyphenyl; carboxyphenyl, trifluoromethylphenyl, methoxyethylphenyl, acetamidophenyl, dimethyl carbamylphenyl, tolyl, xylyl, and the like.
  • Illustrative specific organophosphines include, e.g., triphenylphosphine, tris-p-tolyl phosphine, tris-p- methoxyphenylphosphine, tris-p-fluorophenylphosphine, tris-p- chlorophenylphosphine, tris-dimethylaminophenylphosphine, propyldiphenylphosphine, t-butyldiphenylphosphine, n- butyldiphenylphosphine, n-hexyldiphenyl phosphine, cyclohexyldiphenylphosphine, dicyclohexylphenylphosphine, tricyclohexylphenylphosphine, tribenzylphosphine as well as the alkali and alkaline earth metal salts of sulfonated triphenylphosphines, e
  • illustrative metal-organophosphine complex catalysts and illustrative free organophosphine ligands include, e.g., those disclosed in U.S. Patent Nos. 3,527,809; 4,148,830; 4,247,486; 4,283,562; 4,400,548; 4,482,749 and 4,861,918, the disclosures of which are incorporated herein by reference.
  • organophosphites that may serve as the ligand of the metal-organophosphite complex catalyst and/or free organophosphite ligand of the hydroformylation reaction mixture starting materials are monoorganophosphites, diorganophosphites, triorganophosphites and organopolyphosphites.
  • the organophosphite ligands employable in this invention and/or methods for their preparation are known in the art.
  • Representative monoorganophosphites may include those having the formula:
  • R3 represents a substituted or unsubstituted trivalent hydrocarbon radical containing from 4 to 40 carbon atoms or greater, such as trivalent acyclic and trivalent cyclic radicals, e.g., trivalent alkylene radicals such as those derived from 1,2,2-trimethylolpropane and the like, or trivalent cycloalkylene radicals such as those derived from 1,3,5-trihydroxycyclohexane, and the like.
  • trivalent acyclic and trivalent cyclic radicals e.g., trivalent alkylene radicals such as those derived from 1,2,2-trimethylolpropane and the like, or trivalent cycloalkylene radicals such as those derived from 1,3,5-trihydroxycyclohexane, and the like.
  • Such monoorganophosphites may be found described in greater detail, for example, in U.S. Patent No. 4,567,306, the disclosure of which is incorporated herein by reference.
  • Representative diorganophosphites may include those having the formula:
  • R ⁇ represents a substituted or unsubstituted divalent hydrocarbon radical containing from 4 to 40 carbon atoms or greater and W represents a substituted or unsubstituted monovalent hydrocarbon radical containing from 1 to 18 carbon atoms or greater.
  • Representative substituted and unsubstituted monovalent hydrocarbon radicals represented by W in the above formula (V) include alkyl and aryl radicals, while representative substituted and unsubstituted divalent hydrocarbon radicals represented by R ⁇ include divalent acyclic radicals and divalent aromatic radicals.
  • Illustrative divalent acyclic radicals include, for example, alkylene, alkylene-oxy-alkylene, alkylene-NX-alkylene wherein X is hydrogen or a substituted or unsubstituted monovalent hydrocarbon radical, alkylene-S-alkylene, and cycloalkylene radicals, and the like.
  • divalent acyclic radicals are the divalent alkylene radicals such as disclosed more fully, for example, in U.S. Patent Nos. 3,415,906 and 4,567,302 and the like, the disclosures of which are incorporated herein by reference.
  • Illustrative divalent aromatic radicals include, for example, arylene, bisarylene, arylene- alkylene, arylene-alkylene-arylene, arylene-oxy-arylene, arylene-NX- arylene wherein X is as defined above, arylene-S-arylene, and arylene- S-alkylene, and the like.
  • More preferably ⁇ is a divalent aromatic radical such as disclosed more fully, for example, in U.S. Patent Nos. 4,599,206 and 4,717,775, and the like, the disclosures of which are incorporated herein by reference.
  • each Ar is the same or different and represents a substituted or unsubstituted aryl radical, each y. is the same or different and is a value of 0 or 1
  • Q represents a divalent bridging group selected from -C(R 5 )2-, -O-, -S-, -NR 6 ', Si(R 7 )2- and - CO-, wherein each R ⁇ is the same or different and represents hydrogen, alkyl radicals having from 1 to 12 carbon atoms, phenyl, tolyl, and anisyl, R > represents hydrogen or a methyl radical, each R? is the same or different and represents hydrogen or a methyl radical, and m is a value of 0 or 1.
  • Such diorganophosphites are described in greater detail, for example, in U.S. Patent Nos. 4,599,206, 4,717,775 and 4,835,299, the disclosures of which are incorporated herein by reference.
  • Representative triorganophosphites may include those having the formula:
  • each R ⁇ is the same or different and is a substituted or unsubstituted monovalent hydrocarbon radical e.g., an alkyl, cycloalkyl, aryl, alkaryl and aralkyl radicals which may contain from 1 to 24 carbon atoms.
  • Suitable hydrocarbon radicals may contain from 1 to 24 carbon atoms or greater and may include those described above for Rl in formula (III).
  • Illustrative triorganophosphites include, for example, trialkyl phosphites, dialkylaryl phosphites, alkyldiaryl phosphites, triaryl phosphites, and the like, such as, for example, trimethyl phosphite, triethyl phosphite, butyldiethyl phosphite, tri-n- propyl phosphite, tri-n-butyl phosphite, tri-2-ethylhexyl phosphite, tri- n-octyl phosphite, tri-n-dodecyl phosphite, dimethylphenyl phosphite, diethylphenyl phosphite, methyldiphenyl phosphite, ethyldiphenyl phosphite, triphenyl phosphite, trinaphth
  • triorganophosphite triphenylphosphite.
  • triorganophosphites are described in greater detail, for example, in U.S. Patent Nos. 3,527,809 and 5,277,532, the disclosures of which are incorporated herein by reference.
  • organopolyphosphites contain two or more tertiary (trivalent) phosphorus atoms and may include those having the formula:
  • X represents a substituted or unsubstituted n-valent hydrocarbon bridging radical containing from 2 to 40 carbon atoms
  • each 9 is the same or different and is a divalent hydrocarbon radical containing from 4 to 40 carbon atoms
  • each R--* is the same or different and is a substituted or unsubstituted monovalent hydrocarbon radical containing from 1 to 24 carbon atoms
  • a and b can be the same or different and each have a value of 0 to 6, with the proviso that the sum of a + b is 2 to 6 and n equals a + b.
  • each R ⁇ radical may be the same or different
  • each II-® radical may also be the same or different.
  • n-valent (preferably divalent) hydrocarbon bridging radicals represented by X include both acyclic radicals and aromatic radicals, such as alkylene, alkylene-Q m - alkylene, cycloalkylene, arylene, bisarylene, arylene-alkylene, and arylene-(CH2)y-Qm-(CH2)y-arylene radicals, and the like, wherein Q, m and y are as defined above for formula (VIII).
  • the more preferred acyclic radicals represented by ⁇ l and R ⁇ above are divalent alkylene radicals
  • the more preferred aromatic radicals represented by ⁇ l and R9 above are divalent arylene and bisarylene radicals, such as disclosed more fully, for example, in U.S. Patent Nos. 4,769,498; 4,774,361: 4,885,401; 5,179,055; 5,113,022; 5,202,297; 5,235,113; 5,264,616 and 5,364,950, and European Patent Application Publication No. 662,468, and the like, the disclosures of which are incorporated herein by reference.
  • Representative monovalent hydrocarbon radicals represented by each R-® radical above include alkyl and aromatic radicals.
  • Illustrative preferred organopolyphosphites may include bisphosphites such as those of formulas (IX) to (XI) below:
  • each R ⁇ , R ⁇ O and X ⁇ of formulas (IX) to (XI) are the same as defined above for formula (VIII).
  • each R ⁇ and ⁇ l represents a divalent hydrocarbon radical selected from alkylene, arylene, arylene-alkylene-arylene, and bisarylene
  • each R*0 represents a monovalent hydrocarbon radical selected from alkyl and aryl radicals.
  • Organophosphite ligands of such Formulas (VIII) to (XI) may be found disclosed, for example, in U.S. Patent Nos.
  • organ obisphosphites are those of the following formulas (XII) to (XTV):
  • ⁇ l represents a divalent aryl-(CH2)y-(Q)m-(CH2)y-aryl radical wherein each y individually has a value of 0 or 1; m has a value of 0 or 1 and Q is -O-, -S- or-C(R ⁇ )2- wherein each R5 is the same or different and represents a hydrogen or methyl radical.
  • each alkyl radical of the above defined lO groups may contain from 1 to 24 carbon atoms and each aryl radical of the above-defined Ar, X-, R9 and R*0 groups ofthe above formulas (VIII) to (XTV) may contain from 6 to 18 carbon atoms and said radicals may be the same or different, while the preferred alkylene radicals of X may contain from 2 to 18 carbon atoms and the preferred alkylene radicals of R ⁇ may contain from 5 to 18 carbon atoms.
  • the divalent Ar radicals and divalent aryl radicals of ⁇ l ofthe above formulas are phenylene radicals in which the bridging group represented by - (CH2)y—(Q)m-(CH2)y— is bonded to said phenylene radicals in positions that are ortho to the oxygen atoms of the formulas that connect the phenylene radicals to their phosphorus atom ofthe formulae. It is also preferred that any substituent radical when present on such phenylene radicals be bonded in the para and/or ortho position of the phenylene radicals in relation to the oxygen atom that bonds the given substituted phenylene radical to its phosphorus atom.
  • any given organophosphite in the above formulas (IV) to (XTV) may be an ionic phosphite, i.e., may contain one or more ionic moieties selected from the group consisting of:
  • each RU is the same or different and represents a hydrocarbon radical containing from 1 to 30 carbon atoms, e.g., alkyl, aryl, alkaryl, aralkyl, and cycloalkyl radicals, and ⁇ represents inorganic or organic anion,
  • organophosphite ligands may contain from 1 to 3 such ionic moieties, while it is preferred that only one such ionic moiety be substituted on any given aryl moiety in the organophosphite ligand when the ligand contains more than one such ionic moiety.
  • M and ⁇ 2 for the anionic moieties ofthe ionic organophosphites there can be mentioned hydrogen (i.e. a proton), the cations ofthe alkali and alkaline earth metals, e.g., lithium, sodium, potassium, cesium, rubidium, calcium, barium, magnesium and strontium, the ammonium cation and quaternary ammonium cations, phosphonium cations, arsonium cations and iminium cations.
  • Suitable anionic atoms of radicals include, for example, sulfate, carbonate, phosphate, chloride, acetate, oxalate and the like.
  • any of the R 3 , R 4 , R 8 , R 9 , R 10 , X 1 , X 2 , W, Q and Ar radicals of such non-ionic and ionic organophosphites of formulas (IV) to (XTV) above may be substituted if desired, with any suitable substituent containing from 1 to 30 carbon atoms that does not unduly adversely affect the desired result ofthe hydroformylation reaction.
  • Substituents that may be on said radicals in addition of course to corresponding hydrocarbon radicals such as alkyl, aryl, aralkyl, alkaryl and cyclohexyl substituents may include for example silyl radicals such as -Si(Rl2)g; amino radicals such as -N(Rl )2; phosphine radicals such as -aryl-P(Rl )2; acyl radicals such as - C(O)Rl2; acyloxy radicals such as -OC(O)Rl2; amido radicals such as - CON(Rl2) 2 and -N(R1 2 )C0R12; sulfonyl radicals such as -SO 2 R 12 ; alkoxy radicals such as -ORl ; sulfinyl radicals such as -SOR1 ; sulfenyl radicals such as -SRl2; phosphonyl radicals such as -
  • substituents include primary, secondary and tertiary alkyl radicals such as methyl, ethyl, n-propyl, isopropyl, butyl, sec-butyl, t-butyl, neo-pentyl, n-hexyl, amyl, sec-amyl, t-amyl, iso-octyl, decyl, octadecyl, and the like; aryl radicals such as phenyl, naphthyl and the like; aralkyl radicals such as benzyl, phenylethyl, triphenylmethyl, and the like; alkaryl radicals such as tolyl, xylyl, and the like; alicyclic radicals such as cyclopentyl, cyclohexyl, 1-methyl cyclohexyl, cyclooctyl, cyclohexylethyl
  • organophosphite ligands include the following:
  • Ligand B 6,6'-[[4,4 , -bis(l,l-dimethylethyl)-[l,l , -binaphthyl]-2,2'-diyl]bis(oxy)]bis- dibenzo[d,f][l,3,2]-dioxaphosphepin having the formula:
  • Ligand F (2R,4R)-di[2,2'-(3,3 , ,5,5'-tetrakis-tert-amyl-l,l'-biphenyl)]-2,4- pentyldiphosphite having the formula:
  • Ligand R 3-methoxy- 1 ,3-cy clohexamethylene tetrakis [3 ,6-bis( 1 , 1-dimethylethyl )- 2-naphthalenyl] ester of phosphorous acid having the formula:
  • the metal-organophosphorus ligand complex catalysts employable in this invention may be formed by methods known in the art.
  • the metal-organophosphorus ligand complex catalysts may be in homogeneous or heterogeneous form.
  • preformed metal hydrido-carbonyl- organophosphorus ligand catalysts may be prepared and introduced into the reaction mixture of a hydroformylation process.
  • the metal-organophosphorus ligand complex catalysts can be derived from a metal catalyst precursor which may be introduced into the reaction medium for in situ formation of the active catalyst.
  • rhodium catalyst precursors such as rhodium dicarbonyl acetylacetonate, Rh 2 O 3 , Rh 4 (CO) 12> Rh (CO) 16 , Rh(NO 3 ) 3 and the like may be introduced into the reaction mixture along with the organophosphorus ligand for the in situ formation of the active catalyst.
  • rhodium dicarbonyl acetylacetonate is employed as a rhodium precursor and reacted in the presence of a solvent with the organophosphorus ligand to form a catalytic rhodium-organophosphorus ligand complex precursor which is introduced into the reactor along with excess free organophosphorus ligand for the in situ formation of the active catalyst.
  • a solvent with the organophosphorus ligand to form a catalytic rhodium-organophosphorus ligand complex precursor which is introduced into the reactor along with excess free organophosphorus ligand for the in situ formation of the active catalyst.
  • carbon monoxide, hydrogen and organophosphorus compound are all ligands that are capable of being complexed with the metal and that an active metal-organophosphorus ligand catalyst is present in the reaction mixture under the conditions used in the hydroformylation reaction.
  • a catalyst precursor composition can be formed consisting essentially of a solubilized metal-organophosphorus ligand complex precursor catalyst, an organic solvent and free organophosphorus ligand.
  • precursor compositions may be prepared by forming a solution of a metal starting material, such as a metal oxide, hydride, carbonyl or salt, e.g. a nitrate, which may or may not be in complex combination with a organophosphorus ligand as defined herein.
  • a metal starting material such as a metal oxide, hydride, carbonyl or salt, e.g. a nitrate, which may or may not be in complex combination with a organophosphorus ligand as defined herein.
  • Any suitable metal starting material may be employed, e.g. rhodium dicarbonyl acetylacetonate, Rh2 ⁇ 3 ,
  • the preferred catalyst precursor composition of this invention consists essentially of a solubilized rhodium carbonyl organophosphorus ligand complex precursor catalyst, an organic solvent and free organophosphorus ligand prepared by forming a solution of rhodium dicarbonyl acetylacetonate, an organic solvent and a organophosphorus ligand as defined herein.
  • the organophosphorus ligand readily replaces one of the dicarbonyl ligands of the rhodium acetylacetonate complex precursor at room temperature as witnessed by the evolution of carbon monoxide gas. This substitution reaction may be facilitated by heating the solution if desired. Any suitable organic solvent in which both the rhodium dicarbonyl acetylacetonate complex precursor and rhodium organophosphorus ligand complex precursor are soluble can be employed. The amounts of rhodium complex catalyst precursor, organic solvent and organophosphorus ligand, as well as their preferred embodiments present in such catalyst precursor compositions may obviously correspond to those amounts employable in the hydroformylation process of this invention.
  • acetylacetonate ligand of the precursor catalyst is replaced after the hydroformylation process has begun with a different ligand, e.g., hydrogen, carbon monoxide or organophosphorus ligand, to form the active complex catalyst as explained above.
  • a different ligand e.g., hydrogen, carbon monoxide or organophosphorus ligand
  • the acetylacetone which is freed from the precursor catalyst under hydroformylation conditions is removed from the reaction medium with the product aldehyde and thus is in no way detrimental to the hydroformylation process.
  • the use of such preferred rhodium complex catalytic precursor compositions provides a simple economical and efficient method for handling the rhodium precursor metal and hydroformylation start-up.
  • the metal-organophosphorus ligand complex catalysts used in the process of this invention consists essentially of the metal complexed with carbon monoxide and a organophosphorus ligand, said ligand being bonded (complexed) to the metal in a chelated and/or non-chelated fashion.
  • the terminology "consists essentially of, as used herein, does not exclude, but rather includes, hydrogen complexed with the metal, in addition to carbon monoxide and the organophosphorus ligand. Further, such terminology does not exclude the possibility of other organic ligands and/or anions that might also be complexed with the metal.
  • the catalyst most desirably is free of contaminants such as metal-bound halogen (e.g., chlorine, and the like) although such may not be absolutely necessary.
  • metal-bound halogen e.g., chlorine, and the like
  • the hydrogen and/or carbonyl ligands of an active metal-organophosphorus ligand complex catalyst may be present as a result of being ligands bound to a precursor catalyst and/or as a result of in situ formation, e.g., due to the hydrogen and carbon monoxide gases employed in hydroformylation process of this invention.
  • hydroformylation reactions involve the use of a metal-organophosphorus ligand complex catalyst as described herein. Of course mixtures of such catalysts can also be employed if desired.
  • the amount of metal-organophosphorus ligand complex catalyst present in the reaction medium of a given hydroformylation reaction need only be that minimum amount necessary to provide the given metal concentration desired to be employed and which will furnish the basis for at least the catalytic amount of metal necessary to catalyze the particular hydroformylation reaction involved such as disclosed, for example, in the above-mentioned patents.
  • metal e.g., rhodium
  • concentrations in the range of from about 10 ppm to about 1000 ppm, calculated as free rhodium, in the hydroformylation reaction medium should be sufficient for most processes, while it is generally preferred to employ from about 10 to 500 ppm of metal, e.g., rhodium, and more preferably from 25 to 350 ppm to metal, e.g., rhodium.
  • free organophosphorus ligand i.e., ligand that is not complexed with the metal
  • the free organophosphorus ligand may correspond to any of the above-defined organophosphorus hgands discussed above as employable herein. It is preferred that the free organophosphorus ligand be the same as the organophosphorus ligand of the metal-organophosphorus ligand complex catalyst employed. However, such ligands need not be the same in any given process.
  • the hydroformylation process of this invention may involve from about 0.1 moles or less to about 100 moles or higher, of free organophosphorus ligand per mole of metal in the hydroformylation reaction medium.
  • the hydroformylation process of this invention is carried out in the presence of from about 1 to about 50 moles of organophosphorus ligand, and more preferably from about 1 to about 4 moles of organophosphorus ligand, per mole of metal present in the reaction medium; said amounts of organophosphorus ligand being the sum of both the amount of organophosphorus ligand that is bound (complexed) to the metal present and the amount of free (non-complexed) organophosphorus ligand present.
  • the more preferred organophosphorus ligands are achiral type organophosphite ligands, especially those encompassed by Formula (VIII) above, and more preferably those of Formulas (IX) and (XII) above.
  • make-up or additional organophosphorus ligand can be supplied to the reaction medium of the hydroformylation process at any time and in any suitable manner, e.g. to maintain a predetermined level of free ligand in the reaction medium.
  • the hydroformylation catalyst may be in heterogeneous form during the reaction and/or during the product separation.
  • Such catalysts are particularly advantageous in the hydroformylation of olefins to produce high boiling or thermally sensitive aldehydes, so that the catalyst may be separated from the products by filtration or decantation at low temperatures.
  • the rhodium catalyst may be attached to a support so that the catalyst retains its solid form during both the hydroformylation and separation stages, or is soluble in a liquid reaction medium at high temperatures and then is precipitated on cooling.
  • the rhodium catalyst may be impregnated onto any solid support, such as inorganic oxides, (i.e. alumina, silica, titania, or zirconia) carbon, or ion exchange resins.
  • the catalyst may be supported on, or intercalated inside the pores of, a zeolite or glass; the catalyst may also be dissolved in a liquid film coating the pores of said zeolite or glass.
  • Such zeolite-supported catalysts are particularly advantageous for producing one or more regioisomeric aldehydes in high selectivity, as determined by the pore size ofthe zeolite.
  • the solid catalyst thus formed may still be complexed with one or more ofthe ligands defined above.
  • Descriptions of such solid catalysts may be found in for example: J. Mol. Cat. 1991, 70, 363-368; Catal. Lett. 1991, 8, 209-214; J. Organomet. Chem, 1991, 403, 221-227; Nature, 1989, 339, 454-455; J. Catal. 1985, 96, 563-573; J. Mol. Cat. 1987, 39, 243-259.
  • the metal, e.g., rhodium, catalyst may be attached to a thin film or membrane support, such as cellulose acetate or polyphenylenesulfone, as described in for example J. Mol. Cat. 1990, 63, 213-221.
  • the metal, e.g., rhodium, catalyst may be attached to an insoluble polymeric support through an organophosphorus-containing ligand, such as a phosphine or phosphite, incorporated into the polymer.
  • organophosphorus-containing ligand such as a phosphine or phosphite
  • polymer-supported ligands are well known, and include such commercially available species as the divinylbenzene/polystyrene-supported triphenylphosphine.
  • the supported ligand is not limited by the choice of polymer or phosphorus-containing species incorporated into it. Descriptions of polymer-supported catalysts may be found in for example: J. Mol. Cat. 1993, 83, 17-35; Chemtech 1983, 46; J. Am. Chem. Soc. 1987, 109, 7122-7127.
  • the catalyst may remain in its heterogeneous form during the entire hydroformylation and catalyst separation process.
  • the catalyst may be supported on a polymer which, by the nature of its molecular weight, is soluble in the reaction medium at elevated temperatures, but precipitates upon cooling, thus facilitating catalyst separation from the reaction mixture.
  • soluble polymer-supported catalysts are described in for example: Polymer, 1992, 33, 161; J. Org. Chem. 1989, 54, 2726-2730.
  • the reaction may be carried out in the gas phase. More preferably, the reaction is carried out in the slurry phase due to the high boiling points of the products, and to avoid decomposition of the product aldehydes.
  • the catalyst may then be separated from the product mixture, for example, by filtration or decantation.
  • the reaction product fluid may contain a heterogeneous metal- organophosphorus ligand complex catalyst, e.g., slurry, or at least a portion ofthe reaction product fluid may contact a fixed heterogeneous metal-organophosphorus ligand complex catalyst during the hydroformylation process.
  • the metal-organophosphorus ligand complex catalyst may be slurried in the reaction product fluid.
  • the substituted or unsubstituted olefinic unsaturated starting material reactants that may be employed in the hydroformylation processes of this invention include both optically active (prochiral and chiral) and non-optically active (achiral) olefinic unsaturated compounds containing from 2 to 30, preferably 4 to 20, carbon atoms.
  • Such olefinic unsaturated compounds can be terminally or internally unsaturated and be of straight-chain, branched chain or cyclic structures, as well as olefin mixtures, such as obtained from the oligomerization of propene, butene, isobutene, etc. (such as so called dimeric, trimeric or tetrameric propylene and the like, as disclosed, for example, in U.
  • Such olefin compounds may further contain one or more ethylenic unsaturated groups, and of course, mixtures of two or more different olefinic unsaturated compounds may be employed as the starting hydroformylation material if desired.
  • commercial alpha olefins containing four or more carbon atoms may contain minor amounts of corresponding internal olefins and/or their corresponding saturated hydrocarbon and that such commercial olefins need not necessarily be purified from same prior to being hydroformylated.
  • olefinic unsaturated compounds and the corresponding aldehyde products derived therefrom may also contain one or more groups or substituents which do not unduly adversely affect the hydroformylation process or the process of this invention such as described, for example, in U. S. Patent Nos. 3,527,809, 4,769,498 and the like.
  • the subject invention is especially useful for the production of non-op tically active aldehydes, by hydroformylating achiral alpha-olefins containing from 2 to 30, preferably 4 to 20, carbon atoms, (including isobutylene), and achiral internal olefins containing from 4 to 20 carbon atoms as well as starting material mixtures of such alpha olefins and internal olefins.
  • Illustrative achiral alpha and internal olefins include, for example, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1- tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1- octadecene, 1-nonadecene, 1-eicosene, 2-butene, 2-methyl propene (isobutylene), 2-methylbutene, 2-pentene, 2-hexene, 3-hexane, 2- heptene, 2-octene, cyclohexene, propylene dimers, propylene trimers, propylene tetramers, butadiene, piperylene, isoprene, 2-ethyl-l-
  • Prochiral and chiral olefins useful in the asymmetric hydroformylation that can be employed to produce enantiomeric aldehyde mixtures that may be encompassed by in this invention include those represented by the formula:
  • R, , Rg, and R . are the same or different (provided R, is different from R « or Ro is different from R and are selected from hydrogen; alkyl; substituted alkyl, said substitution being selected from dialkylamino such as benzylamino and dibenzylamino, alkoxy such as methoxy and ethoxy, acyloxy such as acetoxy, halo, nitro, nitrile, thio, carbonyl, carboxamide, carboxaldehyde, carboxyl, carboxylic ester; aryl including phenyl; substituted aryl including phenyl, said substitution being selected from alkyl, amino including alkylamino and dialkylamino such as benzylamino and dibenzylamino, hydroxy, alkoxy such as methoxy and ethoxy, acyloxy such as acetoxy, halo, nitrile, nitro, carboxyl, carboxaldehyde, carboxy
  • Illustrative optically active or prochiral olefinic compounds useful in asymmetric hydroformylation include, for example, p-isobutylstyrene, 2-vinyl-6-methoxy-2-naphthylene, 3- ethenylphenyl phenyl ketone, 4-ethenylphenyl-2-thienylketone, 4- ethenyl-2-fluorobiphenyl, 4-(l,3-dihydro-l-oxo-2H-isoindol-2- yDstyrene, 2-ethenyl-5-benzoylthiophene, 3-ethenylphenyl phenyl ether, propenylbenzene, isobutyl-4-propenylbenzene, phenyl vinyl ether and the like.
  • Other olefinic compounds include substituted aryl ethylenes as described, for example, in U.S. Patent Nos. 4,3
  • hydroformylation reactions are especially useful for the production of aldehydes, by hydroformylating alpha olefins containing from 2 to 30, preferably 4 to 20, carbon atoms, including isobutylene, and internal olefins containing from 4 to 20 carbon atoms as well as starting material mixtures of such alpha olefins and internal olefins.
  • alpha olefins containing four or more carbon atoms may contain minor amounts of corresponding internal olefins and or their corresponding saturated hydrocarbon and that such commercial olefins need not necessarily be purified from same prior to being hydroformylated.
  • Illustrative mixtures of olefinic starting materials that can be employed in the hydroformylation reactions include, for example, mixed butenes, e.g., Raf ⁇ nate I and II.
  • suitable substituted and unsubstituted olefinic starting materials include those permissible substituted and unsubstituted olefinic compounds described in Kirk-Othmer, Encyclopedia of Chemical Technology, Third Edition, 1984, the pertinent portions of which are incorporated herein by reference.
  • the reaction conditions of the hydroformylation processes encompassed by this invention may include any suitable type hydroformylation conditions heretofore employed for producing optically active and/or non-optically active aldehydes.
  • the total gas pressure of hydrogen, carbon monoxide and olefin starting compound ofthe hydroformylation process may range from about 1 to about 10,000 psia. In general, however, it is preferred that the process be operated at a total gas pressure of hydrogen, carbon monoxide and olefin starting compound of less than about 1500 psia and more preferably less than about 500 psia.
  • the minimum total pressure being limited predominately by the amount of reactants necessary to obtain a desired rate of reaction.
  • the carbon monoxide partial pressure of the hydroformylation process of this invention is preferable from about 1 to about 360 psia, and more preferably from about 3 to about 270 psia, while the hydrogen partial pressure is preferably about 15 to about 480 psia and more preferably from about 30 to about 300 psia.
  • H2:CO molar ratio of gaseous hydrogen to carbon monoxide may range from about 1:10 to 100:1 or higher, the more preferred hydrogen to carbon monoxide molar ratio being from about 1:1 to about 10:1.
  • the hydroformylation process may be conducted at a reaction temperature from about -25°C to about 200°C.
  • hydroformylation reaction temperature of about 50°C to about 120°C are preferred for all types of olefinic starting materials.
  • achiral type olefin starting materials and organophosphorus ligands are employed and when optically active aldehyde products are desired prochiral or chiral type olefin starting materials and organophosphorus ligands are employed.
  • the hydroformylation reaction conditions employed will be governed by the type of aldehyde product desired.
  • hydroformylation processes encompassed by this invention are also conducted in the presence of water or an organic solvent for the metal-organophosphorus ligand complex catalyst and free organophosphorus ligand.
  • suitable organic solvents include, for example, alcohols, alkanes, alkenes, alkynes, ethers, aldehydes, higher boiling aldehyde condensation byproducts, ketones, esters, amides, tertiary amines, aromatics and the like. Any suitable solvent which does not unduly adversely interfere with the intended hydroformylation reaction can be employed and such solvents may include those disclosed heretofore commonly employed in known metal catalyzed hydroformylation reactions.
  • aldehyde compounds corresponding to the aldehyde products desired to be produced and/or higher boiling aldehyde liquid condensation byproducts as the main organic solvents as is common in the art.
  • aldehyde condensation byproducts can also be preformed if desired and used accordingly.
  • Illustrative preferred solvents employable in the production of aldehydes include ketones (e.g. acetone and methylethyl ketone), esters (e.g. ethyl acetate), hydrocarbons (e.g.
  • Suitable solvents are disclosed in U.S. Patent No. 5,312,996.
  • the amount of solvent employed is not critical to the subject invention and need only be that amount sufficient to solubilize the catalyst and free ligand of the hydroformylation reaction mixture to be treated. In general, the amount of solvent may range from about 5 percent by weight up to about 99 percent by weight or more based on the total weight of the hydroformylation reaction mixture starting material.
  • non-optically active aldehyde products include e.g., propionaldehyde, n-butyraldehyde, isobutyraldehyde, n-valeraldehyde, 2-methylbutyraldehyde, hexanal, hydroxy hexanal, 2-methylvaleraldehyde, heptanal, 2-methyl 1- hexanal, octanal, 2-methyl 1-heptanal, nonanal, 2-methyl- 1-octanal, 2- ethyl 1-heptanal, 3-propyl 1-hexanal, decanal, adipaldehyde, 2- methylglutaraldehyde, 2-methyladipaldehyde, 3-methyladipaldehyde, 3-hydroxypropionaldehyde, 3-pentenal, alkyl 5-formylvalerate, 2- methyl-1-nonanal, undecanal, 2-methyl 1-decanal, do
  • Illustrative optically active aldehyde products include (enantiomeric) aldehyde compounds prepared by the asymmetric hydroformylation process of this invention such as, e.g. S-2-(p- isobutylphenyD-propionaldehyde, S-2-(6-methoxy-2- naphthyDpropionaldehyde, S-2-(3-benzoylphenyl)-propionaldehyde, S- 2-(p-thienoylphenyl)propionaldehyde, S-2-(3-fluoro-4- phenyDphenylpropionaldehyde, S-2-[4-(l,3-dihydro-l-oxo-2H-isoindol- 2-yl)phenyl]propionaldehyde, S-2-(2-methylacetaldehyde)-5- benzoylthiophene and the like.
  • Suitable substituted and unsubstituted aldehyde products include those permissible substituted and unsubstituted aldehyde compounds described in Kirk-Othmer, Encyclopedia of Chemical Technology, Third Edition, 1984, the pertinent portions of which are incorporated herein by reference.
  • continuous hydroformylation processes are well known in the art and may involve: (a) hydroformylating the olefinic starting material(s) with carbon monoxide and hydrogen in a liquid homogeneous reaction mixture comprising a solvent, the metal- organophosphorus ligand complex catalyst, and free organophosphorus ligand; (b) maintaining reaction temperature and pressure conditions favorable to the hydroformylation ofthe olefinic starting material(s); (c) supplying make-up quantities of the olefinic starting material(s), carbon monoxide and hydrogen to the reaction medium as those reactants are used up; and (d) recovering the desired aldehyde hydroformylation product(s) in any manner desired.
  • the continuous process can be carried out in a single pass mode, i.e., wherein a vaporous mixture comprising unreacted olefinic starting material(s) and vaporized aldehyde product is removed from the liquid reaction mixture from whence the aldehyde product is recovered and make-up olefinic starting material(s), carbon monoxide and hydrogen are supplied to the liquid reaction medium for the next single pass through without recycling the unreacted olefinic starting material(s).
  • a continuous process that involves either a liquid and/or gas recycle procedure.
  • Such types of recycle procedure are well known in the art and may involve the liquid recycling of the metal-organophosphorus complex catalyst fluid separated from the desired aldehyde reaction product(s), such as disclosed, for example, in U.S. Patent 4,148,830 or a gas cycle procedure such as disclosed, for example, in U.S. Patent 4,247,486, as well as a combination of both a liquid and gas recycle procedure if desired.
  • the disclosures of said U.S. Patents 4,148,830 and 4,247,486 are incorporated herein by reference thereto.
  • the most preferred hydroformylation process of this invention comprises a continuous liquid catalyst recycle process. Suitable liquid catalyst recycle procedures are disclosed, for example, in U. S. Patent Nos. 4,668,651; 4,774,361; 5,102,505 and 5,110,990.
  • the aldehyde mixtures may be separated from the other components ofthe crude reaction mixtures in which the aldehyde mixtures are produced by any suitable method. Suitable separation methods include, for example, solvent extraction, crystallization, distillation, vaporization, wiped film evaporation, falling film evaporation, phase separation, filtration and the like. It may be desired to remove the aldehyde products from the crude reaction mixture as they are formed through the use of trapping agents as described in published Patent Cooperation Treaty Patent Application WO 88/08835. A preferred method for separating the aldehyde mixtures from the other components of the crude reaction mixtures is by membrane separation. Such membrane separation can be achieved as set out in U.S. Patent No.
  • the desired aldehydes may be recovered from the reaction mixtures used in the process of this invention.
  • the recovery techniques disclosed in U.S. Patents 4,148,830 and 4,247,486 can be used.
  • reaction product fluid i.e., reaction product fluid
  • a separation zone e.g., vaporizer/separator
  • the desired aldehyde product can be separated via distillation, in one or more stages, under normal, reduced or elevated pressure, from the liquid reaction fluid, condensed and collected in a product receiver, and further purified if desired.
  • the remaining non-volatilized catalyst containing liquid reaction mixture may then be recycled back to the reactor as may if desired any other volatile materials, e.g., unreacted olefin, together with any hydrogen and carbon monoxide dissolved in the liquid reaction after separation thereof from the condensed aldehyde product, e.g., by distillation in any conventional manner.
  • any other volatile materials e.g., unreacted olefin
  • hydrogen and carbon monoxide dissolved in the liquid reaction after separation thereof from the condensed aldehyde product, e.g., by distillation in any conventional manner.
  • Another suitable recovery technique is solvent extraction or crystallization.
  • the desired aldehydes In general, it is preferred to separate the desired aldehydes from the catalyst-containing reaction mixture under reduced pressure and at low temperatures so as to avoid possible degradation of the organophosphorus ligand and reaction products.
  • the aldehyde derivative thereof can also be separated by the above methods.
  • distillation and separation of the desired aldehyde product from the metal-organophosphorus complex catalyst containing reaction product fluid may take place at any suitable temperature desired.
  • a common practice is to subject the liquid reaction product medium removed from the hydroformylation reactor to a pressure reduction so as to volatilize a substantial portion of the unreacted gases dissolved in the liquid medium which now contains a much lower synthesis gas concentration than was present in the hydroformylation reaction medium to the distillation zone, e.g. vaporizer/separator, wherein the desired aldehyde product is distilled.
  • distillation pressures ranging from vacuum pressures on up to total gas pressure of about 50 psig should be sufficient for most purposes.
  • the aldol condensation involves condensing a substituted first aldehyde, e.g., 2-methylbutyraldehyde, with a substituted or unsubstituted second aldehyde, e.g., formaldehyde, in the presence of an aldol condensation catalyst to produce a reaction mixture comprising a substituted hydroxyaldehyde, e.g., 2-ethyl-2- methyl-3-hydroxypropanal .
  • a substituted hydroxyaldehyde e.g., 2-ethyl-2- methyl-3-hydroxypropanal .
  • Illustrative substituted first aldehydes include, for example, those aldehydes produced by the hydroformylation step described above or those aldehydes produced by other conventional processes.
  • Illustrative substituted or unsubstituted second aldehydes include, for example, formaldehyde, acetaldehyde and those aldehydes produced by the hydroformylation step described above or those aldehydes produced by other conventional processes.
  • the substituted first aldehyde and the substituted or unsubstituted second aldehyde can be the same or different.
  • the amounts of substituted first aldehydes and substituted or unsubstituted second aldehydes employed in the aldol condensation step is not narrowly critical and can be any amounts sufficient to produce the substituted hydroxyaldehydes, preferably in high selectivities. Employing excess amounts ofthe substituted first aldehyde in the aldol condensation step may be desirable for improving product selectivity.
  • the aldehydes e.g., formaldehyde, may be employed as aqueous solutions.
  • aldol condensation reaction conditions are not narrowly critical and can be any effective aldol condensation procedures sufficient to produce the substituted hydroxyaldehyde intermediates.
  • the aldol condensation reaction can be conducted at a temperature of from about 60°C to 120°C for a period of about 1 hour or less to about 4 hours or longer with the longer time being used at the lower temperature, preferably from about 80°C to about 100°C for about 1 hour or less to about 2 hours or longer, and more preferably at about 85°C to 95°C for about 1 hour or less.
  • the aldol condensation reaction can be conducted over a wide range of pressures ranging from about 1 psig to about 300 psig. It is preferable to conduct the aldol condensation reaction at pressures of from about 5 psig to about 40 psig.
  • the aldol condensation reaction is preferably effected in the liquid or vapor states or mixtures thereof.
  • aldol condensation reaction can be conducted using known aldol condensation catalysts in conventional amounts.
  • suitable aldol condensation catalysts include, for example, tertiary amines and the like.
  • Tertiary amines that may be employed in the aldol condensation reaction include trialkylamines such as methyldiethylamine, ethyldimethylamine, tripropylamine, dimethyltertiary butylamine, and the like.
  • aromatic amines derived from aniline and its derivatives may be employed such as diarylalkylamines and dialkylarylamines, e.g., phenyldimethylamine, phenyldiethylamine, methyldiphenylamine, and the like.
  • Heterocyclic tertiary amines wherein the nitrogen moiety is included as part of a heterocyclic ring may also be used effectively as aldol condensation catalysts.
  • Such amines may include methylpiperidine, dimethylpiperazine, methylmorpholine, methylthiamorpholine, and the like.
  • the preferred aldol condensation catalysts are trialkylamines, e.g., triethylamine.
  • the amount of aldol condensation catalyst used is dependent on the particular aldol condensation catalyst employed and can range from about 0.01 weight percent or less to about 10 weight percent or greater ofthe total weight ofthe starting materials.
  • Illustrative of substituted hydroxyaldehyde intermediates produced by the aldol condensation step include, for example, 2-ethyl-2-methyl-3-hydroxypropanal, 2,2-dimethyl-3- hydroxypropanal, 3-ethyl-2-methyl-3-hydroxypropanal, 2-ethyl-3- propyl-3-hydroxypropanal, 2,2-dimethyl-3-ethyl-3-hydroxypropanal, 2- ethyl-3-methyl-3-propyl-3-hydroxypropanal, 2,2-diethyl-3-methyl-3- hydroxypropanal, 3-ethyl-2,2-dimethyl-3-hydroxypropanal, 2,2- dimethyl-3-ethyl-3-propyl-3-hydroxypropanal, 2-methyl-2-propyl-3- hydroxypropanal, 2,3-dimethyl-3-ethyl-2-propyl-3-hydroxypropanal.
  • the substituted hydroxyaldehyde intermediates produced by the aldol condensation step of this invention can be separated by conventional techniques such as distillation or other suitable means.
  • a crude reaction product can be subjected to a distillation-separation at atmospheric or reduced pressure through a packed distillation column.
  • Reactive distillation may be useful in conducting the aldol condensation reaction step.
  • the subsequent hydrogenation of the aldol condensation reaction mixtures may be conducted without the need to separate the hydroxyaldehydes from the other components of the crude reaction mixtures.
  • the particular hydrogenation reaction conditions are not narrowly critical and can be any effective hydrogenation procedures sufficient to produce the substituted hydrocarbon diols of this invention.
  • the hydrogenation reaction may proceed in the presence of water, e.g., less than about 40 weight percent water, without substantial degradation of the hydrogenation catalyst.
  • the hydrogenation reaction can be conducted at a temperature of from about 60°C to 180°C for a period of about 1 hour or less to about 12 hours or longer with the longer time being used at the lower temperature, preferably from about 80°C to about 140°C for about 1 hour or less to about 8 hours or longer, and more preferably at about 115 C C to 125°C for about 1 hour or less to about 3 hours or longer.
  • a free radical inhibitor can be added to the reaction mass.
  • the hydrogenation reaction can be conducted over a wide range of hydrogen pressures ranging from about 50 psig to about 10000 psig, preferably from about 200 psig to about 1500 psig. It is most preferable to conduct the hydrogenation reaction at hydrogen pressures of from about 500 psig to about 1000 psig.
  • the reaction is preferably effected in the liquid or vapor states or mixtures thereof.
  • a favorable weight hourly space velocity can be practiced. Even at hydrogenation pressures as low as 500 psig, a weight hourly space velocity of 1.0 hour"l to 0.1 hour'l can be maintained. Higher hydrogenation pressures are not required to maintain these favorable space velocities and the favorable yields and process economics for the substituted hydrocarbon diols obtained therefrom.
  • the hydrogenation reaction can be conducted using known hydrogenation catalysts in conventional amounts.
  • suitable hydrogenation catalysts include, for example, Raney-type compounds such as Raney nickel and modified Raney nickels; molybdenum-promoted nickel, chromium-promoted nickel, cobalt- promoted nickel; platinum; palladium; iron; cobalt molybdate on alumina; copper chromite; barium promoted copper chromite; tin- copper couple; zinc-copper couple; aluminum-cobalt; aluminum-copper; and aluminum-nickel; platinum; nickel; and the like.
  • the preferred catalysts are manganese-promoted copper-chromate heterogeneous catalysts, e.g., manganese oxide-promoted copper oxide/copper chromite catalysts. See, for example, U.S. Patent Nos. 4,855,515 and 4,393,251, the disclosures of which are incorporated herein by reference.
  • the amount of catalyst used in the hydrogenation reaction is dependent on the particular catalyst employed and can range from about 0.01 weight percent or less to about 10 weight percent or greater ofthe total weight ofthe starting materials.
  • substituted 1,3-propanediols prepared by the processes of this invention include, for example, 2-ethyl-2-methyl- 1,3-propanediol, 2,2-dimethyl-l,3-propanediol, 3-ethyl-2-methyl-l,3- propanediol, 2-ethyl-3-propyl-l,3-propanediol, 2,2-dimethyl-3-ethyl- 1,3-propanediol, 2-ethyl-3-methyl-3-propyl-l,3-propanediol, 2,2- diethyl-3-methyl-l,3-propanediol, 3-ethyl-2,2-dimethyl-l,3- propanediol, 2,2-dimethyl-3-ethyl-3-propyl-l,3-propanediol, 2-methyl- 2-propyl-l,3-propanediol, 2,3-
  • the substituted hydrocarbon diols and, in particular, the substituted 1,3-propanediols preferably have (i) a non-symmetrical structure which contributes to increased flexibility while maintaining hardness, low viscosity and low crystallinity, (ii) primary hydroxyl groups which contribute to energy efficiency and low resin color, and (iii) no beta hydrogen which contributes to increased stability of ester linkage and excellent weatherability.
  • the substituted hydrocarbon diol products produced by the processes of this invention can be separated by conventional techniques such as distillation.
  • a crude reaction product can be subjected to a distillation-separation at atmospheric or reduced pressure through a packed distillation column.
  • Reactive distillation may be useful in conducting certain reaction steps of this invention.
  • Saponification sodium hydroxide
  • the processes of this invention may be carried out using, for example, a fixed bed reactor, a fluid bed reactor, or a slurry reactor.
  • the optimum size and shape of the catalysts will depend on the type of reactor used. In general, for fluid bed reactors, a small, spherical catalyst particle is preferred for easy fluidization. With fixed bed reactors, larger catalyst particles are preferred so the back pressure within the reactor is kept reasonably low.
  • the processes of this invention can be conducted in a batch or continuous fashion, with recycle of unconsumed starting materials if required.
  • the reaction can be conducted in a single reaction zone or in a plurality of reaction zones, in series or in parallel or it may be conducted batchwise or continuously in an elongated tubular zone or series of such zones.
  • the materials of construction employed should be inert to the starting materials during the reaction and the fabrication ofthe equipment should be able to withstand the reaction temperatures and pressures.
  • Means to introduce and/or adjust the quantity of starting materials or ingredients introduced batchwise or continuously into the reaction zone during the course of the reaction can be conveniently utilized in the processes especially to maintain the desired molar ratio ofthe starting materials.
  • the reaction steps may be effected by the incremental addition of one of the starting materials to the other. Also, the reaction steps can be combined by the joint addition of the starting materials. When complete conversion is not desired or not obtainable, the starting materials can be separated from the product, for example by distillation, and the starting materials then recycled back into the reaction zone.
  • the processes are conducted for a period of time sufficient to produce the substituted hydrocarbon diol products.
  • the exact reaction time employed is dependent, in part, upon factors such as temperature, nature and proportion of starting materials, and the like.
  • the reaction time will normally be within the range of from about one-half to about 100 hours or more, and preferably from less than about one to about ten hours.
  • the process may be conducted in either glass lined, stainless steel or similar type reaction equipment.
  • the reaction zone may be fitted with one or more internal and or external heat exchanger(s) in order to control undue temperature fluctuations, or to prevent any possible "runaway" reaction temperatures.
  • the products produced by the processes of this invention include substituted hydrocarbon diols, particularly those substituted 1,3-propanediols encompassed within formulas (I) and (II), which may be useful in a number of ways including imparting excellent physical characteristics, such as water resistance, chemical resistance and the like, to coatings, inks, adhesives, and sealants prepared from the substituted hydrocarbon diols or derivatives thereof.
  • IPreferred applications include, for example, coil coatings, high solids coatings, polyesters, polyurethanes, polyester polyols, gel coats, powder coatings, adhesives and waterborne coatings.
  • Coil coating compositions can be prepared by conventional methods from various resins including, but not limited to, polyester, alkyd, acrylic, vinyl and epoxy resins and combinations thereof.
  • the formula (I) substituted hydrocarbon diols may be used in preparation of such resins.
  • the formula (I) substituted hydrocarbon diols may be used in preparation of polyester resins.
  • An illustrative coil coating composition can be made from a polyester resin solution by dispersing in the polyester resin solution a desired concentration of pigment filler such as titanium dioxide, aromatic hydrocarbon solvent, melamine resin in a sufficient amount to crosslink the polyester resin and a crosslinking catalyst such as p- toluene sulfonic acid.
  • a leveling agent may also be added.
  • This coil coating composition can then be spread as a thin film on a metal coil substrate, for example, steel, copper, aluminum or the like to typically provide, when cured, a film thickness of about 0.3-1.2 mils.
  • the coating is cured by crosslinking. See, for example, U.S. Patent Nos. 4,968,775 and 4,520,188, the disclosures of which are incorporated herein by reference.
  • suitable coil coating compositions include those permissible coil coating compositions which are described in Kirk-Othmer, Encyclopedia of Chemical Technology, Third Edition, 1984, the pertinent portions of which are incorporated herein by reference.
  • Gel coat compositions can be prepared by conventional methods from various resins including, but not limited to, polyester, acrylic and urethane type resins and combinations thereof.
  • the formula (I) substituted hydrocarbon diols may be used in preparation of such resins.
  • the formula (I) substituted hydrocarbon diols may be used in preparation of polyester resins.
  • Conventional gel coat compositions are useful as the exterior paint layer for boats and bathroom fixtures such as shower stalls, bath tub enclosures and the like.
  • a gel coat is a pigmented, filled and prepromoted resin (usually polyester) which is sprayed with an initiator onto molds from a high pressure spray gun to a film thickness of up to 0.75 mm. The film cures prior to reinforcement with glass fibers and laminating resins.
  • the gel coat should exhibit low viscosity at high shear, should resist sagging, and have a gel time of about 8-12 minutes.
  • the products require hydrolytic stability and good weatherability. See, for example, U.S. Patent No. 4,587,323, the disclosure of which is incorporated herein by reference.
  • suitable gel coat compositions include those permissible gel coat compositions which are described in Kirk-Othmer, Encyclopedia of Chemical Technology, Third Edition, 1984, the pertinent portions of which are incorporated herein by reference.
  • Thermoplastic and thermosetting powder coating compositions can be prepared by conventional methods from various resins including, but not limited to, carboxyl polyester, hydroxyl polyester, acrylic and epoxy type resins and combinations thereof.
  • the formula (I) substituted hydrocarbon diols may be used in preparation of such resins.
  • the formula (I) substituted hydrocarbon diols may be used in preparation of polyester resins.
  • the powder coating compositions may be used to coat articles of various shapes and sizes constructed of heat-resistance materials such as glass, ceramic and various metal materials.
  • the powder coating compositions can be especially useful for producing coatings on articles constructed of metals and metal alloys, particularly steel articles.
  • the substituted hydrocarbon diols produced by the processes of this invention can undergo further reaction(s) to afford desired derivatives thereof.
  • Such permissible derivatization reactions can be carried out in accordance with conventional procedures known in the art.
  • Illustrative derivatization reactions include, for example, esterification, etherification, alkoxylation, amination, alkylation, hydrogenation, dehydrogenation, reduction, acylation, condensation, carboxylation, oxidation, silylation and the like, including permissible combinations thereof.
  • This invention is not intended to be limited in any manner by the permissible derivatization reactions or permissible derivatives of substituted hydrocarbon diols or substituted hydroxy aldehydes .
  • the substituted hydrocarbon diols produced by the processes of this invention can undergo any ofthe known reactions of hydroxyl groups illustrative of which are reactions with acyl halides to form esters; with ammonia, a nitrile, or hydrogen cyanide to form amines; with alkyl acid sulfates to form disulfates; with carboxylic acids and acid anhydrides to form esters and polyesters; with alkali metals to form salts; with ketenes to form esters; with acid anhydrides to form carboxylic acids; with oxygen to form aldehydes and carboxylic acids; ring-opening reactions with lactones, tetrahydrofuran, and alkylene oxides such as ethylene oxide, propylene oxide, epichlorohydrin; dehydrogenation to form aldehydes, isocyanates to form urethanes, and the like.
  • Products containing free carboxylic acid groups can be made by conventional methods by reacting the substituted hydrocarbon diols of formula (I) with acid anhydrides in which one equivalent of acid anhydride is used for each equivalent of hydroxyl.
  • the product containing free carboxylic acid groups can be prepared by heating the substituted hydrocarbon diol of formula (I) and an acid anhydride at a temperature of about 60°C to about 200°C, preferably from about 80°C to about 160°C, and most preferably from about 100°C to about 140°C for a period of time ranging from about 30 minutes to about 8 hours or more, preferably from about 1 hour to about 4 hours, or until substantially all ofthe acid anhydride has reacted with the hydroxyl groups.
  • the reaction may be carried out in the presence of a solvent that is inert to reaction with hydroxyl groups or anhydride groups such as benzene, toluene, methyl ethyl ketone, methyl i-butyl ketone, methyl amyl ketone, ethoxyethyl acetate, ethoxyethyl butyrate, and the like.
  • a solvent that is inert to reaction with hydroxyl groups or anhydride groups such as benzene, toluene, methyl ethyl ketone, methyl i-butyl ketone, methyl amyl ketone, ethoxyethyl acetate, ethoxyethyl butyrate, and the like.
  • a catalyst may be used in preparation of the free carboxylic acid products.
  • the catalysts that can be used to prepare the free carboxylic acid products of this invention are dibutyltin dioxide, antimony oxide, tin oxide, titanium alkoxides, alkali metal salts or metallic salts of manganese, cadmium, magnesium, zinc, tin, and the like.
  • the free carboxylic acid products e.g., substituted 1,3- dicarboxylic acids
  • polyols including formula (I) substituted hydrocarbon diols, having two or more hydroxyl groups to produce polyesters that can be used in coatings, adhesives, inks, fibers, fabrics, shaped articles, and the like.
  • Ester products can be prepared by conventional methods by reacting formula (I) substituted hydrocarbon diols with an anhydride such as acetic anhydride which would form the dimethyl ester when one equivalent of acetic anhydride is reacted with each equivalent of formula (I) substituted hydrocarbon diols. It is understood by those skilled in the art that less than a 1:1 equivalency of anhydride per hydroxyl group will result in a partially esterified product that will contain both ester and hydroxyl groups. Esterified and partially esterified products such as these are useful as inert solvents or intermediates for further reaction through free hydroxyl groups or through transesterification with suitable compounds including themselves.
  • anhydride such as acetic anhydride which would form the dimethyl ester when one equivalent of acetic anhydride is reacted with each equivalent of formula (I) substituted hydrocarbon diols. It is understood by those skilled in the art that less than a 1:1 equivalency of anhydride per hydroxyl group will result
  • Silicone-containing compounds can be prepared by conventional methods by either end capping, coupling, or other reaction when formula (I) substituted hydrocarbon diols or mixtures of formula (I) substituted hydrocarbon diols and optionally other polyols are reacted with silanes. It is understood by those skilled in the art that when polyfunctional compounds are combined, a variety of products, including chain extended products, can be obtained.
  • silanes include, for example, chloroalkylchloro and arylchlorosilanes, diphenylethylchlorosilane, trimethylchlorosilane, dimethyldichloromethylsilane, triphenylchlorosilane, methyldichlorsilane, dimethylethylchlorosilane, dichlorosilane; alkoxysilanes such as methoxysilane, dimethoxysilane, diethyoxysilane, triethoxysilane, dimethylmethoxychlorsilane, dimethylmethoxysilane, tris(methoxy)-3-chloropropylsilane, and the like.
  • the silicone-containing compounds can be used as solvents, surfactants, reactive diluents or other components, as hydraulic fluids, as intermediates for the formation of other compounds, as components in polyesters that have utility in coatings, inks, adhesives, fibers, and molded articles, as well as in other end uses.
  • Illustrative polyols that can be used in combination with the formula (I) substituted hydrocarbon diols to prepare derivatives thereof include, for example, diethylene glycol, 1,4- butanediol, 1,6-hexanediol, 1,4-dihydroxyquinone, 2,2-dimethyl-l,3- propanediol, hydroxyl-terminated polyesters, ethylene oxide/propylene oxide copolymer polyols, poly(ethylene oxide) polyols, poly(propylene oxide) polyols, poly(alkylene oxide) polyols, poly(tetramethylene oxide) polyols, polyether polyols, polycarbonate polyols, polylactone polyols, and the like, including mixtures thereof.
  • Polylactone polyols can be prepared by conventional methods by reacting from 1 to 50 moles, preferably from 1 to 25, and most preferably from 1 to 10 moles of a lactone with one mole of one of the substituted hydrocarbon diols of this invention.
  • the polylactone polyols are prepared by heating the lactone and substituted hydrocarbon diol at a temperature of about 140°C to about 210°C, preferably from about 150°C to about 180°C for a period of time of about 6 hours to about 36 hours, preferably from 8 hours to about 24 hours. It is preferred to use from about 10 to 5000 or more parts per million, preferably from about 20 to about 1500 parts per million, of a catalyst to promote the ring- opening polymerization.
  • a catalyst to promote the ring- opening polymerization.
  • organometallics such as stannous octanoate, dibutyltin dilaurate, zinc octanoate, and the like.
  • Such polylactone polyols have many uses, illustrative of which are intermediates for the preparation of polyurethane elastomers and foams, aminoplast-cured coatings, radiation-cured coatings and inks, and the like.
  • Use of the substituted hydrocarbon diols of this invention in preparation ofthe polyols may result in improved hydrolytic stability for materials prepared from the polylactone polyols.
  • certain substituted hydroxyaldehyde intermediates can be isolated and used in a variety of ways including as reactive diluents for cycloaliphatic epoxide systems that are curable by either thermal means when cation- generating catalysts/initiators such as boron trifluoride, boron trifluoride etherate, triflic acid or its salts such as diethyl ammonium triflate, ammonium triflate, and the like are used, or by photochemical means when photolyzable Bronsted or Lewis acid- generating photoinitiators such as the onium salts which can be illustrated by the arylsulfonium hexafluorophosphates, the arylsulfonium hexafluoroarsenates, the arylsulfonium hexafluoroantimonates, diazonium hexafluorophosphate, iodonium hexafluorophosphate,
  • polyol is contemplated to include all permissible hydrocarbon compounds having 2 or more hydroxyl groups, e.g., diols, triols and the like.
  • ester-diol is contemplated to include all permissible ester-diols formed from the Tischenko reaction of substituted hydroxyaldehydes during the processes of this invention.
  • 2-methyl-2-hydroxymethylbutyl 2-methyl-2- hydroxymethylbutyrate may be formed from the Tischenko reaction of 2-ethyl-2-methyl-3-hydroxyaldehyde during the processes of this invention.
  • hydrocarbon is contemplated to include all permissible compounds having at least one hydrogen and one carbon atom.
  • permissible hydrocarbons include acyclic and cyclic, branched and unbranched, carbocyclic and heterocyclic, aromatic and nonaromatic organic compounds which can be substituted or unsubstituted.
  • the term "substituted" is contemplated to include all permissible substituents of hydrocarbon compounds unless otherwise indicated.
  • the permissible substituents include acyclic and cyclic, branched and unbranched, carbocyclic and heterocyclic, aromatic and nonaromatic substituents of hydrocarbon compounds.
  • Illustrative substituents include, for example, alkyl, alkyloxy, aryl, aryloxy, hydroxy, hydroxyalkyl, amino, aminoalkyl, halogen and the like in which the number of carbons can range from 1 to about 20 or more, preferably from 1 to about 12.
  • the permissible substituents can be one or more and the same or different for appropriate hydrocarbon compounds. This invention is not intended to be limited in any manner by the permissible substituents of hydrocarbon compounds.
  • Double Rubs - Solvent resistance was measured as the number of solvent (methyl ethyl ketone) double rubs that were required to cut through the coating. If 300 rubs or more did not cut through the coating, the coating was recorded as >300. To perform the test, the solvent-soaked cloth was rubbed back and forth with hand pressure. A rub back and forth was designated as one "double rub.”
  • a Fini automatic transfer pipette was used to place a series of 50 micro-liter droplets of 15% sulfuric acid solution at approximately 1/4-inch intervals in two rows along the length of one or more coated panels. Usually two panels were required to provide the length of surface needed to examine the temperature range of 40°C to 100°C that is achieved in the gradient temperature oven. Two rows of spots are used for duplication of the test.
  • the coated panels are placed in an end-to-end position on the heating bank of a BYK Chemie gradient temperature oven. The first spots are aligned with the #1 rod which is at 40°C. This results in the various spots being at temperatures that range to 100°C.
  • the sulfuric acid solution droplets are allowed to contact the coating for various times at the indicated temperatures. After the desired heating time, the panels are removed from the gradient oven, cooled to room temperature, rinsed thoroughly with distilled water, lightly patted dry, and evaluated.
  • Evaluation consists of examining the areas that had been covered with the droplets with a 10-power, lighted magnifier. The following are points of comparison observed and recorded for each coating. a) The lowest temperature spot area with a visible defect in the coating. A "visible defect” is the first sign of any blush, bubbling, yellowing, or other visible change. b) The lowest temperature spot with a severe defect. A “several defect” is blistering or complete removal of the coating with the substrate visible. This latter factor means the acidic solution has cut through the coating to the substrate.
  • Shrinkage - Measurement (mils/inch) of dimension of a cold part compared to the dimension of a cold mold.
  • Catalyst I - A 40 percent solution of p-toluenesulfonic acid in methanol.
  • Catalyst II - A solution of butyl stannoic acid commercially available from Atochem North America as Fascat®4100.
  • Melamine I A polymethoxymethyl melamine commercially available from American Cyanamid as Cymel® 303.
  • Surfactant I - A solution of a polyether modified dimethylpolysiloxane copolymer commercially available from BYK Chemie as BYK® - 300.
  • Surfactant II A 25 percent solution of a methoxy- terminated poly( ethylene oxide) modified polydimethylsiloxane in methyl amyl ketone commercially available from OSi Specialties Inc. as Silwet® L-77.
  • Surfactant III A 25 percent solution of a methoxy- terminated ethylene oxide/propylene oxide copolymer modified polydimethylsiloxane in methyl amyl ketone commercially available from OSi Specialties Inc. as Silwet® L-7001.
  • Polymeric Isocyanate I An aliphatic polyisocyanate commercially available from Bayer as Desmodur® N-3300.
  • the reactor was cooled to 60°C and 200 grams of a crude 2-ethyl-2-methyl-3-hydroxypropanal mixture was charged.
  • the crude 2-ethyl-2-methyl-3-hydroxypropanal mixture was 0.03 % methanol, 0.9 % 2-methybutyraldehyde, 1.0 % triethylamine, 0.08 % 2-methylbutanol, 81.0 % 2-ethyl-2-methyl-3-hydroxypropanal, 4.3 % 2-ethyl-2-methyl-l,3-propanediol and 10.2 % ester-diol.
  • the reactor was heated to 120°C and pressurized to 700 psig hydrogen. The reaction solution was rapidly stirred.
  • reaction solution samples were taken every 30 minutes. The reaction was complete in 1.5 hours.
  • the 1.5 hour reaction sample analyzed as 2.2 % methanol, 0.04 % 2-methylbutyraldehyde, 0.9 % triethylamine, 0.5 % 2-methylbutanol, 0.14 % 2-ethyl-2-methyl-3- hydroxypropanal, 81.4 % 2-ethyl-2-methyl-l,3-propanediol, and 13.0 % ester-diol.
  • polyester resins with the same acid to diol molar ratio were prepared from 2-ethyl-2-methyl-l,3-propanediol (Example 2) and 2-methyl-l,3-propanediol, 2,2-dimethyl-l,3-propanediol (neopentyl glycol), 1,6-hexanediol and 2,2,4-trimethyl-l,3-pentanediol (Control Examples A, B, C, & D) to compare the relative efficacy of the various diols to provide good properties.
  • the coatings of Example 3 have an excellent combination of high gloss, solvent resistance, and adhesion.
  • the polyester of Example 2 exhibited the best combination of hardness and flexibility measured by pencil hardness and forward and reverse impact resistance and acid etch resistance.
  • the polymers from Example 2 (2-ethyl-2-methyl-l,3- propanediol) and Example B (neopentyl glycol) were compared for compatibility with a range of different resins including melamines, epoxies, ureas, and acrylics (see Table B).
  • the polyester of Example 2 was compatible with all of the other resins tested; however, the polyester derived from neopentyl glycol showed only partial solubility with many of the other resins.
  • Example C showed poor adhesion to the metal substrate; it failed the adhesion test and exhibited stress cracking upon standing. Very brittle films were observed for the polyester of Example D, 25 and ⁇ 5 for direct and reverse impact. Acid etch resistance was also poor for this polymer.
  • Example 2 A four-necked, one-liter round bottom flask equipped with a mechanical stirrer, thermometer, nitrogen sparging tube, and a simple distillation head was charged with 722.2 grams ( 6.12 mole) of 2- ethyl-2-methyl-l,3-propanediol, 79.1 grams ( 0.59 mole) of trimethylolpropane, 553 grams ( 3.33 mole) of isophthalic acid, 250 grams ( 1.71 mole) of adipic acid, and 0.39 grams ( 0.02 weight percent) dibutyltin oxide catalyst. The ingredients were kept under a nitrogen sparge with stirring throughout the course of the reaction. The system was gradually heated to 160°C.
  • the temperature was maintained with a Therm-O-Watch controller until no more water was generated, and then the temperature was increased in 10°C increments to a maximum temperature of 240°C. All water of condensation formed by the reaction was removed with xyiene azeotroping agent during the esterification reaction.
  • the resulting polyester had a Brookfield viscosity of 51,100 centipoise at 60°C, a hydroxyl number of 138, and an acid number of 0.33.
  • Molecular weight determination by gel permeation chromatography using a polystyrene standard resulted in an apparent number average molecular weight of 1072, a weight-average molecular weight of 1892, and a polydispersity of 1.76.
  • control polyesters were prepared from a four-carbon diol, a five-carbon diol, a linear six-carbon diol, and an eight-carbon diol using the same molar ratios with the ingredients listed in Table A below.
  • the control polyesters had the properties given in Table A.
  • thermally curable coatings prepared from a polyester identified in Table C below and an aminoplast crosslinking agent.
  • the ingredients listed in Table C, except for Catalyst I were placed in a glass container and thoroughly mixed for each example. When they were well mixed, Catalyst I was stirred into the blend. The blended components were allowed to stand under ambient conditions to allow escape of entrapped air. The liquid coating was then applied with a 10-mil wet-clearance film applicator to Bonderite cold-rolled steel panels using the draw-down technique. The coated panels were then baked in an air-circulating oven at 140°C for 30 minutes. The coatings were then tested by the indicated tests with the results given in Table D below.
  • polyesters of varying molecular weights were prepared from 2-ethyl-2-methyl-l,3-propanediol in the same manner as that of Example 2 except the ingredients listed in Table E below were used. The polyesters had the properties given in Table E.
  • Hydroxyl capped polyurethanes were prepared by the reaction of 2-ethyl-2-methyl-l,3-propanediol and neopentyl glycol with either isophorone diisocyanate (Examples 8 and 9) or hexamethylene diisocyanate (Examples 12 and 13), in the presence of 0.02 % of dibutyltin dilaurate catalyst with a hydroxyl to isocyanate ratio was 2:1.
  • Coatings were prepared by reacting these polyurethanes with either polyfunctional isocyanates (Examples 10, 11, 14 and 15) or aminoplast crosslinking agents (Examples 16, 17, 18 and 19). Improved coating hardness (measured by Pencil Hardness) and better acid etch resistance were observed for the 2-ethyl-2-methyl-l,3-propanediol based polyurethanes.
  • Example 8 59.68 grams (0.5 moles) of 2-ethyl-2-methyl-l,3- propanediol, 0.0296 grams (0.025%) of dibutyltin dilaurate and 16.2 grams of n-methyl-2-pyrrolidone were charged to a 500 milliliter, 4- necked flask equipped with a mechanical stirrer, nitrogen sparger, inlet and outlet nitrogen connection which also functioned as a feeding port, and thermometer. While sparging with nitrogen and stirring, these ingredients were heated to 80°C and held at this temperature for 1 hour to remove water. The temperature was then decreased to 55°C and 56.68 grams (0.25 moles) of isophorone diisocyanate were slowly added dropwise to the reaction mass.
  • Example 9 A polyurethane was prepared in the same manner as that of Example 8 except the following ingredients were used: 52.59 grams (0.5 mole) of 2,2-dimethyl-l,3-propanediol (neopentyl glycol), 56.68 grams (0.25 mole) of isophorone diisocyanate, 25.6 grams of n- methyl-2-pyrrolidone, and 0.0278 grams (0.025 weight percent) dibutyltin dilaurate catalyst. The resulting polyurethane had a hydroxyl number of 259. Molecular weight determination by gel permeation chromatography using a polystyrene standard resulted in an apparent number average molecular weight of 834, a weight-average molecular weight of 904, and a polydispersity of 1.08.
  • Examples 10 and 11 These examples describe the preparation of thermally curable coatings prepared from the polyurethanes of Examples 8 and 9, an isocyanate crosslinking agent and other ingredients listed in Table G below. After thorough mixing of the ingredients, the resulting mixtures were coated onto phosphatized steel panels with a No. 20 wire-wound rod and cured at 100°C for 30 minutes. Hard clear coatings resulted. The coatings were then tested by the indicated tests with the results given in Table G.
  • Example 12 59.68 grams (0.5 moles) of 2-ethyl-2-methyl-l,3- propanediol, 0.0261grams (0.025%) of dibutyltin dilaurate catalyst and 14.5 grams of n-methyl-2-pyrrolidone were charged to a 500 milliliter, 4-necked flask equipped with a mechanical stirrer, nitrogen sparger, inlet and outlet nitrogen connection which also functioned as a feeding port, and thermometer. While sparging with nitrogen and stirring, these ingredients were heated to 80°C and held at this temperature for one hour to remove water. The temperature was then decreased to 55 C C and 42.89 grams (0.25 moles) of hexam ethylene diisocyanate were slowly added to the reaction mass.
  • the reaction was allowed to proceed at 55°C for three hours, and then the reaction mass was allowed to cool to room temperature.
  • the resulting polyurethane had a hydroxyl number of 291.
  • Molecular weight determination by gel permeation chromatography using a polystyrene standard resulted in an apparent number average molecular weight of 484, a weight-average molecular weight of 516, and a polydispersity of 1.07.
  • Example 13 A polyurethane was prepared in the same manner as that of Example 12 except the following ingredients were used: 52.59 grams (0.5 mole) of 2,2-dimethyl-l,3-propanediol (neopentyl glycol), 42.89 grams (0.25 mole) of an hexamethylene diisocyanate, 13.5 grams of n-methyl-2-pyrrolidone, and 0.0243 grams (0.025 weight percent) dibutyltin dilaurate catalyst.
  • the resulting polyurethane had a hydroxyl number of 313.
  • Molecular weight determination by gel permeation chromatography using a polystyrene standard resulted in an apparent number average molecular weight of 487, a weight-average molecular weight of 527, and a polydispersity of 1.08.
  • Examples 14 and 15 These examples describe the preparation of thermally curable coatings prepared from the polyurethanes of Examples 12 and 13, an isocyanate crosslinking agent and other ingredients listed in Table H below. After thorough mixing of the ingredients, the resulting mixtures were coated onto phosphatized steel panels with a No. 20 wire-wound rod and cured at 90°C for 30 minutes. Hard clear coatings resulted. The coatings were then tested by the indicated tests with the results given in Table H.
  • Example 16-19 The polyurethane polymers of Example 8, 9, 12 and 13 were formulated in a 3 to 1 ratio by weight with Melamine I crosslinking agent. To each of these mixtures, 0.5% by weight of Catalyst I, 0.5% by weight of Surfactant II, and 0.5% by weight of Surfactant III were added and then well mixed. The resultant liquid coating formulations were applied to steel panels with a wire-wound draw-down rod and baked for 30 minutes in a 140°C oven. The resulting coatings had the properties set out in Table I below:
  • Examples 20 and 21 Polyurethane reactions were conducted in the same manner as that of Examples 8 and 9 except no solvent was used for the reaction.
  • the resulting polyurethane for Example 20 had an hydroxyl number of 261.
  • Molecular weight determination by gel permeation chromatography using a polystyrene standard resulted in an apparent number average molecular weight of 331, a weight-average molecular weight of 392, and a polydispersity of 1.19.
  • neopentyl glycol remained solid at the reaction temperature, therefore, no product was produced.
  • Example 22 This example describes the preparation of a thermally curable coating prepared from the polyurethane of Example 20.
  • a polyurethane coating was prepared following the procedure in Example 10. After thorough mixing of the ingredients, the resulting mixtures were coated onto phosphatized steel panels with a No. 20 wire-wound rod and cured at 90°C for 45 minutes. The coating was examined and found to be smooth and clear. The resulting coating had a B Pencil Hardness, a 5B Crosshatch Adhesion, a Specular Gloss (20°C/60°C) of 83.8/93.9, an Impact Resistance (forward/reverse) of 300+/295 in-lbs, and an Acid Etch Resistance (1st visible/lst severe) of 68/76. Solvent resistance was found to be 70 double rubs.
  • Example 23 A four-necked, one-liter round bottom flask equipped with a mechanical stirrer, thermometer, nitrogen sparging tube, and a simple distillation head was charged with 118.18 grams (1.0884 mole) of 2- ethyl-2-methyl-l,3-propanediol, and 73.75 grams (0.44395 mole) of terephthalic acid. The ingredients were kept under a nitrogen sparge with stirring throughout the course of the reaction. The system was gradually heated to 140°C.
  • the temperature was maintained with a Therm-O-Watch controller until ingredients were softened, and then 73.75 grams (0.44395 mole) of terephthalic acid, 6.2 grams (0.0323 mole) of 1,2,4-benzenetricarboxylic anhydride, and 0.142 grams (0.0463%) of Catalyst II were added.
  • the temperature was increased in 10°C increments to a maximum temperature of 240°C. All water of condensation formed by the reaction was removed with xyiene azeotroping agent during the esterification reaction. The reaction was continued until the acid number was less than 10.
  • the reaction flask was cooled to 190°C and 24.6 grams (0.1481 mole) of isophthalic acid was added.
  • the system was reheated to 240°C, and the reaction was continued until the acid number stopped declining.
  • the resulting polyester had a I.C.I, melt viscosity of 20 poise at 200°C, a measured Tg of 55°C, and an acid number of 42.0.
  • Molecular weight determination by gel permeation chromatography using a polystyrene standard resulted in an apparent number average molecular weight of 2664, a weight-average molecular weight of 6435 and a polydispersity of 2.42.
  • Example 24 Polyester powder was prepared in the same manner as that of Example 23 except 104.15 grams (1.0884 mole) of neopentyl glycol was used instead of 2-ethyl-2-methyl-l,3-propanediol.
  • the resulting polyester had a I.C.I, melt viscosity of 58 poise at 200°C, a measured glass transition temperature (Tg) of 64.7°C, and an acid number of 37.0.
  • Tg glass transition temperature
  • Molecular weight determination by gel permeation chromatography using a polystyrene standard resulted in an apparent number average molecular weight of 2230, a weight-average molecular weight of 4845, and a polydispersity of 2.17.
  • Example 25 A four-necked, one-liter round bottom flask equipped with a mechanical stirrer, thermometer, nitrogen sparging tube, and a simple distillation head was charged with 118.18 grams (1.0884 mole) of 2-ethyl-2-methyl-l,3-propanediol, and 172.42 grams (0.0.8879 mole) of dimethyl terephthalate, 6.2 grams (0.0323 mole) of 1,2,4- benzenetricarboxylic anhydride, and 0.142 grams (0.0463 %) of Catalyst II were added. The ingredients were kept under a nitrogen sparge with stirring throughout the course of the reaction. The system was gradually heated to 140°C.
  • the temperature was maintained with a Therm-O-Watch controller until no more methanol was generated, and then the temperature was increased in 10°C increments to a maximum temperature of 240°C.
  • the reaction was continued until the acid number was less than 10.
  • the reaction flask was cooled to 190°C and 24.6 grams (0.1481 mole) of isophthalic acid were added.
  • the system was reheated to 240°C, and the reaction continued until the acid Number stopped declining.
  • the resulting polyester had a I.C.I, melt viscosity of 4 poise at 200°C, a measured glass transition temperature (Tg) of 46.4°C, and an acid number of 4.4.
  • Tg measured glass transition temperature
  • Example 26 Polyester powder was prepared in the same manner as that of Example 25 except 104.15 grams (1.0884 mole) of neopentyl glycol was used in place ofthe 2-ethyl-2-methyl-l,3-propanediol.
  • the resulting polyester had a I.C.I, melt viscosity of 17 poise at 200°C, a measured glass transition temperature (Tg) of 47.8°C, and an acid number of 47.9.
  • Tg glass transition temperature
  • Molecular weight determination by gel permeation chromatography using a polystyrene standard resulted in an apparent number average molecular weight of 1529, a weight-average molecular weight of 2608, and a polydispersity of 1.71
  • Unsaturated Polyesters/Gel Coats Three runs were performed to assess the advantage of 2- ethyl-2-methyl-l,3-propanediol in unsaturated polyesters for fiberglass reinforced composites, e.g., sheet molding compound, applications.
  • the three unsaturated polyesters are respectively, a mixture of propylene glycol, 2-ethyl-2-methyl-l,3-propanediol and maleic anhydride; a mixture of propylene glycol, neopentyl glycol and maleic anhydride; and a mixture of propylene glycol and maleic anhydride.
  • the three unsaturated polyesters were evaluated in a sheet molding compound formulation (see Table J below).
  • Neulon® H is a polyester modifier commercially available from Union Carbide Corporation.
  • VR3 is a viscosity reducer commercially available from Union Carbide Corporation. Shrinkage, flexibility and toughness of the polymers were measured. All three samples exhibited similar shrinkage results; however, the 2-ethyl-2-methyl-l,3-propanediol based unsaturated polyester (Example 27) demonstrated the best flexibility and toughness which were represented by low Flex Modulus and high Flex Strength (see Table K below).
  • Example 27 A four-necked, five-liter round bottom flask equipped with a mechanical stirrer, thermometer, nitrogen sparging tube, and a simple distillation head was charged with 486.8 grams (4.125 mole) of 2-ethyl-2-methyl-l,3-propanediol, 313.5 grams (4.125 mole) of propylene glycol, 735 grams (7.5 mole) of maleic anhydride, and 0.3078 grams (200 ppm) of hydroquinone. The ingredients were kept under a nitrogen sparge with stirring throughout the course of the reaction. The system was gradually heated to 140°C.
  • the temperature was maintained with a Therm-O-Watch controller until no more water was generated, and then the temperature was increased in 10°C increments to a maximum temperature of 200°C. All water of condensation formed by the reaction was removed with xyiene azeotroping agent during the esterification reaction. The reaction was continued until the acid number was between 20 and 30.
  • the reaction flask was cooled to 100°C and 613.4 grams (30%) styrene and 0.2021 grams (100 ppm) of hydroquinone were added.
  • the resulting polyester had an acid number of 27.0.
  • Molecular weight determination by gel permeation chromatography using a polystyrene standard resulted in an apparent number average molecular weight of 3129, a weight-average molecular weight of 8027, and a polydispersity of 2.57.
  • Example 28 A four-necked, five-liter round bottom flask equipped with a mechanical stirrer, thermometer, nitrogen sparging tube, and a simple distillation head was charged with 429.0 grams (4.125 mole) of 2,2-dimethyl-l,3-propanediol, 313.5 grams (4.125 mole) of propylene glycol, 735 grams (7.5 mole) of maleic anhydride, and 0.2962 grams (200 ppm) of hydroquinone. The ingredients were kept under a nitrogen sparge with stirring throughout the course of the reaction. The system was gradually heated to 140°C.
  • the temperature was maintained with a Therm-O- Watch controller until no more water was generated, and then the temperature was increased in 10°C increments to a maximum temperature of 200°C. All water of condensation formed by the reaction was removed with xyiene azeotroping agent during the esterification reaction. The reaction was continued until the acid number was between 20 and 30.
  • the reaction flask was cooled to 100°C and 586.6 grams (30%) of styrene and 0.1933 grams (100 ppm) of hydroquinone were added.
  • the resulting polyester had an acid number of 26.4.
  • Molecular weight determination by gel permeation chromatography using a polystyrene standard resulted in an apparent number average molecular weight of 2937, a weight-average molecular weight of 7375, and a polydispersity of 2.51.
  • Example 29 A four-necked, five-liter round bottom flask equipped with a mechanical stirrer, thermometer, nitrogen sparging tube, and a simple distillation head was charged with 688.1 grams (9.05 mole) of propylene glycol, 806.0 grams (8.22 mole) of maleic anhydride, and 0.2995 grams (200 ppm) of hydroquinone. The ingredients were kept under a nitrogen sparge with stirring throughout the course of the reaction. The system was gradually heated to 140°C. The temperature was maintained with a Therm-O- Watch controller until no more water was generated, and then the temperature was increased in 10°C increments to a maximum temperature of 200°C.

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  • Polymers & Plastics (AREA)
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Abstract

La présente invention concerne des procédés de préparation de mélanges réactionnels contenant des diols d'hydrocarbures substitués tels que les 1,3-propanediols comme principaux produits de réaction. L'invention concerne également des mélanges réactionnels contenant des diols d'hydrocarbures substitués comme principaux produits de réaction. Ces diols d'hydrocarbures substitués et leurs dérivés, qui s'utilisent seuls ou pour préparer des intermédiaires, conviennent particulièrement à la préparation de revêtements, d'adhésifs, d'encres, de fibres, d'intermédiaires pharmaceutiques, d'étanchéifiants, à l'utilisation en stéréolithographie ou à d'autres utilisations finales.
PCT/US1996/017885 1995-11-03 1996-11-01 Melanges reactionnels contenant des diols d'hydrocarbures substitues et procedes de preparation WO1997016401A1 (fr)

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WO1999005572A2 (fr) * 1997-07-21 1999-02-04 Ciba Specialty Chemicals Holding Inc. Stabilisation de viscosite de compositions chargees durcissables par rayonnement
EP1090899A2 (fr) * 1999-10-06 2001-04-11 Basf Aktiengesellschaft Procédé de préparation de 1,3-dioles
WO2003099902A1 (fr) * 2002-05-24 2003-12-04 Basf Aktiengesellschaft Procede de production de polyols de polyesters a partir d'alcools polyvalents

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WO1999005572A2 (fr) * 1997-07-21 1999-02-04 Ciba Specialty Chemicals Holding Inc. Stabilisation de viscosite de compositions chargees durcissables par rayonnement
WO1999005572A3 (fr) * 1997-07-21 1999-04-15 Ciba Geigy Ag Stabilisation de viscosite de compositions chargees durcissables par rayonnement
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US6380443B1 (en) 1999-10-06 2002-04-30 Basf Aktiengesellschaft Preparation of 1,3-diols
EP1090899A3 (fr) * 1999-10-06 2003-10-15 Basf Aktiengesellschaft Procédé de préparation de 1,3-dioles
WO2003099902A1 (fr) * 2002-05-24 2003-12-04 Basf Aktiengesellschaft Procede de production de polyols de polyesters a partir d'alcools polyvalents
CN1300211C (zh) * 2002-05-24 2007-02-14 巴斯福股份公司 制备多元醇的聚酯多元醇的方法
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