US20030078311A1 - Process for the alkoxylation of organic compounds in the presence of novel framework materials - Google Patents

Process for the alkoxylation of organic compounds in the presence of novel framework materials Download PDF

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US20030078311A1
US20030078311A1 US10/039,733 US3973301A US2003078311A1 US 20030078311 A1 US20030078311 A1 US 20030078311A1 US 3973301 A US3973301 A US 3973301A US 2003078311 A1 US2003078311 A1 US 2003078311A1
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polyurethane
process according
reacting
obtainable
organic
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US10/039,733
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English (en)
Inventor
Ulrich Muller
Michael Stober
Raimund Ruppel
Eva Baum
Edward Bohres
Marcus Sigl
Lisa Lobree
Omar Yaghi
Mohamed Eddaoudi
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University of Michigan System
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Priority to US10/039,733 priority Critical patent/US20030078311A1/en
Assigned to BASF AKTIENGESELLSCHAFT reassignment BASF AKTIENGESELLSCHAFT ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: BOHRES, EDWARD, EDDAOUDI, MOHAMED, LOBREE, LISA, MULLER, ULRICH, SIGL, MARCUS, STOSSER, MICHAEL, YAGHI, OMAR, BAUM, EVA, RUPPEL, RAIMUND
Priority to EP02781271A priority patent/EP1440106B1/en
Priority to KR1020047005723A priority patent/KR100940290B1/ko
Priority to JP2003538229A priority patent/JP4173101B2/ja
Priority to CA002464352A priority patent/CA2464352A1/en
Priority to CNB028207831A priority patent/CN100424115C/zh
Priority to AT02781271T priority patent/ATE535560T1/de
Priority to PCT/EP2002/011700 priority patent/WO2003035717A1/en
Priority to PL02370429A priority patent/PL370429A1/xx
Priority to RU2004115338/04A priority patent/RU2308465C2/ru
Priority to ES02781271T priority patent/ES2376050T3/es
Priority to MXPA04003467A priority patent/MXPA04003467A/es
Priority to US10/492,192 priority patent/US7279517B2/en
Priority to TW091124078A priority patent/TWI300072B/zh
Publication of US20030078311A1 publication Critical patent/US20030078311A1/en
Assigned to REGENTS OF THE UNIVERSITY OF MICHIGAN (50%), THE reassignment REGENTS OF THE UNIVERSITY OF MICHIGAN (50%), THE ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: BASF AKTIENGESELLSCHAFT
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • 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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
    • C08G65/2645—Metals or compounds thereof, e.g. salts
    • C08G65/266—Metallic elements not covered by group C08G65/2648 - C08G65/2645, or compounds 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
    • 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
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers

Definitions

  • the present invention relates to a process for the alkoxylation of organic compounds in the presence of catalyst systems comprising a metallo-organic frame-work material comprising pores and a metal ion and an at least bidentate organic compound, said bidentate organic compound being coordinately bound to the metal ion.
  • the invention further encompasses an integrated process for preparing polyurethanes from isocyanate and polyether alcohol or modified polyether alcohols, which have been obtained by using the alkoxylation process according to the invention. Still further, the present invention is directed to polyurethanes being obtainable by the process according to the invention, as well as shaped bodies comprising the polyurethanes as prepared according to the invention.
  • polyurethanes prepared according to the invention are particularly useful for the preparation of polyurethane foams, polyurethane cast skins and elastomers.
  • polyurethanes such as mechanical properties and smell
  • isocyanate and polyether alcohols which are respectively used for their preparation, and optionally upon the used driving agents.
  • the structure of the polyether alcohol has a strong influence on the characteristics of the obtained polyurethane.
  • the properties of the polyether alcohols are in turn strongly influenced by their method of preparation and particularly by the characteristics and the process for preparation of the starting materials. A detailed discussion of the phenomena may be found in WO 01/7186 and DE 10143195.3 of the present applicant. As further prior art for preparing polyether alcohol, WO 01/16209 and WO 00/78837 are to be mentioned.
  • Polyether alcohols may be prepared e.g. by way of base or acid catalyzed polyaddition of alkaline oxides to polyfunctional organic compounds (starters).
  • Suitable starters are e.g. water, alcohols, acids or amines or mixtures of two or more thereof.
  • the side products generated by side reactions within the base or acid catalyzed reaction are furthermore partly contained in the polyurethane as smelling impurities.
  • aldehydes e.g. propionic aldehyde, cycloacetales, allylic alcohol and their reaction products.
  • the automotive and furniture industry request in increasing amounts polyetheroles and polyurethanes having reduced or no smell.
  • An object of the invention is therefore to provide a process for the preparation of polyether alcohols and polyurethanes, respectively, which yields polyether alcohols and polyurethanes, respectively, having a low amount of impurities, particularly low molecular weight substances having intensive smell, which process does not comprise elaborate purifying steps of starting materials and/or intermediate products.
  • This object is solved by a process for the alkoxylation of organic compounds comprising the reaction of at least one organic compound, which is capable of being alkoxylated, with at least one alkoxylating agent in the presence of a catalyst system, wherein a polyether alcohol is obtained, characterized in that the catalyst system comprises a metallo-organic framework material comprising pores and at least one metal ion and at least one at least bidentate organic compound, which is coordinately bound to said metal ion, and
  • alkoxylating agent in step (2) preferably mono- or multifunctional expoxide having two to 30 carbon atoms or mono- or multifunctional polyester polyoles having a molar mass of above 600 g/mol or a mixture of two or more thereof are used.
  • substituted or unsubstituted alkylene oxides having two to 24 C-atoms e.g. alkylene oxides having halogen, hydroxy, non-cyclic ether or ammonium substituents are used.
  • ethylene oxide 1,2-epoxypropane, 1,2-methyl-2-methylpropane, 1,2-epoxybutane, 2,3-epoxybutane, 1,2-methyl-3-methylbutane, 1,2-epoxypentane, 1,2-methyl-3-methylpentane, 1,2-epoxyhexane, 1,2-epoxyheptane, 1,2-epoxyoctane, 1,2-epoxynonane, 1,2-epoxydecane, 1,2-epoxyundecane, 1,2-epoxydodecane, 1,2-epoxycyclopentane, 1,2-epoxycyclohexane, (2,3-epoxypropyl)benzene, vinyloxirane, 3-phenoxy-1,2-epoxypropane, 2,3-epoxymethyl ether, 2,3-epoxylethyl ether, 2,3-epoxyl isopropyl ether
  • aliphatic 1,2-alkylene oxide having 2 to 4 C-atoms such as ethylene oxide, 1,2-butylene oxide, 2,3-butylene oxide or isobutylene oxide
  • aliphatic 1,2-alkylene oxides having 5 to 24 C-atoms aliphatic 1,2-alkylene oxides having 5 to 24 C-atoms
  • cycloaliphatic alkylene oxide such as cyclopentane oxide, cyclohexane oxide or cyclododecatriane-(1,5,9)-monoxide
  • araliphatic alkylene oxide e.g. styrene oxide.
  • polyether alcohols within the present invention, particularly polyester polyoles and modified polyetheroles are used, which are obtainable by using ethylene oxide or propylene oxide, which may be prepared according to step (1), preferably according to an embodiment outlined hereinunder. Subsequently, step (1) of the present invention is exemplarily described in detail by use of propylene oxide as an example:
  • propylene oxide may be obtained by reacting propylene with oxygen; hydrogen and oxygen; hydrogen peroxide; organic hydroperoxides; or halohydrines, preferably by reacting propylene with hydrogen peroxide, more preferred by reacting propylene with hydrogen peroxide in the presence of a catalyst comprising a zeolithic material, particularly by reacting propylene with hydrogen peroxide in the presence of a catalyst comprising a titanium-containing zeolithic material having CS-1-structure.
  • hydrogen peroxide is to be mentioned. This can be either prepared outside the reaction according to (1) or by starting from hydrogen and oxygen in situ within the reaction according to (1), respectively.
  • the present invention also relates in a preferred embodiment to a process for the alkoxylation of organic compounds and an integrated process for preparing a polyurethane, respectively, wherein the hydroperoxide as used in step (1) is hydrogen peroxide.
  • the epoxidation according to step (1) is in principle known from e.g. DE 100 55 652.3 and further patent applications of the present applicant, such as DE 100 32 885.7, DE 100 32 884.9, DE 100 15 246.5, DE 199 36 547.4, DE 199 26 725.1, DE 198 47 629.9, DE 198 35 907.1, DE 197 23 950.1, which are fully encompassed within the content of the present application with respect to their respective content.
  • propylene oxide is obtained in high purity.
  • the propylene oxide as such obtained exhibits a content of C 6 -compunds of ⁇ 1 ppm.
  • C6-compounds e.g. the following compounds are underdstood: 2-methylpentane, 4-methylpentene-1, n-hexane, hexenes, such as 1-hexene, and components having 6 C-atoms and in addition thereto one or more functional groups selected among the class of aldehydes, carboxylic acids, alcohols, ketones and ethers.
  • propane derivatives particularly chlorinated propane derivatives, acetaldehyde, propione aldehyde, acetone, dioxolanes, allylic alcohol, pentane, methylpentane, furane, hexane, hexene, methoxypropane and methanol.
  • the propylene oxide obtained according to step (1) may further comprise as further side components, up to 100 ppm, particularly up to 40 ppm, methanol and up to 10 ppm, preferably up to 4 ppm, acetaldehyde.
  • step (1) yields propylene oxide having only minor impurities of C 6 -components and contain no chloro-organic impurities.
  • ethylene oxide which may also serve as an alkoxylating agent and which may also be prepared prior to conducting the process for the alkoxylation of an organic compound being capable of being alkoxylated
  • ethylene oxide which may also serve as an alkoxylating agent and which may also be prepared prior to conducting the process for the alkoxylation of an organic compound being capable of being alkoxylated
  • the alkoxylating agent obtained according to step (1) may be directly used in the reaction according to step (2). It is, however, also possible within the present invention that the alkoxylating agent, particularly propylene oxide, yielded according to step (1) is beforehand treated, e.g. purified. As the purification method, mention can be made of a fine distillation. Suitable processes are e.g. disclosed in EP-B 0 557 116.
  • the alkoxylating agent as obtained according to step (1) may be used within the present invention alone or together with at least one further alkoxylating agent, particularly together with at least one further alkylene oxide.
  • step (2) For preparing a polyether alcohol according to step (2), it is possible within the present invention to use instead of or besides propylene oxide all alkoxylating agents, particularly alkylene oxides, which are known to the person skilled in the art, particularly the above-mentioned compounds.
  • alkoxylating agent obtained according to step (1) particularly propylene oxide
  • at least one further alkoxylating agent, particularly a further alkylene oxide it is possible within the present invention that a mixture of the alkoxylating agent as obtained according to step (1), particularly propylene oxide, and at least one further alkoxylating agent, particularly alkylene oxide, is employed. It is, however, also possible within the present invention that the alkoxylating agent as obtained according to step (1), particularly propylene oxide, and the at least one further alkoxylating agent, particularly an alkylene oxide, are added subsequently.
  • the polyether alcohols as obtained according to step (2) may e.g. comprise also block structures.
  • the structure of the polyether alcohols may be controlled in wide ranges by appropriate reaction conditions. Suitable reaction conditions for the reaction according to step (2) are e.g. disclosed in WO 99/16775.
  • the polyether alcohols as obtained according to step (2) may be modified for the reaction according to step (3).
  • modified polyether alcohols particularly to be mentioned are grafted polyether polyoles, particularly those which are prepared by polymerizing styrene and acrylonitril in the presence of polyetheroles; polyurea dispersions (PHD-polyoles) which are prepared by reacting diisocyanates and diamines in the presence of polyetheroles; and polyisocyanate polyaddition polyoles (PIPA polyoles), which are prepared by reacting diisocyanates and amino alcohols in the presence of polyetheroles.
  • PPD-polyoles polyurea dispersions
  • PIPA polyoles polyisocyanate polyaddition polyoles
  • step (2) The reaction according to step (2) is carried out in the presence of a catalyst system.
  • the catalyst system as used according to the invention in step (2) comprises a metallo-organic pore containing framework material, which in turn comprises a metal ion and an at least bidentate organic compound, said bidentate organic compound being coordinately bound to the metal ion.
  • a metallo-organic pore containing framework material which in turn comprises a metal ion and an at least bidentate organic compound, said bidentate organic compound being coordinately bound to the metal ion.
  • Such catalyst systems are known as such and described in e.g. U.S. Pat. No. 5,648,508, EP-A-0 709 253, J. Sol. State Chem., 152 (2000) p. 3-20, Nature 402 (1999), p. 276 seq., Topics in Catalysis 9 (1999), p. 105-111, Science 291 (2001), p. 1021-23.
  • An inexpensive way for their preparation is the subject of DE 10111230.0.
  • the metallo-organic framework materials comprise pores, particularly micro- and/or mesopores, wherein micropores are defined as being pores having a diameter of 2 nm or below and mesopores being pores having a diameter in the range of above 2 nm to 50 nm, respectively, according to the definition in Pure Applied Chem. 45, p. 71 seq., particularly p. 79 (1976).
  • the presence of the micro- and/or mesopores may be monitored by sorption measurements for determining the capacity of the metallo-organic framework materials to take up nitrogen at 77 K according to DIN 66131, 66134.
  • a type-I-form of the isothermal curve indicates the presence of micropores.
  • the specific surface areas are preferably above 5 m 2 /g, more preferably above 50 m 2 /g, particularly above 500 m 2 /g and may increase into the region of to above 2000 m 2 /g.
  • metal component within the framework material as used according to the present invention particularly to be mentioned are metal ions of elements of groups Ia, IIa, IIIa, IVa to VIIIa and Ib to VIb of the periodic system; among those particularly to be mentioned are Mg, Ca, Sr, Ba, Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, Al, Ga, In, Tl, Si, Ge, Sn, Pb, As, Sb, and Bi, more preferably Zn, Cu, Ni, Pd, Pt, Ru, Rh and Co.
  • metal ions of these elements are: Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Sc 3+ , Y 3+ , Ti 4+ , Zr 4+ , Hf 4+ , V 4+ , V 3+ , V2+ , Nb 3+ , Ta 3+ , Cr 3+ , Mo 3+ , W 3+ , Mn 3+ , Mn 3+ , Mn 2+ , Re 3+ , Re 2+ , Fe 3+ , Fe 2+ , Ru 3+ , Ru 2+ , Os 3+ , Os 2+ , Co 3+ , Co 2+ , Rh 2+ , Rh + , Ir 2+ , Ir + , Ni 2+ , Ni + , Pd 2+ , Pd + , Pt 2+ , Pt + , Cu 2+ , Cu + , Ag + , Au + , Zn 2+ , Cd 2+ ,
  • the at least bidentate organic compound which is capable to coordinate with the metal ion, in principle all compounds which are suitable for this purpose and which fulfill the above requirements of being at least bidentate, may be used.
  • the organic compound must have at least two centers, which are capable to coordinate with the metal ions of a metal salt, particularly with the metals of the aforementioned groups.
  • alkyl or aryl amine substructure consisting of alkyl groups having from 1 to 10 carbon atoms or aryl groups having from 1 to 5 phenyl rings,
  • said substructures having bound thereto at least one at least bidentate functional group “X”, which is covalently bound to the substructure of said compound, and wherein X is selected from the group consisting of
  • a preferred ligand is 1,3,5-benzene tricarboxyllic acid (BCT), particularly preferred metal ions are Co 2+ and Zn 2+ .
  • the framework material as used in accordance with the present invention may also comprise one or more mono-dentate ligands, which are preferably derived from the following mono-dentate substances:
  • alkyl amines and their corresponding alkyl ammonium salts containing linear, branched, or cyclic aliphatic groups, having from 1 to 20 carbon atoms (and their corresponding ammonium salts);
  • aryl amines and their corresponding aryl ammonium salts having from 1 to 5 phenyl rings;
  • alkyl phosphonium salts containing linear, branched, or cyclic aliphatic groups, having from 1 to 20 carbon atoms;
  • aryl phosphonium salts having from 1 to 5 phenyl rings;
  • aryl organic acids and their corresponding aryl organic anions and salts having from 1 to 5 phenyl rings;
  • aliphatic alcohols containing linear, branched, or cyclic aliphatic groups, having from 1 to 20 carbon atoms;
  • solvents which are particularly useful for the preparation of MOF-5, in addition to the solvents disclosed in the above-referenced literature dimethyl formamide, diethyl formamide and N-methylpyrollidone, alone, in combination with each other or in combination with other solvents may be used.
  • the solvents and mother liquors are recycled after crystallization in order to save costs and materials.
  • the separation of the framework materials, particularly of MOF-5, from the mother liquor of the crystallization may be achieved by procedures known in the art such as solid-liquid separations, such as centrifugation, extraction, filtration, membrane filtration, cross-flow filtration, flocculation using flocculation adjuvants (non-ionic, cationic and anionic adjuvants) or by the addition of pH shifting additives such as salts, acids or bases, by flotation, spray-drying or spray granulation as well as by evaporation of the mother liquor at elevated temperature and/or in vacuo and concentrating of the solid.
  • solid-liquid separations such as centrifugation, extraction, filtration, membrane filtration, cross-flow filtration, flocculation using flocculation adjuvants (non-ionic, cationic and anionic adjuvants) or by the addition of pH shifting additives such as salts, acids or bases, by flotation, spray-drying or spray granulation as well as by evaporation of the mother
  • the separated framework materials, particularly MOF-5 may be compounded, melted, extruded, co-extruded, pressed, spinned, foamed and granulated according to processes known within the processing of plastics, respectively.
  • step (2) the alkoxylating agent, particularly propylene oxide from step (1) or a mixture of propylene oxide of step (1) and at least one further alkylene oxide is reacted with an organic alkoxylatable compound (organic compound).
  • organic alkoxylatable compound organic compound
  • organic compounds which can be alkoxylated.
  • organic compounds the following are to be mentioned:
  • organic mono- or dicarboxylic acids such as acrylic acid, methacrylic acid, succenic acid, adipinic acid, phthalic acid and teraphthalic acid, aliphatic and aromatic, optionally N-mono-, N,N- and N,N′-dialkyl-substituted diamine with 1 to 4 carbon atoms in the alkyl group, such as optionally mono- or dialkyl-substituted ethylenediamine, diethylenetriamine, triethylenetetramine, 1,3-propylenediamine, 1,3- or 1,4-butylenediamine, 1,2-, 1,3-, 1,4-, 1,5- and 1,6-hexamethylenediamine, phenylenediamines, 2,3-, 2,4- and 2,6-toluylenediamine and 4,4′-, 2,4′- and 2,2′-diamino-di-phenylmethane, alkanolamines, such as
  • addition products ethylene oxide and/or propylene oxide and water, monoethyleneglycol, diethyleneglykol, propandiol-1,2, diproplyeneglycol, glycerol, trimethylolpropane, ethylendiamine, triethanolamine, pentaerythrit, sorbite and/or saccharose are used alone or in admixture with each other.
  • the organic compounds may also be used in the form of alkoxylates, particularly those having a molecular weight M w in the range of 62 to 15,000 g/mol.
  • macromolecules having functional groups with active hydrogen atoms such as hydroxyl groups, particularly those which are mentioned in WO 01/16209 may be used.
  • step (2) The polyether alcohols as obtained in step (2) may be reacted with isocyanates in step (3).
  • Step (3) may be carried out directly after step (2). It is also possible that an additional step, particularly a purification step, may be carried out between step (2) and (3).
  • one or more isocyanates may be used.
  • further components having groups which are reactive towards isocyanates, particularly those having hydroxyl groups, may be additionally used.
  • OH-components use can be made of e.g. polyesters, further polyethers, polyacetales, polycarbonates, polyesterethers, and similar compounds.
  • Suitable polyesterpolyoles may be prepared by reacting organic dicarboxylic acids having 2 to 23 carbon atoms, preferably aliphatic dicarboxylic acids having 4 to 6 carbon atoms, with polyvalent alcohols, preferably dioles, respectively having 2 to 12 carbon atoms, preferably 2 to 6 carbon atoms.
  • dicarboxylic acids the following may be preferably used:
  • succinic acid glutaric acid, adipinic acid, suberic acid, azelaic acid, sebacinic acid, decanedicarboxylic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid and teraphthalic acid.
  • the dicarboxylic acids may be used alone or in admixture with each other.
  • the free dicarboxylic acid also the corresponding dicarboxylic acid derivatives, such as dicarboxylic esters of alcohols having 1 to 4 carbon atoms or dicarboxylic acid anhydrides may be used. Examples for polyvalent alcohols are:
  • ethanediole diethyleneglycol, 1,2- and 1,3-propanediole, dipropyleneglycol, 1,4-butanediole, 1,5-pentanediole, 1,6-hexanediole, 1,10-decanediole, 1,12-dodecanediole, glycerol and trimethylolpropane.
  • ethanediole diethyleneglycol, 1,4-butanediole, 1,5-pentanediole, 1,6-hexanediole, glycerol and/or trimethylolpropane.
  • polyesterpolyoles made of lactones, e.g. caprolactone or hydroxy carboxylic acid, such as ⁇ -hxydroxycarpronic acid may be used.
  • the organic, e.g. aromatic or preferably aliphatic polycarboxylic acids and/or derivatives thereof may be reacted acted with the polyvalent alcohol in the absence of a catalyst or preferably in the presence of an esterifying catalyst.
  • the reaction is carried out in an inert atmosphere, e.g. in a nitrogen, carbon monoxide, helium, argon, etc. atmosphere.
  • the whole reaction is carried out in a melt at temperatures from 150 to 250° C., preferably 180 to 220° C., optionally under reduced pressure, up to the desired acid number, which preferably is lower than 10, more preferably lower than 2.
  • the mixture to be esterified is first reacted up to an acid number of 80 to 30, preferably 40 to 30, under normal pressure and at the above-mentioned temperatures, and subsequently polycondensated at a pressure of lower than 500 mbar, preferably 50 to 150 mbar.
  • esterifying catalyst mention can be made of e.g. Fe, Cd, Co, Pb, Zn, Sb, Mg, Ti and Sn catalysts in the form of metals, metal oxides or metal salts.
  • the polycondensation may be also carried out in the liquid phase in the presence of a thinning and/or entraining agent, such as benzene, toluene, xylene or chlorobenzene, in order to azeotropically distillate the water generated during condensation.
  • a thinning and/or entraining agent such as benzene, toluene, xylene or chlorobenzene
  • the organic polycarboxylic acids and/or acid derivatives and the polyvalent alcohols are preferably polycondensated in molar ratios of 1:1.8, preferably 1:1.05 to 1:1.2.
  • the obtained polyesterpolyoles exhibit preferably a functionality of 2 to 4, particularly 2 to 3 and a hydroxyl number of preferably 22 to 100 mg KOH/g.
  • dioles, trioles and/or polyoles having molecular weights of 60 to ⁇ 400 such as aliphatic, cycloaliphatic and/or araliphatic dioles having 2 to 14, preferably 4 to 10 carbon atoms, such as ethyleneglycol, propoanediole-1,3, decanediole-1,10, o-, m-, p-dihydroxycyclohexane, diethyleneglycol, dipropylenglycol and preferably butanediole-1,4, hexanediole-1,6 and bis-(2-hydroxyethyl)-hydroquinone; triole, such as 1,2,4-, 1,3,5-trihydroxy cyclohexane, glycol and trimethylolproprane; and low molecular weight polyalkyleneoxides having hydroxyl groups, such as those obtained by reacting ethylene oxide and/or 1,
  • the polyether alcohol of step (2) is reacted with at least one isocyanate.
  • isocyanates which are known to the person skilled in the art, may be used within the present invention. Particularly, the following are to be mentioned:
  • aromatic, araliphatic, aliphatic and/or cycloaliphatic organic isocyanates preferably diisocyanates.
  • alkylenediisocyanates having 4 to 12 carbon atoms in the alkylene group such as 1,12-dodecanediisocyanate, 2-ethyl-tetramethylenediisocyanate-1,4, 2-methylpentamethylenediisocyanate-1,5, tetramethylenediisocyanate-1,4, lysinesterdiisocyanate (LDI) and/or hexamethylenediisocyanate-1,6 (HDI); cycloaliphatic diisocyanates, such as cyclohexane-1,3- and 1,4-diisocyanate and arbitrary mixtures of these isomers, 2,4- and 2,6-hexahydrotoluylenediisocyanate and the respective mixtures of isomers, 4,4′-, 2,2′- and 2,4′-dicyclohexylmethanediisocyanate and the respective mixtures of isomers and/or 1-isocyana
  • mixtures comprising at least two of the above-mentioned isocyanates may also be used.
  • modified isocyanates having isocyanurate, bouret, ester, urea, allophanate, carbodiimid, uretdione, and/or urethane groups (in the following also denoted urethane group modified) containing di- and/or polyisocyanates may be used.
  • urethane group containing organic polyisocyanates having an NCO-content of 50 to 10 wt.-%, preferably 35 to 15 wt.-%, relative to the total weight, such as 4,4′-diphenylmethanediisocyanate, 4,4′- and 2,4′-diphenylmethanediisocyanate mixtures, raw-MDI or 2,4- and 2,6-toluylendiisocyanates, which are respectively modified, e.g.
  • dioles, trioles, dialkyleneglycoles, trialkyleneglycoles or polyoxyalkyleneglycoles having molecular weights of up to 6000, particularly molecular weights of up to 1500, may be used alone or in admixture with each other.
  • di- or polyoxyalkyleneglycoles which may in turn also be used alone or in admixture with each other, the following are to be mentioned:
  • diethylene- and dipropyleneglycol polyoxyethylene-, polyoxypropylene- and polyoxypropylenepolyoxyetheneglycoles, -trioles and/or tetroles.
  • prepolymers comprising NCO-groups, and respectively having NCO-contents of 25 to 3.5 wt.-%, preferably 21 to 14 wt.-%, respectively relative to the total weight, may be also used.
  • These compounds are prepared from the above-described polyester- and/or preferably polyether polyoles and 4,4′-diphenylmethanediisocyanate, mixtures of 2,4′- and 4,4′-diphenylmethanediisocyanate, 2,4- and/or 2,6-toluylenediisocyanate or raw-MDI.
  • use can also be made of liquid polyisocyanates containing carbodiimide groups, respectively having NCO-contents of 36.6 to 15, preferably 31 to 21 wt.-%, relative to the total weight, e.g.
  • modified polyisocyanates may be mixed with each other or together with non-modified organic polyisocyanates, such as e.g. 2,4′-, 4,4′-diphenylmethanediisocyanate, raw-MDI, 2,4- or 2,6-toluylenediisocyanate.
  • modified isocyanates preferably use is made of isocyanurate, biuret and/or urethane group modified aliphatic and/or cycloaliphatic diisocyanates, e.g. those which are already mentioned, which are provided with biuret and/or cyanurate groups according to known processes, and which comprise at least one, preferably at least two and more preferably at least three free isocyanate groups, respectively.
  • the trimerization of the isocyanates for preparing isocyanates having isocyanurate groups may be carried out at common temperatures in the presence of known catalysts, such as phosphines and/or phosphorine derivatives, amines, alkali metal salts, metal compounds and/or Mannich bases.
  • trimers of isocyanates containing isocyanurate groups are furthermore commercially available.
  • Isocyanates having biuret groups may also be prepared according to generally known processes, e.g. by reacting the above-mentioned diisocyanates with water or diamines, wherein as an intermediate product, a urea derivative is formed.
  • Isocyanates containing biuret groups are also commercially available.
  • step (3) is carried out under conditions known to the person skilled in the art. Suitable reaction conditions are described in e.g. Becker, Braun “Polyurethanes”, Kunststoffhandbuch, Vol. 7, Carl Hanser, Kunststoff, 3 rd Ed., 1993, p. 139 to 193.
  • low molecular weight compounds may be added as additives.
  • Such compounds may be chain extenders or stopping agents. Particularly useful for this purpose are e.g. primary amino compounds having 2 to about 20, e.g. 2 to about 12 C-atoms. As examples, the following are to be mentioned:
  • the reaction according to step (3) may optionally be carried out in the present of a catalyst.
  • Compounds which are suitably used as catalysts may in principle be all compounds which strongly accelerate the reaction of isocyanates with compounds being reactive towards isocyanates, wherein preferably a total content of catalyst of from 0.001 to 15 wt.-%, particularly 0.05 to 6 wt.-%, relative to the total weight of compounds being reactive towards isocyanates is used.
  • a total content of catalyst of from 0.001 to 15 wt.-%, particularly 0.05 to 6 wt.-%, relative to the total weight of compounds being reactive towards isocyanates is used.
  • possibly used catalysts are exemplarily mentioned:
  • Tertiary amines such as triethylamine, tributylamine, dimethylbenzylamine, dicyclohexylmethylamine, dimethylcyclohexylamine, N,N,N′,N′-tetramethyldiaminodiethylether, bis(dimethylaminopropyl)urea, N-methyl- and N-ethylmorpholine, N-cyclohexylmorpholine, N,N,N′,N′-tetramethylethylenediamine, N,N,N′,N′-tetramethylbutanediamine, N,N,N′,N′-tetramethylhexanediamine-1,6, pentamethyldiethylenetriamine, dimethylpiperazine, N-dimethylaminoethylpiperidine, 1,8-diazabicyclo(5.4.0)undecen-7,1,2-dimethylimidazol, 1-azabicyclo-(2.2.0)oc
  • amidines such as 2,3-dimethyl-3,4,5,6-tetrahydropyrimidine
  • tetraalkylammonium hydroxides such as tetramethylammonium hydroxide
  • alkali metal hydroxides such as sodium hydroxide and alkali metal alcoholates, such as sodium methylate and potasium isopropylate and alkali metal salts of long chain fatty acids having 10 to 20 C-atoms and optionally OH-groups as side groups
  • the exemplarily mentioned catalysts may be used alone or in mixtures of at leas two of the mentioned catalysts.
  • adjuvants and/or additives common substances may be used in the process according to the invention.
  • common substances e.g. surfactants, internal separating agents, fillers, colorants, pigments, flame retardants, protecting agents against hydrolysis, substances having fungi static and/or bacterial static effects, UV-stabilizers and anti oxygens.
  • Pigments and/or colorants may be used in order to obtain toned or colored shaped particles.
  • a solvent or thinning agent is generally not required for the reaction according to step (3).
  • a solvent or a mixture of two or more solvents is used. Suitable solvents are e.g.
  • carbohydrates particularly toluene, xylene or cyclohexane, esters, particularly ethylglycolacetate, ethylacetate or butyacetate, amides, particularly dimethylformamide or N-methylpyrrolidone, sulfoxides, particularly dimethylsulfoxide, ethers, particularly diisopropylether or methyl-tert.-butyl ether or preferably cyclic ethers, particularly THF or dioxane.
  • esters particularly ethylglycolacetate, ethylacetate or butyacetate
  • amides particularly dimethylformamide or N-methylpyrrolidone
  • sulfoxides particularly dimethylsulfoxide
  • ethers particularly diisopropylether or methyl-tert.-butyl ether or preferably cyclic ethers, particularly THF or dioxane.
  • the present invention also relates to a polyurethane, obtainable by an integrated process, comprising at least the following steps:
  • the polyether alcohol obtainable according to step (2), which is used for preparing the polyurethane, comprises preferably at least one mixed block of ethylene oxide-propylene oxide-units or a terminal propylene oxide-block or a combination of both.
  • the present invention relates to a process for preparing a polyurethane foam, starting from a polyurethane, as defined within the present invention, that process comprising at least the following step:
  • the present invention also encompasses the polyurethane foam as such, obtainable by foaming a polyurethane, as obtained by the reaction according to step (3).
  • the polyurethanes according to the present invention are predominantly characterized by their low content of impurities, such as C6-compounds. This renders the polyurethanes according to the invention particularly suitable for the preparation of polyurethane foams, polyurethane cast skins and elastomers.
  • polyurethane foams preferably polyurethane foams are prepared, which are used in the automotive and furniture industry, such as semi-rigid foams, hard and soft integral foams or RIM (reaction injection moulding)-materials.
  • the present invention relates to a polyurethane, which is derived from a polyether alcohol, obtainable according to step (2), which comprises at least one mixed block of ethylene oxide-propylene oxide-units.
  • the present invention also relates to a polyurethane, derived from a polyether alcohol, obtainable according to step (2), which comprises a terminal propylene oxide block.
  • the polyurethane according to the present invention may suitably be used for preparing shaped bodies, particularly shaped bodies made of soft slab-stock foams on the basis of polyurethane.
  • Particularly advantageous in this respect is the low amount of impurities, which results in that no disturbing smells evolve from the shaped body made of the soft foam.
  • the present invention also relates to a shaped body comprising a polyurethane or a polyurethane foam, respectively obtainable by the integrated process of the invention.
  • Shaped bodies according to the invention are e.g. mattresses, pillows, shaped bodies for the automotive industry and upholstery furniture.
  • soft foams particularly mattresses, shaped bodies for the inner section of cars, such as car seats, sound absorbent shaped bodies, such as e.g. carpets and/or upholstery materials, sponges, cushions, pillows, seating furniture, office furniture, particularly seats, back-rests, orthopedic products;
  • thermoplastic polyurethanes particularly for the use of cables, hoses, animal marks, supports for rails, films, shoe soles and accessories, ski tips and rolled bandages;
  • cold casted elastomers particularly for sheathing of lifting and carrying belts, impact protection elements, industrial edge protectors, toothed belts, screens for abrasive bulk materials, blades, rolls, coatings for rolls, soil protecting sheets against heavy building machines, parts of housings, housings, coatings for deburring drums, pump elements and pump housings, coatings for the outer parts of tubes, coatings for the inner walls of containers, mattresses for cars, cyclones, pulleys for heavy loads, sheave pulleys, guide pulleys, block pulleys, coatings for conveyer belts, coatings for channels, said coatings being resistant against hydrolysis and abrasion, coatings for truck loading areas, impact protectors, clutch parts, coatings for bojen (buoys), inline-skate rolls, special rolls, high impact pump elements;
  • polyurethane coatings particularly for floor coverings, refining of materials, such as wood, leather or metal sheets;
  • polyurethane skins particularly for the use as inserts for shaped bodies, such as dashboards, coverings for car doors, truck and car seats, floorings;
  • integral foams particularly for the use as elements in the inner and outer areas of constructions, complex furnitures, elements for car interiors, skis and snow boards as well as technical functioning parts;
  • RIM-foams particularly for producing prefabricated units for use in the exterior parts in automotive industry, such as extensive facings, fenders and bumpers;
  • Thermoformed foams particularly for preparing ultra-light composite structures for the use in car manufacture, e.g. as an element for roof covers;
  • FIG. 1 shows a X-ray powder diffractogramm of the MOF-5 catalyst as prepared according to Example 1;
  • FIG. 2 shows the sorptionisotherme of said catalyst.
  • the resulting product was characterized by X-ray powder diffraction and an adsorptive determination of micropores.
  • the resulting product shows the X-ray diffractogramm according to FIG. 1, which coincides with MOF-5.

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US10/039,733 US20030078311A1 (en) 2001-10-19 2001-10-19 Process for the alkoxylation of organic compounds in the presence of novel framework materials
TW091124078A TWI300072B (en) 2001-10-19 2002-10-18 Process for the Alkoxylation of Organic Compounds in the Presence of Novel Framework Materials
AT02781271T ATE535560T1 (de) 2001-10-19 2002-10-18 Verfahren zur herstellung von organischen verbindungen in gegenwart eines framework- materials
PL02370429A PL370429A1 (en) 2001-10-19 2002-10-18 Process for the alkoxylation of organic compounds in the presence of novel framework materials
JP2003538229A JP4173101B2 (ja) 2001-10-19 2002-10-18 新規のフレーム構造材料の存在下での有機化合物のアルコキシル化法
CA002464352A CA2464352A1 (en) 2001-10-19 2002-10-18 Process for the alkoxylation of organic compounds in the presence of novel framework materials
CNB028207831A CN100424115C (zh) 2001-10-19 2002-10-18 在新的骨架材料存在下烷氧基化有机化合物的方法
EP02781271A EP1440106B1 (en) 2001-10-19 2002-10-18 Process for the alkoxylation of organic compounds in the presence of novel framework materials
PCT/EP2002/011700 WO2003035717A1 (en) 2001-10-19 2002-10-18 Process for the alkoxylation of organic compounds in the presence of novel framework materials
KR1020047005723A KR100940290B1 (ko) 2001-10-19 2002-10-18 신규한 골격 물질의 존재 하에서 유기 화합물의 알콕시화방법
RU2004115338/04A RU2308465C2 (ru) 2001-10-19 2002-10-18 Способ алкоксилирования органических соединений в присутствии новых каркасных материалов
ES02781271T ES2376050T3 (es) 2001-10-19 2002-10-18 Procedimiento para la alcoxilación de compuestos org�?nicos en presencia de nuevos materiales estructurales.
MXPA04003467A MXPA04003467A (es) 2001-10-19 2002-10-18 Procedimiento para la alcoxilacion de compuestos organicos en presencia de materiales estructurales novedosos.
US10/492,192 US7279517B2 (en) 2001-10-19 2002-10-18 Process for the alkoxylation of organic compounds in the presence of novel framework materials

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US20040225134A1 (en) * 2003-05-09 2004-11-11 The Regents Of The University Of Michigan Implementation of a strategy for achieving extraordinary levels of surface area and porosity in crystals
US7652132B2 (en) 2003-05-09 2010-01-26 The Regents Of The University Of Michigan Implementation of a strategy for achieving extraordinary levels of surface area and porosity in crystals
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US20050124819A1 (en) * 2003-12-05 2005-06-09 The Regents Of The University Of Michigan Metal-organic polyhedra
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US20070068389A1 (en) * 2005-09-26 2007-03-29 Yaghi Omar M Metal-organic frameworks with exceptionally high capacity for storage of carbon dioxide at room-temperature
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US20100132549A1 (en) * 2007-05-11 2010-06-03 The Regents Of The University Of California Adsorptive gas separation of multi-component gases
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US20090062498A1 (en) * 2007-08-30 2009-03-05 The Regents Of The University Of Michigan Novel strategies, linkers and coordination polymers for high-performance sorbents
US20090062409A1 (en) * 2007-08-30 2009-03-05 The Regents Of The University Of Michigan Porous coordination copolymers and methods for their production
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US20100286022A1 (en) * 2007-09-25 2010-11-11 The Regents Of The University Of California Edible and biocompatible metal-organic frameworks
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US10065979B2 (en) 2007-10-01 2018-09-04 Centre National De La Recherche Scientifique-Cnrs Organic/inorganic hybrid nanoparticulates made from iron carboxylates
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US8123841B2 (en) 2008-01-16 2012-02-28 The Board Of Trustees Of The University Of Illinois Column design for micro gas chromatograph
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US8152908B2 (en) 2008-01-16 2012-04-10 The Board Of Trustees Of The University Of Illinois Micromachined gas chromatography columns for fast separation of Organophosphonate and Organosulfur compounds and methods for deactivating same
US20090211452A1 (en) * 2008-01-16 2009-08-27 The Regents Of The University Of Illinois Micromachined Gas Chromatography Columns For Fast Separation of Organophosphonate and Organosulfur Compounds and Methods for Deactivating Same
US8142746B2 (en) 2008-02-21 2012-03-27 Exxonmobil Research And Engineering Company Separation of carbon dioxide from methane utilizing zeolitic imidazolate framework materials
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US20100075123A1 (en) * 2008-04-08 2010-03-25 University of Illinois - Office of Technology Management Water repellent metal-organic frameworks, process for making and uses regarding same
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US9512145B2 (en) 2008-12-18 2016-12-06 The Regents Of The University Of California Porous reactive framework
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US8841471B2 (en) 2009-09-25 2014-09-23 The Regents Of The University Of California Open metal organic frameworks with exceptional surface area and high gas storage capacity
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US9978474B2 (en) 2010-09-27 2018-05-22 The Regents Of The University Of California Conductive open frameworks
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US9669098B2 (en) 2011-10-13 2017-06-06 The Regents Of The University Of California Metal-organic frameworks with exceptionally large pore aperatures
US9078922B2 (en) 2011-10-13 2015-07-14 The Regents Of The University Of California Metal-organic frameworks with exceptionally large pore aperatures
US10035127B2 (en) 2013-11-04 2018-07-31 The Regents Of The University Of California Metal-organic frameworks with a high density of highly charged exposed metal cation sites
US10287304B2 (en) 2014-02-19 2019-05-14 The Regents Of The University Of California Acid, solvent, and thermal resistant metal-organic frameworks
US10494386B2 (en) 2014-03-18 2019-12-03 The Regents Of The University Of California Mesoscopic materials comprised of ordered superlattices of microporous metal-organic frameworks
US10087205B2 (en) 2014-03-28 2018-10-02 The Regents Of The University Of California Metal organic frameworks comprising a plurality of SBUS with different metal ions and/or a plurality of organic linking ligands with different functional groups
US10118877B2 (en) 2014-12-03 2018-11-06 The Regents Of The University Of California Metal-organic frameworks for aromatic hydrocarbon separations
US10058855B2 (en) 2015-05-14 2018-08-28 The Regents Of The University Of California Redox-active metal-organic frameworks for the catalytic oxidation of hydrocarbons
US10597408B2 (en) 2015-11-27 2020-03-24 The Regents Of The University Of California Covalent organic frameworks with a woven structure
US10821417B2 (en) 2015-11-27 2020-11-03 The Regents Of The University Of California Zeolitic imidazolate frameworks
CN113828281A (zh) * 2021-09-18 2021-12-24 集美大学 一种聚氨酯复合材料的制备方法、产品及应用

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US20040249189A1 (en) 2004-12-09
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US7279517B2 (en) 2007-10-09
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CA2464352A1 (en) 2003-05-01
EP1440106B1 (en) 2011-11-30
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