CA2464352A1 - 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 PDFInfo
- Publication number
- CA2464352A1 CA2464352A1 CA002464352A CA2464352A CA2464352A1 CA 2464352 A1 CA2464352 A1 CA 2464352A1 CA 002464352 A CA002464352 A CA 002464352A CA 2464352 A CA2464352 A CA 2464352A CA 2464352 A1 CA2464352 A1 CA 2464352A1
- Authority
- CA
- Canada
- Prior art keywords
- polyurethane
- reacting
- organic
- process according
- organic compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- 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
Abstract
The present invention relates to a process for the alkoxylation of organic compounds comprising the reaction of at least one organic compound with at least onealkoxylating agent in the presence of a catalyst system, wherein a polyetheralcohol is obtained. The catalyst system comprises a metallo organi c framework mate-rial comprising pores and at least one metal ion and at least one at least bidentate organic compound, which is coordinately bounded to sa id metal ion. Furthermore it relates to polyurethanes or polyurethane foams, which are obtainable by using a prepared polyether alcohol as a starting material.
Description
Process for the Alkoxylation of Organic Compounds in the Presence of Novel Framework Materials The present invention relates to a process for the alkoxylation of organic com-pounds 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 alco-l0 hols, 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.
The polyurethanes prepared according to the invention are particularly useful for the preparation of polyurethane foams, polyurethane cast skins and elastomers.
The characteristics of polyurethanes, such as mechanical properties and smell, are particularly strongly dependent upon the isocyanate and polyether alcohols, which 2o are respectively used for their preparation, and optionally upon the used driving agents. Particularly the structure of the polyether alcohol has a strong influence on the characteristics of the obtained polyurethane. The properties of the poly-ether 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.
The reduction of the impurities within the preparation of polyether alcohols and/or polyurethanes is of high interest for various applications. The automotive and furniture industry request in increasing amounts polyurethanes, which possibly are free of emissions and smelling substances. According to the guideline of Daimler CONFIRMATION COPY
The polyurethanes prepared according to the invention are particularly useful for the preparation of polyurethane foams, polyurethane cast skins and elastomers.
The characteristics of polyurethanes, such as mechanical properties and smell, are particularly strongly dependent upon the isocyanate and polyether alcohols, which 2o are respectively used for their preparation, and optionally upon the used driving agents. Particularly the structure of the polyether alcohol has a strong influence on the characteristics of the obtained polyurethane. The properties of the poly-ether 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.
The reduction of the impurities within the preparation of polyether alcohols and/or polyurethanes is of high interest for various applications. The automotive and furniture industry request in increasing amounts polyurethanes, which possibly are free of emissions and smelling substances. According to the guideline of Daimler CONFIRMATION COPY
Chrysler denoted PB VWL 709 of January 11, 2001 it is required that parts to be used inside of cars exhibit a maximum of 100 ppm for the emission of volatile substances and 250 ppm for condensable substances, respectively.
Impurities, which are present in polyurethanes also negatively influence the me-chanical properties thereof. The impurities and side reactions in many cases lead to mono-functional products. The functionality of the polyetheroles and the me-chanical properties of the polyurethanes, such as elongation, tear strength and hardness generally deteriorate.
to Polyether alcohols may be prepared e.g. by way of base or acid catalyzed polyad-dition of allcaline oxides to polyfiznctional organic compounds (starters).
Suitable starters are e.g. water, alcohols, acids or amines or mixtures of two or more thereof. These prepaxation methods are particularly disadvantageous in that sev-eral elaborate purifying steps are necessary in order to separate the catalyst resi-due from the reaction product. Furthermore, with increasing chain length of poly-ether polyoles prepared, the content of mono-functional products and substances with intensive smell, which are not desired within polyurethane production, in-creases.
The reduction of the functionality is particularly disadvantageous for elastomers, since the used polyether alcohols should generally be bi-functional. Due to the mono-functional impurities within the polyether alcohol, the functionality de-creases below 2, resulting in a significant deterioration of the mechanical charac-teristics of the polyurethanes, particularly tear strength and elongation.
The side products generated by side reactions within the base or acid catalyzed reaction are furthermore partly contained in the polyurethane as smelling impuri-ties. Particularly to be mentioned are aldehydes, e.g. propionic aldehyde, cyclo-3o acetales, allylic alcohol and their reaction products. The automotive and furniture industry request in increasing amounts polyetheroles and polyurethanes having reduced or no smell.
Impurities, which are present in polyurethanes also negatively influence the me-chanical properties thereof. The impurities and side reactions in many cases lead to mono-functional products. The functionality of the polyetheroles and the me-chanical properties of the polyurethanes, such as elongation, tear strength and hardness generally deteriorate.
to Polyether alcohols may be prepared e.g. by way of base or acid catalyzed polyad-dition of allcaline oxides to polyfiznctional organic compounds (starters).
Suitable starters are e.g. water, alcohols, acids or amines or mixtures of two or more thereof. These prepaxation methods are particularly disadvantageous in that sev-eral elaborate purifying steps are necessary in order to separate the catalyst resi-due from the reaction product. Furthermore, with increasing chain length of poly-ether polyoles prepared, the content of mono-functional products and substances with intensive smell, which are not desired within polyurethane production, in-creases.
The reduction of the functionality is particularly disadvantageous for elastomers, since the used polyether alcohols should generally be bi-functional. Due to the mono-functional impurities within the polyether alcohol, the functionality de-creases below 2, resulting in a significant deterioration of the mechanical charac-teristics of the polyurethanes, particularly tear strength and elongation.
The side products generated by side reactions within the base or acid catalyzed reaction are furthermore partly contained in the polyurethane as smelling impuri-ties. Particularly to be mentioned are aldehydes, e.g. propionic aldehyde, cyclo-3o acetales, 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 alco-hols and polyurethanes, respectively, having a low amount of impurities, particu-larly 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 to being alkoxylated, with at least one alkoxylating agent in the presence of a cata-lyst system, wherein a polyether alcohol is obtained. This process is characterized in that the catalyst system comprises a metallo-organic framework material com-prising pores and at least one metal ion and at least one at least bidentate organic compound, which is coordinately bound to said metal ion. Furthermore it is solved by an integrated process for the preparation of a polyurethane comprising at least the following steps:
(2) reacting at least one organic compound, which is capable of being alkoxy-lated, with at least one alkoxylating agent via a process as described above, 2o wherein a polyether alcohol is obtained;
v (3) reacting the polyether alcohol of step (2) with at least one isocyanate.
As the alkoxylating agent in step (2) preferably mono- or multifunctional expox-ide 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. Particularly, substituted or unsubstituted alkylene oxides having two to C-atoms, e.g. allcylene oxides having halogen, hydroxy, non-cyclic ether or am-monium substituents are used.
3o As suitable compounds, the following are exemplarily to be mentioned:
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, vinyloxi-rane, 3-phenoxy-1,2-epoxypropane, 2,3-epoxymethyl ether, 2,3-epoxylethyl ether, 2,3-epoxyl isopropyl ether, 2,3-epoxyl-1-propanol, (3,4-epoxybutyl)stearate, 4,5-epoxypentylacetate, 2,3-epoxy propane methacrylate, 2,3-epoxy propane acrylat, glycidylbutyrate, methylglycidate, ethyl-2,3-epoxybutanoate, 4-(trimethylsilyl)butane-1,2-epoxide, 4-(triethylsilyl)butane-1,2-epoxide, 3-(perfluoromethyl)propane oxide, 3-(perfluoroethyl)propane oxide, 3-to (perfluorobutyl)propane oxide, 4-(2,3-epoxypropyl)morpholine, 1-(oxirane-2-ylmethyl)pyrrolidin-2-one, and mixtures of two or more thereof.
Particularly to be mentioned are: aliphatic 1,2-alkylene oxide having 2 to 4 C-atoms, such as ethylene oxide, 1,2-butylene oxide, 2,3-butylene oxide or isobuty-lene oxide, aliphatic 1,2-alkylene oxides having 5 to 24 C-atoms, cycloaliphatic alkylene oxide, such as cyclopentane oxide, cyclohexane oxide or cyclododecatri-ane-(1,5,9)-monoxide, araliphatic alkylene oxide, e.g. styrene oxide.
Particularly preferred are within the present invention ethylene oxide, propylene 2o oxide, 1,2-epoxybutane, 2,3-epoxybutane, styrene oxide, vinyloxirane and any mixtures of two or more thereof within each other, particularly ethylene oxide, propylene oxide and mixtures of ethylene oxide, 1,2-epoxypropane.
As polyether alcohols, within the present invention, particularly polyester polyoles and modified polyetheroles are used, which are obtainable by using eth-ylene 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:
Generally, propylene oxide may be obtained by reacting propylene with oxygen;
hydrogen and oxygen; hydrogen peroxide; organic hydroperoxides; or halohy-drines, preferably by reacting propylene with hydrogen peroxide, more preferred by reacting propylene with hydrogen peroxide in the presence of a catalyst com-prising a zeolithic material, particularly by reacting propylene with hydrogen per-oxide in the presence of a catalyst comprising a titanium-containing zeolithic ma-terial having CS-1-structure.
As a particularly suitable hydroperoxide for the epoxidation according to step (1), 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.
Thus, 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 hy-drogen peroxide.
The epoxidation according to step (1) is in principle known from e.g. DE 100 652.3 and further patent applications of the present applicant, such as DE 100 885.7, 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 encom-passed within the content of the present application with respect to their respective content. By the epoxidation according to step (1), propylene oxide is obtained in high purity. Particularly, the propylene oxide as such obtained exlvbits a content of C6-compunds of < 1 ppm.
Within the present invention, as 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, alco-3o hols, ketones and ethers. Further undesired impurities are propane derivatives, particularly chlorinated propane derivatives, acetaldehyde, propione aldehyde, acetone, dioxolanes, allylic alcohol, pentane, methylpentane, furane, hexane, hex-ene, methoxypropane and methanol.
The propylene oxide obtained according to step (1) may further comprise as fur-s ther side components, up to 100 ppm, particularly up to 40 ppm, methanol and up to 10 ppm, preferably up to 4 ppm, acetaldehyde.
Compared to other known methods for preparing propylene oxide, which are not excluded from the present application, and which are e.g. described in Weisser-to mel, Arpe "Industrielle Organische Chemie", publisher VCH, Weinheim, 4~' Ed., pages 288 to 318, the preferred embodiments of step (1) according to the inven-tion yields propylene oxide having only minor impurities of C6-components and contain no chloro-organic impurities.
15 A summary of the above-referenced prior art and the procedure when preparing polyether alcohols starting from propylene oxide is given in DE 10143195.3.
With regard to the preparation of ethylene oxide, which may also serve as an allc-oxylating agent and which may also be prepared prior to conducting the process 20 for the alkoxylation of an organic compound being capable of being alkoxylated, is e.g. broadly disclosed in U. Onken, Anton Behr, "Chemische Prozesskunde", Vol. 3, Thieme, 1996, pages 303 to 305 and Weissermel, Arpe "Industrial Organic Chemistry", 5th Ed., Wiley, 1998, pages 159 to 181.
25 Within the reaction yielding the polyether alcohols, the alkoxylating agent ob-tamed according to step (1), particularly propylene oxide, 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 ac-cording to step ( 1 ) is beforehand treated, e.g. purified. As the purification 3o method, mention can be made of a fine distillation. Suitable processes are e.g.
disclosed in EP-B 0 557 116.
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 to being alkoxylated, with at least one alkoxylating agent in the presence of a cata-lyst system, wherein a polyether alcohol is obtained. This process is characterized in that the catalyst system comprises a metallo-organic framework material com-prising pores and at least one metal ion and at least one at least bidentate organic compound, which is coordinately bound to said metal ion. Furthermore it is solved by an integrated process for the preparation of a polyurethane comprising at least the following steps:
(2) reacting at least one organic compound, which is capable of being alkoxy-lated, with at least one alkoxylating agent via a process as described above, 2o wherein a polyether alcohol is obtained;
v (3) reacting the polyether alcohol of step (2) with at least one isocyanate.
As the alkoxylating agent in step (2) preferably mono- or multifunctional expox-ide 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. Particularly, substituted or unsubstituted alkylene oxides having two to C-atoms, e.g. allcylene oxides having halogen, hydroxy, non-cyclic ether or am-monium substituents are used.
3o As suitable compounds, the following are exemplarily to be mentioned:
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, vinyloxi-rane, 3-phenoxy-1,2-epoxypropane, 2,3-epoxymethyl ether, 2,3-epoxylethyl ether, 2,3-epoxyl isopropyl ether, 2,3-epoxyl-1-propanol, (3,4-epoxybutyl)stearate, 4,5-epoxypentylacetate, 2,3-epoxy propane methacrylate, 2,3-epoxy propane acrylat, glycidylbutyrate, methylglycidate, ethyl-2,3-epoxybutanoate, 4-(trimethylsilyl)butane-1,2-epoxide, 4-(triethylsilyl)butane-1,2-epoxide, 3-(perfluoromethyl)propane oxide, 3-(perfluoroethyl)propane oxide, 3-to (perfluorobutyl)propane oxide, 4-(2,3-epoxypropyl)morpholine, 1-(oxirane-2-ylmethyl)pyrrolidin-2-one, and mixtures of two or more thereof.
Particularly to be mentioned are: aliphatic 1,2-alkylene oxide having 2 to 4 C-atoms, such as ethylene oxide, 1,2-butylene oxide, 2,3-butylene oxide or isobuty-lene oxide, aliphatic 1,2-alkylene oxides having 5 to 24 C-atoms, cycloaliphatic alkylene oxide, such as cyclopentane oxide, cyclohexane oxide or cyclododecatri-ane-(1,5,9)-monoxide, araliphatic alkylene oxide, e.g. styrene oxide.
Particularly preferred are within the present invention ethylene oxide, propylene 2o oxide, 1,2-epoxybutane, 2,3-epoxybutane, styrene oxide, vinyloxirane and any mixtures of two or more thereof within each other, particularly ethylene oxide, propylene oxide and mixtures of ethylene oxide, 1,2-epoxypropane.
As polyether alcohols, within the present invention, particularly polyester polyoles and modified polyetheroles are used, which are obtainable by using eth-ylene 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:
Generally, propylene oxide may be obtained by reacting propylene with oxygen;
hydrogen and oxygen; hydrogen peroxide; organic hydroperoxides; or halohy-drines, preferably by reacting propylene with hydrogen peroxide, more preferred by reacting propylene with hydrogen peroxide in the presence of a catalyst com-prising a zeolithic material, particularly by reacting propylene with hydrogen per-oxide in the presence of a catalyst comprising a titanium-containing zeolithic ma-terial having CS-1-structure.
As a particularly suitable hydroperoxide for the epoxidation according to step (1), 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.
Thus, 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 hy-drogen peroxide.
The epoxidation according to step (1) is in principle known from e.g. DE 100 652.3 and further patent applications of the present applicant, such as DE 100 885.7, 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 encom-passed within the content of the present application with respect to their respective content. By the epoxidation according to step (1), propylene oxide is obtained in high purity. Particularly, the propylene oxide as such obtained exlvbits a content of C6-compunds of < 1 ppm.
Within the present invention, as 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, alco-3o hols, ketones and ethers. Further undesired impurities are propane derivatives, particularly chlorinated propane derivatives, acetaldehyde, propione aldehyde, acetone, dioxolanes, allylic alcohol, pentane, methylpentane, furane, hexane, hex-ene, methoxypropane and methanol.
The propylene oxide obtained according to step (1) may further comprise as fur-s ther side components, up to 100 ppm, particularly up to 40 ppm, methanol and up to 10 ppm, preferably up to 4 ppm, acetaldehyde.
Compared to other known methods for preparing propylene oxide, which are not excluded from the present application, and which are e.g. described in Weisser-to mel, Arpe "Industrielle Organische Chemie", publisher VCH, Weinheim, 4~' Ed., pages 288 to 318, the preferred embodiments of step (1) according to the inven-tion yields propylene oxide having only minor impurities of C6-components and contain no chloro-organic impurities.
15 A summary of the above-referenced prior art and the procedure when preparing polyether alcohols starting from propylene oxide is given in DE 10143195.3.
With regard to the preparation of ethylene oxide, which may also serve as an allc-oxylating agent and which may also be prepared prior to conducting the process 20 for the alkoxylation of an organic compound being capable of being alkoxylated, is e.g. broadly disclosed in U. Onken, Anton Behr, "Chemische Prozesskunde", Vol. 3, Thieme, 1996, pages 303 to 305 and Weissermel, Arpe "Industrial Organic Chemistry", 5th Ed., Wiley, 1998, pages 159 to 181.
25 Within the reaction yielding the polyether alcohols, the alkoxylating agent ob-tamed according to step (1), particularly propylene oxide, 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 ac-cording to step ( 1 ) is beforehand treated, e.g. purified. As the purification 3o method, mention can be made of a fine distillation. Suitable processes are e.g.
disclosed in EP-B 0 557 116.
_7-The allcoxylating agent as obtained according to step (1), particularly propylene oxide, 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.
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.
to In cases where, besides the alkoxylating agent obtained according to step (1), par-ticularly propylene oxide, at least one further alkoxylating agent, particularly a further alkylene oxide is used, it is possible within the present invention that a mixture of the alkoxylating agent as obtained according to step (1), particularly is 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 ox-ide, 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). Regarding these modified polyether alcohols, par-ticularly to be mentioned are grafted polyether polyoles, particularly those which are prepared by polymerizing styrene and acrylonitril in the presence of polyeth-3o eroles; polyurea dispersions (PHD-polyoles) which are prepared by reacting di-isocyanates and diamines in the presence of polyetheroles; and polyisocyanate polyaddition polyoles (PIPA polyoles), which are prepared by reacting diisocya-nates and amino alcohols in the presence of polyetheroles.
The reaction according to step (2) is carried out in the presence of a catalyst sys-tem.
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 to compound being coordinately bound to the metal ion. Such catalyst systems are known as such and described in e.g. LJS 5,645,50, EP-A-0 709 253, J. Sol.
State Chem.; 152 (2000) p. 3-20, Nature 402 (1999), p. 276 seq., Topics in Catalysis (1999), p. 105-111, Science 291 (2001), p. 1021-23. An inexpensive way for their preparation is the subject of DE 10111230Ø The content of the above-mentioned literature, to which reference is made herein, is fully incorporated in the content of the present application.
The metallo-organic framework materials, as used in the present invention, com-prise 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 measure-ments for deterW fining 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. In a preferred embodi ment, the specific surface areas, as calculated according to the Langmuir model (DIN 66131, 66134) are preferably above 5 m2/g, more preferably above 50 m2/g, particularly above 500 m2/g and may increase into the region of to above 2000 3o m2/g.
_g_ As the 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. As metal ions of these elements, particularly to be mentioned are: Mga+ Caa+ Srz+ Baa+ Scs+ Y3+ Tia+ Zr4+ H f + V4+ V3+ va+ ~3+ Tas+
> > > > > > > > > > > > > >
Cr3+ M03+ W3+ Mn3+ j~3+ ~2+ Re3+ Rea+ Fe3+ Fez+ Rus+ Rua+ Os3+ Osa+
, , o , , o > > 0 0 0 0 to Co3+ Co2+ gha+ ~+~ ha+~ Ir+ Ni2+ Ni+ Pda+ Pd+ Pt~+ Pt+ Cu2+ Cu~ A +
a > > > > > > > > > g~
Au+, Zna+, Cd2+, Hgz+, Al3+, Ga3+, In3+, Tl3+, Si4+, Si2+, Ge4+, Ge2+, Sn4+, Sn2+, Pb4+, Pb2+, As5+, As3+, As+, Sbs+, Sb3+, Sb+ and Bis+, Bi3+, Bi+.
With regard to the preferred metal ions and further details regarding the same, we particularly refer to: EP-A 0 790 253, particularly p. 10, 1. 8-30, section "The Metal Ions", which section is incorporated herein by reference.
As 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 2o 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 aforemen-tioned groups. With regard to the at least bidentate organic compound, specific mention is to be made of compounds having i) an alkyl group substructure, having from 1 to 10 carbon atoms, ii) an aryl group substructure, having from 1 to 5 phenyl rings, iii) an 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 3o group "X", which is covalently bound to the substructure of said compound, and wherein X is selected from the group consisting of C02H, CS2H, NOZ, S03H, Si(OH)s, Ge(OH)3, Sn(OH)3, Si(SH)4, Ge(SH)4, Sn(SH)3, P03H, As03H, As04H, P(SH)3, As(SH)3, CH(RSH)2, C(RSH)3, CH(RNHZ)2, C(RNHZ)3, CH(ROH)2, C(ROH)3, CH(RCN)2, C(RCN)3, wherein R
is an alkyl group having from 1 to 5 carbon atoms, or an aryl group consisting of 1 to 2 phenyl rings, and CH(SH)a, C(SH)3, CH(NH2)2, C(NHa)2, CH(OH)2, C(OH)3, CH(CN)2 and C(CN)3.
Particularly to be mentioned are substituted or unsubstituted, mono- or polynu-clear aromatic di-, tri- and tetracaxboxylic acids and substituted or unsubstituted, 1o aromatic, at least one hetero atom comprising aromatic di-, tri- and tetracarboxylic acids, which have one or more nuclei.
A preferred ligand is 1,3,5-benzene tricarboxyllic acid (BCT), particularly pre-ferred metal ions are Co2+ and Zn2+.
Besides the at least bidentate organic compound, 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:
a. alkyl amines and their corresponding alkyl ammonium salts, containing linear, branched, or cyclic aliphatic groups, having from 1 to 20 carbon at-oms (and their corresponding ammonium salts);
b. aryl amines and their corresponding aryl ammonium salts having from 1 to 5 phenyl rings;
c. alkyl phosphonium salts, containing linear, branched, or cyclic aliphatic groups, having from 1 to 20 carbon atoms;
d. aryl phosphonium salts, having from 1 to 5 phenyl rings;
e. alkyl organic acids and the corresponding alkyl organic anions (and salts) containing linear, branched, or cyclic aliphatic groups, having from 1 to 20 carbon atoms;
f. aryl organic acids and their corresponding aryl organic anions and salts, having from 1 to 5 phenyl rings;
g. aliphatic alcohols, containing linear, branched, or cyclic aliphatic groups, having from 1 to 20 carbon atoms;
h. aryl alcohols having from 1 to 5 phenyl rings;
inorganic anions from the group consisting of:
to sulfate, nitrate, nitrite, sulfite, bisulfate, phosphate, hydrogen phosphate, dihydrogen phosphate, diphosphate, triphosphate, phosphate, phosphate, chloride, chlorate, bromide, bromate, iodide, iodate, carbonate, bicarbon-ate, and the corresponding acids and salts of the aforementioned inorganic anions, j. ammonia, carbon dioxide, methane, oxygen, ethylene, hexane, benzene, toluene, xylene, chlorobenzene, nitrobenzene, naphthalene, thiophene, pyridine, acetone, 1-2-dichloroethane, methylenechloride, tetrahydrofuran, ehtanolamine, triethylamine and trifluoromethylsulfonic acid.
2o Further details regarding the at least bidentate organic compounds and the mono-dentate substances, from which the ligands of the framework material as used in the present application are derived, may be deduced from EP-A 0 790 253, whose respective content is incorporated into the present application by reference.
Particularly preferred are within the present application framework materials of the kind described herein, which comprise Zn2+ as a metal ion and ligands derived from teraphthalic acid as the bidentate compound, which are known as M~F-5 in the literature.
Further metal ions and at least bidentate organic compounds and mono-dentate substances, which are respectively useful for the preparation of the framework materials used in the present invention as well as processes for their preparation are particularly disclosed in EP-A 0 790 253, US 5,648,508 and DE 10111230Ø
As solvents, which are particularly useful for the preparation of MOF-5, in addi-tion to the solvents disclosed in the above-referenced literature dimethyl form-amide, diethyl formamide and N-methylpyrollidone, alone, in combination with each other or in combination with other solvents may be used. Within the prepa-1o ration of the framework materials, particularly within the preparation of MOF-5, 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 adju-vants (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 granula-2o tion as well as by evaporation of the mother liquor at elevated temperature and/or in vacuo and concentrating of the solid.
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.
In step (2) according to the invention, the alkoxylating agent, particularly propyl-ene 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).
Within the present invention, in principle all organic compounds, which can be alkoxylated, may be used. As particularly suitable organic compounds, the fol lowing are to be mentioned:
water, 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 l0 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 etha-nolamine, N-methyl- and N-ethyl-ethanolamine, dialkanolamines, such as dietha-nolamine, N-methyl- and N-ethyl-diethanolamine, and trialkanolamines, such as triethanolamine, and ammonia and polyvalent alcohols, such as monoethylenegly-col, propandiol-1,2 and-1,3 diethyleneglykol, dipropyleneglycol, butanediol-1,4, hexanediol-1,6, glycerol, trimethylolpropane, pentaerythrit, sorbite and saccha-rose. As the preferred polyether polyalcohols, addition products ethylene oxide and/or propylene oxide and water, monoethyleneglycol, diethyleneglykol, pro-pandiol-1,2, diproplyeneglycol, glycerol, trimethylolpropane, ethylendiamine, triethanolamine, pentaerythrit, sorbite and/or saccharose are used alone or in ad-mixture with each other.
The organic compounds may also be used in the form of alkoxylates, particularly those having a molecular weight MW in the range of 62 to 15,000 g/mol.
Furthermore, also macromolecules having functional groups with active hydrogen atoms, such as hydroxyl groups, particularly those which are mentioned in WO
01/16209 may be used.
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).
to Within the present invention, one or more isocyanates may be used. Besides the polyether alcohols as obtained according to step (2) within the reaction according to step (3), further components having groups which are reactive towards isocya-nates, particularly those having hydroxyl groups, may be additionally used.
As further 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 2o carbon atoms, with polyvalent alcohols, preferably dioles, respectively having 2 to 12 carbon atoms, preferably 2 to 6 carbon atoms. As the dicarboxylic acids, the following may be preferably used:
succinic acid, glutaric acid, adipinic acid, suberic acid, azelaic acid, sebacinic acid, decanedicarboxylic acid, malefic acid, fumaric acid, phthalic acid, isophthalic acid and teraphthalic acid. The dicarboxylic acids may be used alone or in ad-mixture with each other. Instead of the free dicarboxylic acid, also the corre-sponding dicarboxylic acid derivatives, such as dicarboxylic esters of alcohols having 1 to 4 carbon atoms or dicarboxylic acid anhydrides may be used. Exam-ples 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. Preferably used are ethanediole, diethyleneglycol, 1,4-butanediole, 1,5-pentanediole, 1,6-hexanediole, glycerol and/or trimethylolpropane. Furthermore, polyesterpolyoles made of lactones, e.g.
caprolactone or hydroxy carboxylic acid, such as oc-hxydroxycarpronic acid may be used. For the preparation of the polyesterpolyoles, the organic, e.g.
aromatic or to preferably aliphatic polycarboxylic acids and/or derivatives thereof may be re-acted with the polyvalent alcohol in the absence of a catalyst or preferably in the presence of an esterifying catalyst. Preferably, the reaction is carried out in an inert atmosphere, e.g. in a nitrogen, carbon monoxide, helium, argon, etc.
atmos-phere. 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. According to a preferred embodiment of this condensation reaction, the mixture to be esterified is first reacted up to an acid number of 80 to 30, prefera-bly 40 to 30, under normal pressure and at the above-mentioned temperatures, and 2o subsequently polycondensated at a pressure of lower than 500 mbar, preferably 50 to 150 mbar. As 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.
However, 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. For the preparation of the polyesterpolyoles, the organic polycar-boxylic 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 3o and a hydroxyl number of preferably 22 to 100 mg KOH/g. Furthermore, use can be made of compounds which are reactive towards isocyanates, such as 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 buta-nediole-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 ob-tained by reacting ethylene oxide and/or 1,2-propylene oxide with the above-mentioned dioles and/or trioles as an H-functional compound.
According to the present invention, the polyether alcohol of step (2) is reacted with at least one isocyanate. In principle, all 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, prefera-bly diisocyanates.
The following individual compounds are particularly to be mentioned:
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, lysines-terdiisocyanate (LDI) and/or hexamethylenediisocyanate-1,6 (HDI); cyclo-aliphatic diisocyanates, such as cyclohexane-1,3- and 1,4-diisocyanate and arbi-trary 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-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (IPDI).
Furthermore, the following isocyanates are exemplary to be mentioned:
2,4- and 2,6-toluyliendiisocyanate and the respective mixtures of isomers, 4,4'-, 2,4'- and 2,2'-diphenylinethanediisocyanate and the respective mixtures of iso-mers, mixtures of 4,4'- and 2,2'-diphenylmethanediisocyanates, polyphenyl-polymethylenepolyisocyanates, mixtures of 4,4'-, 2,4'- and 2,2'-diphenylinethanediisocyanates and polyphenylpolymethylene-polyisocyanates (raw-MDI) and mixtures of raw-MDl and toluylendiisocyanates. Furthermore, mixtures comprising at least two of the above-mentioned isocyanates may also be used. Furthermore, modified isocyanates having isocyanurate, bouret, ester, urea, allophanate, carbodiimid, uretdione, and/or urethane groups (in the following also l0 denoted urethane group modified) containing di- and/or polyisocyanates may be used.
Among those, the following indivial compounds may be mentioned:
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 mix tures, raw-MDI or 2,4- and 2,6-toluylendiisocyanates, which are respectively modified, e.g. with low molecular weight dioles, trioles, dialkyleneglycoles, trial kyleneglycoles or polyoxyalkyleneglycoles having molecular weights of up to 6000, particularly molecular weights of up to 1500, may be used alone or in ad-mixture with each other. As the 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. Furthermore, 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.
Furthermore, use can also be made of liquid polyisocyanates containing carbodi-imide groups, respectively having NCO-contents of 36.6 to 15, preferably 31 to 21 wt.%, relative to the total weight, e.g. on the basis of 4,4'-, 2,4'-and/or 2,2'-diphenylinethanediisocyanate and/or 2,4- and/or 2,6-toluylenediisocyanate. The 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. As modified isocyanates, preferably use is made of isocyanurate, biuret and/or ure-thane group modified aliphatic and/or cycloaliphatic diisocyanates, e.g. those which are already mentioned, which are provided with biuret and/or cyanurate l0 groups according to known processes, and which comprise at least one, preferably at least tyvo 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 andlor Mannich bases. Furthermore, trimers of isocya-nates 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.
Iso-2o cyanates containing biuret groups are also commercially available.
The reaction according to 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, Munich, 3'd Ed., 1993, p. 139 to 193.
Optionally, within the reaction according to step (3), further, 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 3o amino compounds having 2 to about 20, e.g. 2 to about 12 C-atoms. As examples, the following are to be mentioned:
ethylamine, n-propylamine, i-propylamine, n-propylamin, sec.-propylamine, tert.-butylamine, 1-aminoisobutane, substituted amines having 2 to about 20 C-atoms, such as 2-(N,N-dimethylamino)-1-aminoethane, aminomercaptanes, such as 1-amino-2-mercaptoethane, diamines, aliphatic aminoalkohols having 2 to about 20, preferably 2 to about 12 C-atoms, such as methanolamine, 1-amino-3,3-dimethyl-pentane-5-ol, 2-aminohexane-2',2"-diethanolamine, 1-Amino-2,5-dimethylcyclohexane-4-ol, 2-aminopropanol, 2-aminobutanol, 3-aminopropanol, 1-amino-2-propanol, 2-amino-2-methyl-1-propanol, 5-aminopentanol, 3-aminomethyl-3,5,5-trimethylcyclohexanol, 1-amino-1-cyclopentane-methanol, 2-amino-2-ethyl-1,3-propandiole, aromatic-aliphatic or aromatic or aromatic-cycloaliphatic aminoalcohols having 6 to about 20 C-atoms, wherein as the aro-matic structures heterocyclic ring systems or preferably isocyclic ring systems such as naphthalene or particularly benzene derivatives, such as 2-aminobenzylalcohol, 3-(hydroxymethyl)anilin, 2-amino-3-phenyl-1-propanol, 2-amino-1-phenylethanol, 2-phenylglycinol or 2-amino-1-phenyl-1,3-propandiole and mixtures of two or more of such compounds.
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. In the following, possi-bly used catalysts are exemplarily mentioned:
Tertiary amines, such as triethylamine, tributylamine, dirnethylbenzylamine, dicy-clohexylmethylamine, dimethylcyclohexylamine, N,N,N',N'-tetramethyldiaminodiethylether, bis(dimethylaminopropyl)urea, N-methyl- and N-ethyhnorpholine, N-cyclohexylmorpholine, N,N,N',N'-3o tetramethylethylenediamine, N,N,N',N'-tetramethylbutanediamine, N,N,N',N'-tetramethylhexanediamine-1,6, pentamethyldiethylenetriamine, dimethylpiper-azine, N-dimethylaminoethylpiperidine, 1,8-diazabicyclo(5.4.0)undecen-7,1,2-dimethylimidazol, 1-azabicyclo-(2.2.0)octane, 1,4-diazabicyclo(2.2.2)octan (DABCO), alkonolamine compounds, such as triethanolamine, triisopropano-lamine, N-methyl-and N-ethyl diethanolamine, dimethylaminoethanol, 2-(N,N-dimethylaminoethoxy)ethanol, N,N,N',N"-tris(dialkylaminoalkyl)hexahydrotriazines, such as N,N',N"-tris(dimethylaminopropyl)-s-hexahydrotriazine, preferably triethylenediamine, pentamethylenediethylentriamin and/or bis(dimethylamino)ether; metal salts, e.g.
inorganic andlor organic compounds of Fe, Pb, Zn and/or Sn, in common oxidea-tion stages of the metals, respectively, such as Fe(II)-chloride, Zn-chloride, Pb-octoate and preferably Sn-compounds, such as Sn(II)-compounds, particularly Sn-dioctoate, Sn-diethylhexlmaleate and/or Sn(IV)-compounds, such as dialkyl-Sn-di(isooctylmercaptoacetate), dialkyl-Sn-di(2-ethylhexylmaleate), dialkyl-Sn-di(2-ethylhexylmercaptoacetate), dialkyl-Sn-di(isooctylmercaptoacetate), dialkyl-Sn-i s dilaurate, dialkyl-Sn-dimaleate, diallcyl-Sn-di(mercaptoacetate).
Furthermore, amidines, such as 2,3-dimethyl-3,4,5,6-tetrahydropyrimidine, tetraalkylammo-nium hydroxides, such as tetramethylammonium hydroxide, alkali metal hydrox-ides, such as sodium hydroxide and alkali metal alcoholates, such as sodium methylate and potasium isopropylate and alkali metal salts of long chain fatty ac-2o ids having 10 to 20 C-atoms and optionally OH-groups as side groups, may re-spectively be used as catalysts. The exemplarily mentioned catalysts may be used alone or in mixtures of at leas two of the mentioned catalysts.
Optionally, as adjuvants and/or additives common substances may be used in the 25 process according to the invention. To be mentioned are 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.
In general, the use of a solvent or thinning agent is generally not required for the reaction according to step (3). However, within a preferred embodiment of said reaction, a solvent or a mixture of two or more solvents is used. Suitable solvents are e.g. carbohydrates, particularly toluene, xylene or cyclohexane, esters, par-ticularly ethylglycolacetate, ethylacetate or butyacetate, amides, particularly di-methylformamide or N-methylpyrrolidone, sulfoxides, particularly dimethylsul-foxide, ethers, particularly diisopropylether or methyl-tert.-butyl ether or prefera-bly cyclic ethers, particularly THF or dioxane.
l0 Furthermore, the present invention also relates to a polyurethane, obtainable by an integrated process, comprising at least the following steps, (2) reacting at least one organic compound with at least one allcoxy-lating agent via a process as described above, wherein a polyether alcohol is obtained;
(3) reacting the polyether alcohol of step (2) with at least one isocya-nate.
The polyether alcohol, obtainable according to step (2), which is used for prepar-ing 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.
Furthermore, the present invention relates to a process for preparing a polyure-thane foam, starting from a polyurethane, as defined within the present invention, that process comprising at least the following step, (4) foaming the polyurethane as used as a starting material:
The present invention also encompasses the polyurethane foam as such, obtain-3o able by foaming a polyurethane, as obtained by the reaction according to step (3).
The polyurethanes according to the present invention are predominantly charac-terized by their low content of impurities, such as C6-compounds. This renders the polyurethanes according to the invention particularly suitable for the prepara-tion of polyurethane foams, polyurethane cast skins and elastomers.
Among the polyurethane foams preferably polyurethane foams axe 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.
to Processes for the preparation of polyurethane foams are described in Becker, Braun, "Polyurethanes", Kunststoffhandbuch, vol. 7, Carl Hanser, Munich, 3ra edition, 1993, p. 193 to 265.
In a preferred embodiment, the present invention relates to a polyurethane, which is derived from a polyether alcohol, obtainable according to step (2), which com-prises at least one mixed block of ethylene oxide-propylene oxide-units.
The present invention also relates to a polyurethane, derived from a polyether al-cohol, obtainable according to step (2), which comprises a terminal propylene oxide block.
The polyurethane according to the present invention, particularly the above-mentioned polyurethane, may suitably be used for preparing shaped bodies, par-ticularly shaped bodies made of soft slab-stock foams on the basis of polyure-thane. 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.
In addition thereto, the narrower molecular weight distribution due to the lower amount of mono-functional side compounds leads to an improved processing during foaming.
Thus, the present invention also relates to a shaped body comprising a polyure-thane 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 l0 bodies for the automotive industry and upholstery furniture.
The following shaped bodies according to the invention are to be mentioned:
- 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, ani-mal marks, supports for rails, films, shoe soles and accessories, ski tips and 2o 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 debarring drums, pump elements and pump hous-ings, 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 ele-ments;
- soft integral foams, particularly steering wheels, seals for air filters, steer-s ing knob, foaming of wires, casings for containers, arm-rests, shoe soles made of polyurethane;
- polyurethane coatings, particularly for floor coverings, refining of materi-als, such as wood, leather or metal sheets;
- polyurethane skins, particularly for the use as inserts for shaped bodies, 1o such as dashboards, coverings for car doors, truck and car seats, floorings;
- rigid polyurethane foams, particularly for the use as damping material or construction material;
- integral foams, particularly for the use as elements in the inner and outer areas of constructions, complex furnitures, elements for car interiors, skis 15 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 2o structures for the use in car manufacture, e.g. as an element for roof cov-ers;
- semi-rigid foams, particularly for underfoaming of films, skins or leather or fiber reinforced construction elements.
25 The invention is now further described by way of the following examples, which are, however, not meant to limit the scope of the present application.
Examples Figure 1 shows a X-ray powder diffractogramm of the MOF-5 catalyst as pre-pared according to Example 1 (the ordinate Y describes Lin in Counts and the abscisse X the 2-Theta-Scale).
Figure 2 shows the sorptionisotherme of said catalyst (the ordinate ~A
describes the volume as absorbed in cm 3lg STP and the abscisse RP the relative pressure (P/PO)).
Example 1 (Preparation of MOF-5) Starting MaterialMolar CalculatedExperimental Amount terephthalic acid12.3 mmol 2.04 g 2.04 g Zinc nitrate-tetra36.98 mmol 9.67 g 9.68 g hy-drate diethylformamide 2568.8 mmol282.2 282.2 g g (Merck) The above-mentioned amounts of the starting materials were dissolved in a beaker in the order diethylformamide, terephthalic acid and zinc nitride. The resulting solution was introduced into two autoclaves (250 ml), having respectively inner walls which were covered by teflon.
The crystallization occurred at 105° C within twenty hours.
Subsequently, the orange solvent was decanted from the yellow crystals, said crystals were again covered by 20 ml dimethylformamide, the latter being again decanted. This pro-cedure was repeated three times. Subsequently, 20 ml chloroform were poured onto the solid, which was washed and decanted by said solvent two times.
The crystals (14.4 g), which were still moist, were introduced into a vacuum de-vice and first at room temperature in vacuo (10'~ mbar), afterwards dried at 120°C.
Subsequently, the resulting product was characterized by X-ray powder diffrac-tion and an adsorptive determination of micropores. The resulting product shows the X-ray diffractogramm according to Figure l, which coincides with MOF-5.
The determination of the sorptionsisotherme, as depicted in Figure 2, with argon to (87I~; Micromeritics ASAP 2010) shows an isotherme of type I, being typical for microporous materials, and having a specific surface area of 3020 m~'/g, calculated according to Langmuir, and a micropore volume of 0.97 ml/g (at a relative pres-sure pp° = 0,4).
Example 2 Alkox~lation of Dipropylene Glycol with Propylene Oxide) Dipropylene glycol (33.5 g corresponding to 0.25 mol) and 0.75 g of the catalyst prepared according to Example 1 were introduced in an autoclave. Subsequently, the autoclave was filled with 116 g propylene oxide (2 mol). The reaction was 2o carried out at 135°C and a maximum pressure of 12.1 bar, and in total 2.44 mol propylene oxide/mol starting material were reacted to obtain a polyol.
Example 3 (Alkoxylation of Methyl Diprop~ene Glycol with Ethylene Oxide) Methyl dipropylene glycol (30 g corresponding to 0.25 mol) and 0.59 g of the catalyst as prepared according to Example 1 were introduced in an autoclave.
The autoclave was then filled with 88 g ethylene oxide (2 mol). The reaction was car-_27_ ried out at 135°C and a maximum pressure of 21.2 bar. In total, 2.45 mol ethylene oxide/mol starting compound were reacted to obtain a polyol.
Example 4 Allcoxylation of Acrylic Acid with Ethylene Oxide) 33.2 g acrylic acid (stabilized with 2,2',6,6'-tetramethyl-4-hydroxypiperidine-N-oxide and phenothiazine) and 0.5 g catalyst of Example 1 were weighed into a 300 ml steering autoclave under nitrogen atmosphere. The autoclave was closed and pressurized with 10 bar nitrogen. Upon steering 20 g ethylene oxide were to subsequently introduced via a screw press. After five hours at 50°C
the catalyst was filtered off and the raw product was analyzed by gas chromatography. Based on the area percentages the following composition of the solution (residual ethyl-ene oxide not considered):
Acrylic acid 76%, monoethylene glycol acrylate 10%, diethylene glycol acrylate 9%, other side products 5%.
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.
to In cases where, besides the alkoxylating agent obtained according to step (1), par-ticularly propylene oxide, at least one further alkoxylating agent, particularly a further alkylene oxide is used, it is possible within the present invention that a mixture of the alkoxylating agent as obtained according to step (1), particularly is 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 ox-ide, 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). Regarding these modified polyether alcohols, par-ticularly to be mentioned are grafted polyether polyoles, particularly those which are prepared by polymerizing styrene and acrylonitril in the presence of polyeth-3o eroles; polyurea dispersions (PHD-polyoles) which are prepared by reacting di-isocyanates and diamines in the presence of polyetheroles; and polyisocyanate polyaddition polyoles (PIPA polyoles), which are prepared by reacting diisocya-nates and amino alcohols in the presence of polyetheroles.
The reaction according to step (2) is carried out in the presence of a catalyst sys-tem.
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 to compound being coordinately bound to the metal ion. Such catalyst systems are known as such and described in e.g. LJS 5,645,50, EP-A-0 709 253, J. Sol.
State Chem.; 152 (2000) p. 3-20, Nature 402 (1999), p. 276 seq., Topics in Catalysis (1999), p. 105-111, Science 291 (2001), p. 1021-23. An inexpensive way for their preparation is the subject of DE 10111230Ø The content of the above-mentioned literature, to which reference is made herein, is fully incorporated in the content of the present application.
The metallo-organic framework materials, as used in the present invention, com-prise 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 measure-ments for deterW fining 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. In a preferred embodi ment, the specific surface areas, as calculated according to the Langmuir model (DIN 66131, 66134) are preferably above 5 m2/g, more preferably above 50 m2/g, particularly above 500 m2/g and may increase into the region of to above 2000 3o m2/g.
_g_ As the 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. As metal ions of these elements, particularly to be mentioned are: Mga+ Caa+ Srz+ Baa+ Scs+ Y3+ Tia+ Zr4+ H f + V4+ V3+ va+ ~3+ Tas+
> > > > > > > > > > > > > >
Cr3+ M03+ W3+ Mn3+ j~3+ ~2+ Re3+ Rea+ Fe3+ Fez+ Rus+ Rua+ Os3+ Osa+
, , o , , o > > 0 0 0 0 to Co3+ Co2+ gha+ ~+~ ha+~ Ir+ Ni2+ Ni+ Pda+ Pd+ Pt~+ Pt+ Cu2+ Cu~ A +
a > > > > > > > > > g~
Au+, Zna+, Cd2+, Hgz+, Al3+, Ga3+, In3+, Tl3+, Si4+, Si2+, Ge4+, Ge2+, Sn4+, Sn2+, Pb4+, Pb2+, As5+, As3+, As+, Sbs+, Sb3+, Sb+ and Bis+, Bi3+, Bi+.
With regard to the preferred metal ions and further details regarding the same, we particularly refer to: EP-A 0 790 253, particularly p. 10, 1. 8-30, section "The Metal Ions", which section is incorporated herein by reference.
As 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 2o 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 aforemen-tioned groups. With regard to the at least bidentate organic compound, specific mention is to be made of compounds having i) an alkyl group substructure, having from 1 to 10 carbon atoms, ii) an aryl group substructure, having from 1 to 5 phenyl rings, iii) an 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 3o group "X", which is covalently bound to the substructure of said compound, and wherein X is selected from the group consisting of C02H, CS2H, NOZ, S03H, Si(OH)s, Ge(OH)3, Sn(OH)3, Si(SH)4, Ge(SH)4, Sn(SH)3, P03H, As03H, As04H, P(SH)3, As(SH)3, CH(RSH)2, C(RSH)3, CH(RNHZ)2, C(RNHZ)3, CH(ROH)2, C(ROH)3, CH(RCN)2, C(RCN)3, wherein R
is an alkyl group having from 1 to 5 carbon atoms, or an aryl group consisting of 1 to 2 phenyl rings, and CH(SH)a, C(SH)3, CH(NH2)2, C(NHa)2, CH(OH)2, C(OH)3, CH(CN)2 and C(CN)3.
Particularly to be mentioned are substituted or unsubstituted, mono- or polynu-clear aromatic di-, tri- and tetracaxboxylic acids and substituted or unsubstituted, 1o aromatic, at least one hetero atom comprising aromatic di-, tri- and tetracarboxylic acids, which have one or more nuclei.
A preferred ligand is 1,3,5-benzene tricarboxyllic acid (BCT), particularly pre-ferred metal ions are Co2+ and Zn2+.
Besides the at least bidentate organic compound, 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:
a. alkyl amines and their corresponding alkyl ammonium salts, containing linear, branched, or cyclic aliphatic groups, having from 1 to 20 carbon at-oms (and their corresponding ammonium salts);
b. aryl amines and their corresponding aryl ammonium salts having from 1 to 5 phenyl rings;
c. alkyl phosphonium salts, containing linear, branched, or cyclic aliphatic groups, having from 1 to 20 carbon atoms;
d. aryl phosphonium salts, having from 1 to 5 phenyl rings;
e. alkyl organic acids and the corresponding alkyl organic anions (and salts) containing linear, branched, or cyclic aliphatic groups, having from 1 to 20 carbon atoms;
f. aryl organic acids and their corresponding aryl organic anions and salts, having from 1 to 5 phenyl rings;
g. aliphatic alcohols, containing linear, branched, or cyclic aliphatic groups, having from 1 to 20 carbon atoms;
h. aryl alcohols having from 1 to 5 phenyl rings;
inorganic anions from the group consisting of:
to sulfate, nitrate, nitrite, sulfite, bisulfate, phosphate, hydrogen phosphate, dihydrogen phosphate, diphosphate, triphosphate, phosphate, phosphate, chloride, chlorate, bromide, bromate, iodide, iodate, carbonate, bicarbon-ate, and the corresponding acids and salts of the aforementioned inorganic anions, j. ammonia, carbon dioxide, methane, oxygen, ethylene, hexane, benzene, toluene, xylene, chlorobenzene, nitrobenzene, naphthalene, thiophene, pyridine, acetone, 1-2-dichloroethane, methylenechloride, tetrahydrofuran, ehtanolamine, triethylamine and trifluoromethylsulfonic acid.
2o Further details regarding the at least bidentate organic compounds and the mono-dentate substances, from which the ligands of the framework material as used in the present application are derived, may be deduced from EP-A 0 790 253, whose respective content is incorporated into the present application by reference.
Particularly preferred are within the present application framework materials of the kind described herein, which comprise Zn2+ as a metal ion and ligands derived from teraphthalic acid as the bidentate compound, which are known as M~F-5 in the literature.
Further metal ions and at least bidentate organic compounds and mono-dentate substances, which are respectively useful for the preparation of the framework materials used in the present invention as well as processes for their preparation are particularly disclosed in EP-A 0 790 253, US 5,648,508 and DE 10111230Ø
As solvents, which are particularly useful for the preparation of MOF-5, in addi-tion to the solvents disclosed in the above-referenced literature dimethyl form-amide, diethyl formamide and N-methylpyrollidone, alone, in combination with each other or in combination with other solvents may be used. Within the prepa-1o ration of the framework materials, particularly within the preparation of MOF-5, 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 adju-vants (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 granula-2o tion as well as by evaporation of the mother liquor at elevated temperature and/or in vacuo and concentrating of the solid.
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.
In step (2) according to the invention, the alkoxylating agent, particularly propyl-ene 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).
Within the present invention, in principle all organic compounds, which can be alkoxylated, may be used. As particularly suitable organic compounds, the fol lowing are to be mentioned:
water, 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 l0 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 etha-nolamine, N-methyl- and N-ethyl-ethanolamine, dialkanolamines, such as dietha-nolamine, N-methyl- and N-ethyl-diethanolamine, and trialkanolamines, such as triethanolamine, and ammonia and polyvalent alcohols, such as monoethylenegly-col, propandiol-1,2 and-1,3 diethyleneglykol, dipropyleneglycol, butanediol-1,4, hexanediol-1,6, glycerol, trimethylolpropane, pentaerythrit, sorbite and saccha-rose. As the preferred polyether polyalcohols, addition products ethylene oxide and/or propylene oxide and water, monoethyleneglycol, diethyleneglykol, pro-pandiol-1,2, diproplyeneglycol, glycerol, trimethylolpropane, ethylendiamine, triethanolamine, pentaerythrit, sorbite and/or saccharose are used alone or in ad-mixture with each other.
The organic compounds may also be used in the form of alkoxylates, particularly those having a molecular weight MW in the range of 62 to 15,000 g/mol.
Furthermore, also macromolecules having functional groups with active hydrogen atoms, such as hydroxyl groups, particularly those which are mentioned in WO
01/16209 may be used.
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).
to Within the present invention, one or more isocyanates may be used. Besides the polyether alcohols as obtained according to step (2) within the reaction according to step (3), further components having groups which are reactive towards isocya-nates, particularly those having hydroxyl groups, may be additionally used.
As further 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 2o carbon atoms, with polyvalent alcohols, preferably dioles, respectively having 2 to 12 carbon atoms, preferably 2 to 6 carbon atoms. As the dicarboxylic acids, the following may be preferably used:
succinic acid, glutaric acid, adipinic acid, suberic acid, azelaic acid, sebacinic acid, decanedicarboxylic acid, malefic acid, fumaric acid, phthalic acid, isophthalic acid and teraphthalic acid. The dicarboxylic acids may be used alone or in ad-mixture with each other. Instead of the free dicarboxylic acid, also the corre-sponding dicarboxylic acid derivatives, such as dicarboxylic esters of alcohols having 1 to 4 carbon atoms or dicarboxylic acid anhydrides may be used. Exam-ples 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. Preferably used are ethanediole, diethyleneglycol, 1,4-butanediole, 1,5-pentanediole, 1,6-hexanediole, glycerol and/or trimethylolpropane. Furthermore, polyesterpolyoles made of lactones, e.g.
caprolactone or hydroxy carboxylic acid, such as oc-hxydroxycarpronic acid may be used. For the preparation of the polyesterpolyoles, the organic, e.g.
aromatic or to preferably aliphatic polycarboxylic acids and/or derivatives thereof may be re-acted with the polyvalent alcohol in the absence of a catalyst or preferably in the presence of an esterifying catalyst. Preferably, the reaction is carried out in an inert atmosphere, e.g. in a nitrogen, carbon monoxide, helium, argon, etc.
atmos-phere. 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. According to a preferred embodiment of this condensation reaction, the mixture to be esterified is first reacted up to an acid number of 80 to 30, prefera-bly 40 to 30, under normal pressure and at the above-mentioned temperatures, and 2o subsequently polycondensated at a pressure of lower than 500 mbar, preferably 50 to 150 mbar. As 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.
However, 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. For the preparation of the polyesterpolyoles, the organic polycar-boxylic 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 3o and a hydroxyl number of preferably 22 to 100 mg KOH/g. Furthermore, use can be made of compounds which are reactive towards isocyanates, such as 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 buta-nediole-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 ob-tained by reacting ethylene oxide and/or 1,2-propylene oxide with the above-mentioned dioles and/or trioles as an H-functional compound.
According to the present invention, the polyether alcohol of step (2) is reacted with at least one isocyanate. In principle, all 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, prefera-bly diisocyanates.
The following individual compounds are particularly to be mentioned:
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, lysines-terdiisocyanate (LDI) and/or hexamethylenediisocyanate-1,6 (HDI); cyclo-aliphatic diisocyanates, such as cyclohexane-1,3- and 1,4-diisocyanate and arbi-trary 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-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (IPDI).
Furthermore, the following isocyanates are exemplary to be mentioned:
2,4- and 2,6-toluyliendiisocyanate and the respective mixtures of isomers, 4,4'-, 2,4'- and 2,2'-diphenylinethanediisocyanate and the respective mixtures of iso-mers, mixtures of 4,4'- and 2,2'-diphenylmethanediisocyanates, polyphenyl-polymethylenepolyisocyanates, mixtures of 4,4'-, 2,4'- and 2,2'-diphenylinethanediisocyanates and polyphenylpolymethylene-polyisocyanates (raw-MDI) and mixtures of raw-MDl and toluylendiisocyanates. Furthermore, mixtures comprising at least two of the above-mentioned isocyanates may also be used. Furthermore, modified isocyanates having isocyanurate, bouret, ester, urea, allophanate, carbodiimid, uretdione, and/or urethane groups (in the following also l0 denoted urethane group modified) containing di- and/or polyisocyanates may be used.
Among those, the following indivial compounds may be mentioned:
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 mix tures, raw-MDI or 2,4- and 2,6-toluylendiisocyanates, which are respectively modified, e.g. with low molecular weight dioles, trioles, dialkyleneglycoles, trial kyleneglycoles or polyoxyalkyleneglycoles having molecular weights of up to 6000, particularly molecular weights of up to 1500, may be used alone or in ad-mixture with each other. As the 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. Furthermore, 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.
Furthermore, use can also be made of liquid polyisocyanates containing carbodi-imide groups, respectively having NCO-contents of 36.6 to 15, preferably 31 to 21 wt.%, relative to the total weight, e.g. on the basis of 4,4'-, 2,4'-and/or 2,2'-diphenylinethanediisocyanate and/or 2,4- and/or 2,6-toluylenediisocyanate. The 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. As modified isocyanates, preferably use is made of isocyanurate, biuret and/or ure-thane group modified aliphatic and/or cycloaliphatic diisocyanates, e.g. those which are already mentioned, which are provided with biuret and/or cyanurate l0 groups according to known processes, and which comprise at least one, preferably at least tyvo 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 andlor Mannich bases. Furthermore, trimers of isocya-nates 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.
Iso-2o cyanates containing biuret groups are also commercially available.
The reaction according to 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, Munich, 3'd Ed., 1993, p. 139 to 193.
Optionally, within the reaction according to step (3), further, 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 3o amino compounds having 2 to about 20, e.g. 2 to about 12 C-atoms. As examples, the following are to be mentioned:
ethylamine, n-propylamine, i-propylamine, n-propylamin, sec.-propylamine, tert.-butylamine, 1-aminoisobutane, substituted amines having 2 to about 20 C-atoms, such as 2-(N,N-dimethylamino)-1-aminoethane, aminomercaptanes, such as 1-amino-2-mercaptoethane, diamines, aliphatic aminoalkohols having 2 to about 20, preferably 2 to about 12 C-atoms, such as methanolamine, 1-amino-3,3-dimethyl-pentane-5-ol, 2-aminohexane-2',2"-diethanolamine, 1-Amino-2,5-dimethylcyclohexane-4-ol, 2-aminopropanol, 2-aminobutanol, 3-aminopropanol, 1-amino-2-propanol, 2-amino-2-methyl-1-propanol, 5-aminopentanol, 3-aminomethyl-3,5,5-trimethylcyclohexanol, 1-amino-1-cyclopentane-methanol, 2-amino-2-ethyl-1,3-propandiole, aromatic-aliphatic or aromatic or aromatic-cycloaliphatic aminoalcohols having 6 to about 20 C-atoms, wherein as the aro-matic structures heterocyclic ring systems or preferably isocyclic ring systems such as naphthalene or particularly benzene derivatives, such as 2-aminobenzylalcohol, 3-(hydroxymethyl)anilin, 2-amino-3-phenyl-1-propanol, 2-amino-1-phenylethanol, 2-phenylglycinol or 2-amino-1-phenyl-1,3-propandiole and mixtures of two or more of such compounds.
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. In the following, possi-bly used catalysts are exemplarily mentioned:
Tertiary amines, such as triethylamine, tributylamine, dirnethylbenzylamine, dicy-clohexylmethylamine, dimethylcyclohexylamine, N,N,N',N'-tetramethyldiaminodiethylether, bis(dimethylaminopropyl)urea, N-methyl- and N-ethyhnorpholine, N-cyclohexylmorpholine, N,N,N',N'-3o tetramethylethylenediamine, N,N,N',N'-tetramethylbutanediamine, N,N,N',N'-tetramethylhexanediamine-1,6, pentamethyldiethylenetriamine, dimethylpiper-azine, N-dimethylaminoethylpiperidine, 1,8-diazabicyclo(5.4.0)undecen-7,1,2-dimethylimidazol, 1-azabicyclo-(2.2.0)octane, 1,4-diazabicyclo(2.2.2)octan (DABCO), alkonolamine compounds, such as triethanolamine, triisopropano-lamine, N-methyl-and N-ethyl diethanolamine, dimethylaminoethanol, 2-(N,N-dimethylaminoethoxy)ethanol, N,N,N',N"-tris(dialkylaminoalkyl)hexahydrotriazines, such as N,N',N"-tris(dimethylaminopropyl)-s-hexahydrotriazine, preferably triethylenediamine, pentamethylenediethylentriamin and/or bis(dimethylamino)ether; metal salts, e.g.
inorganic andlor organic compounds of Fe, Pb, Zn and/or Sn, in common oxidea-tion stages of the metals, respectively, such as Fe(II)-chloride, Zn-chloride, Pb-octoate and preferably Sn-compounds, such as Sn(II)-compounds, particularly Sn-dioctoate, Sn-diethylhexlmaleate and/or Sn(IV)-compounds, such as dialkyl-Sn-di(isooctylmercaptoacetate), dialkyl-Sn-di(2-ethylhexylmaleate), dialkyl-Sn-di(2-ethylhexylmercaptoacetate), dialkyl-Sn-di(isooctylmercaptoacetate), dialkyl-Sn-i s dilaurate, dialkyl-Sn-dimaleate, diallcyl-Sn-di(mercaptoacetate).
Furthermore, amidines, such as 2,3-dimethyl-3,4,5,6-tetrahydropyrimidine, tetraalkylammo-nium hydroxides, such as tetramethylammonium hydroxide, alkali metal hydrox-ides, such as sodium hydroxide and alkali metal alcoholates, such as sodium methylate and potasium isopropylate and alkali metal salts of long chain fatty ac-2o ids having 10 to 20 C-atoms and optionally OH-groups as side groups, may re-spectively be used as catalysts. The exemplarily mentioned catalysts may be used alone or in mixtures of at leas two of the mentioned catalysts.
Optionally, as adjuvants and/or additives common substances may be used in the 25 process according to the invention. To be mentioned are 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.
In general, the use of a solvent or thinning agent is generally not required for the reaction according to step (3). However, within a preferred embodiment of said reaction, a solvent or a mixture of two or more solvents is used. Suitable solvents are e.g. carbohydrates, particularly toluene, xylene or cyclohexane, esters, par-ticularly ethylglycolacetate, ethylacetate or butyacetate, amides, particularly di-methylformamide or N-methylpyrrolidone, sulfoxides, particularly dimethylsul-foxide, ethers, particularly diisopropylether or methyl-tert.-butyl ether or prefera-bly cyclic ethers, particularly THF or dioxane.
l0 Furthermore, the present invention also relates to a polyurethane, obtainable by an integrated process, comprising at least the following steps, (2) reacting at least one organic compound with at least one allcoxy-lating agent via a process as described above, wherein a polyether alcohol is obtained;
(3) reacting the polyether alcohol of step (2) with at least one isocya-nate.
The polyether alcohol, obtainable according to step (2), which is used for prepar-ing 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.
Furthermore, the present invention relates to a process for preparing a polyure-thane foam, starting from a polyurethane, as defined within the present invention, that process comprising at least the following step, (4) foaming the polyurethane as used as a starting material:
The present invention also encompasses the polyurethane foam as such, obtain-3o able by foaming a polyurethane, as obtained by the reaction according to step (3).
The polyurethanes according to the present invention are predominantly charac-terized by their low content of impurities, such as C6-compounds. This renders the polyurethanes according to the invention particularly suitable for the prepara-tion of polyurethane foams, polyurethane cast skins and elastomers.
Among the polyurethane foams preferably polyurethane foams axe 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.
to Processes for the preparation of polyurethane foams are described in Becker, Braun, "Polyurethanes", Kunststoffhandbuch, vol. 7, Carl Hanser, Munich, 3ra edition, 1993, p. 193 to 265.
In a preferred embodiment, the present invention relates to a polyurethane, which is derived from a polyether alcohol, obtainable according to step (2), which com-prises at least one mixed block of ethylene oxide-propylene oxide-units.
The present invention also relates to a polyurethane, derived from a polyether al-cohol, obtainable according to step (2), which comprises a terminal propylene oxide block.
The polyurethane according to the present invention, particularly the above-mentioned polyurethane, may suitably be used for preparing shaped bodies, par-ticularly shaped bodies made of soft slab-stock foams on the basis of polyure-thane. 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.
In addition thereto, the narrower molecular weight distribution due to the lower amount of mono-functional side compounds leads to an improved processing during foaming.
Thus, the present invention also relates to a shaped body comprising a polyure-thane 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 l0 bodies for the automotive industry and upholstery furniture.
The following shaped bodies according to the invention are to be mentioned:
- 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, ani-mal marks, supports for rails, films, shoe soles and accessories, ski tips and 2o 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 debarring drums, pump elements and pump hous-ings, 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 ele-ments;
- soft integral foams, particularly steering wheels, seals for air filters, steer-s ing knob, foaming of wires, casings for containers, arm-rests, shoe soles made of polyurethane;
- polyurethane coatings, particularly for floor coverings, refining of materi-als, such as wood, leather or metal sheets;
- polyurethane skins, particularly for the use as inserts for shaped bodies, 1o such as dashboards, coverings for car doors, truck and car seats, floorings;
- rigid polyurethane foams, particularly for the use as damping material or construction material;
- integral foams, particularly for the use as elements in the inner and outer areas of constructions, complex furnitures, elements for car interiors, skis 15 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 2o structures for the use in car manufacture, e.g. as an element for roof cov-ers;
- semi-rigid foams, particularly for underfoaming of films, skins or leather or fiber reinforced construction elements.
25 The invention is now further described by way of the following examples, which are, however, not meant to limit the scope of the present application.
Examples Figure 1 shows a X-ray powder diffractogramm of the MOF-5 catalyst as pre-pared according to Example 1 (the ordinate Y describes Lin in Counts and the abscisse X the 2-Theta-Scale).
Figure 2 shows the sorptionisotherme of said catalyst (the ordinate ~A
describes the volume as absorbed in cm 3lg STP and the abscisse RP the relative pressure (P/PO)).
Example 1 (Preparation of MOF-5) Starting MaterialMolar CalculatedExperimental Amount terephthalic acid12.3 mmol 2.04 g 2.04 g Zinc nitrate-tetra36.98 mmol 9.67 g 9.68 g hy-drate diethylformamide 2568.8 mmol282.2 282.2 g g (Merck) The above-mentioned amounts of the starting materials were dissolved in a beaker in the order diethylformamide, terephthalic acid and zinc nitride. The resulting solution was introduced into two autoclaves (250 ml), having respectively inner walls which were covered by teflon.
The crystallization occurred at 105° C within twenty hours.
Subsequently, the orange solvent was decanted from the yellow crystals, said crystals were again covered by 20 ml dimethylformamide, the latter being again decanted. This pro-cedure was repeated three times. Subsequently, 20 ml chloroform were poured onto the solid, which was washed and decanted by said solvent two times.
The crystals (14.4 g), which were still moist, were introduced into a vacuum de-vice and first at room temperature in vacuo (10'~ mbar), afterwards dried at 120°C.
Subsequently, the resulting product was characterized by X-ray powder diffrac-tion and an adsorptive determination of micropores. The resulting product shows the X-ray diffractogramm according to Figure l, which coincides with MOF-5.
The determination of the sorptionsisotherme, as depicted in Figure 2, with argon to (87I~; Micromeritics ASAP 2010) shows an isotherme of type I, being typical for microporous materials, and having a specific surface area of 3020 m~'/g, calculated according to Langmuir, and a micropore volume of 0.97 ml/g (at a relative pres-sure pp° = 0,4).
Example 2 Alkox~lation of Dipropylene Glycol with Propylene Oxide) Dipropylene glycol (33.5 g corresponding to 0.25 mol) and 0.75 g of the catalyst prepared according to Example 1 were introduced in an autoclave. Subsequently, the autoclave was filled with 116 g propylene oxide (2 mol). The reaction was 2o carried out at 135°C and a maximum pressure of 12.1 bar, and in total 2.44 mol propylene oxide/mol starting material were reacted to obtain a polyol.
Example 3 (Alkoxylation of Methyl Diprop~ene Glycol with Ethylene Oxide) Methyl dipropylene glycol (30 g corresponding to 0.25 mol) and 0.59 g of the catalyst as prepared according to Example 1 were introduced in an autoclave.
The autoclave was then filled with 88 g ethylene oxide (2 mol). The reaction was car-_27_ ried out at 135°C and a maximum pressure of 21.2 bar. In total, 2.45 mol ethylene oxide/mol starting compound were reacted to obtain a polyol.
Example 4 Allcoxylation of Acrylic Acid with Ethylene Oxide) 33.2 g acrylic acid (stabilized with 2,2',6,6'-tetramethyl-4-hydroxypiperidine-N-oxide and phenothiazine) and 0.5 g catalyst of Example 1 were weighed into a 300 ml steering autoclave under nitrogen atmosphere. The autoclave was closed and pressurized with 10 bar nitrogen. Upon steering 20 g ethylene oxide were to subsequently introduced via a screw press. After five hours at 50°C
the catalyst was filtered off and the raw product was analyzed by gas chromatography. Based on the area percentages the following composition of the solution (residual ethyl-ene oxide not considered):
Acrylic acid 76%, monoethylene glycol acrylate 10%, diethylene glycol acrylate 9%, other side products 5%.
Claims (12)
1. 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 com-prises a metallo-organic framework material comprising pores and at least one metal ion and at least one at least bidentate organic compound, which is coor-dinately bounded to said metal ion.
2. Process according to claim 1, characterized in that the metal ion is selected among ions of elements of groups Ia, IIa, IIIa, IVa to VIIIa and Ib to VIb of the periodic table of the elements.
3. Process according to claim 1 or 2, characterized in that the bidentate organic compound is selected among substituted or unsubstituted aromatic polycar-boxylic acids, which may comprise one or more nuclei; and substituted or un-substituted aromatic polycarboxylic acids, which comprise at least one hetero-atom and which may have one or more nuclei.
4. Process according to any of claims 1 to 3, characterized in that the metallo-organic framework material comprising pores exhibits a specific surface area, as determined via adsorption (BET according to DIN 66131) of larger than 20 m2/g.
5. Process according to any of claims 1 to 4, characterized in that the alkoxyla-tion agent is selected among mono- or multi-functional epoxides having 2 to 30 carbon atoms and mono- or multi-functional polyetherpolyoles having a molar mass of above 600 g/mol and a mixture of two or more thereof.
6. Integrated process for the preparation of a polyurethane comprising at least the following steps, (2) reacting at least one organic compound, which is capable of being alkoxylated, with at least one alkoxylating agent via a process ac-cording to any of claims 1 to 5, wherein a polyether alcohol is ob-tamed;
(3) reacting the polyether alcohol of step (2) with at least one isocya-nate.
(3) reacting the polyether alcohol of step (2) with at least one isocya-nate.
7. Integrated process according to claim 6, characterized in that the alkoxylating agent is propylene oxide, which has been obtained in a step (1) by reacting propylene with oxygen, hydrogen and oxygen; hydrogen peroxide; organic hydroperoxides; or halohydrins; preferably by reacting propylene with hydro-gen peroxide; further preferred by reacting propylene with hydrogen peroxide in the presence of a catalyst comprising a zeolitic material; particularly by re-acting propylene with hydrogen peroxide in the presence of a catalyst com-prising a titanium containing zeolitic material having TS-1 structure.
8. Polyurethane, obtainable by an integrated process, comprising at least the fol-lowing steps, (2) reacting at least one organic compound, which is capable of being alkoxylated, with at least one alkoxylating agent via a process ac-cording to any of claims 1 to 5, wherein a polyether alcohol is ob-tained;
(3) Reacting the polyether alcohol of step (2) with at least one isocya-nate.
(3) Reacting the polyether alcohol of step (2) with at least one isocya-nate.
9. Polyurethane according to claim 8, characterized in that the polyether alcohol, which is obtainable according to step (2) and which is used as an starting ma-terial for the preparation of the polyurethane, comprises at least a mixed block of ethylene oxide-propylene oxide-units or a terminal propylene oxide block or a combination of both.
10. Process for preparing a polyurethane foam starting from a polyurethane ob-tainable by an integrated process according to any of claims 1 to 7 or starting from a polyurethane according to claims 8 or 9, which comprises at least the following step, (4) foaming of the said polyurethane.
11. Polyurethane foam, obtainable by an integrated process according to any of claims 1 to 7 or starting from a polyurethane according to claims 8 or 9, said integrated process comprising at least the following further step, (4) foaming the polyurethane, which has been obtained in the reaction according to step (3).
12. Shaped body comprising a polyurethane, which is obtainable by an integrated process according to any of claims 1 to 7 or a polyurethane according to claim 8 or 9 or a polyurethane foam obtainable by the process according to claim 10 or a polyurethane foam according to claim 11.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
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 |
US10/039,733 | 2001-10-19 | ||
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 |
Publications (1)
Publication Number | Publication Date |
---|---|
CA2464352A1 true CA2464352A1 (en) | 2003-05-01 |
Family
ID=21907076
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA002464352A Abandoned CA2464352A1 (en) | 2001-10-19 | 2002-10-18 | Process for the alkoxylation of organic compounds in the presence of novel framework materials |
Country Status (13)
Country | Link |
---|---|
US (2) | US20030078311A1 (en) |
EP (1) | EP1440106B1 (en) |
JP (1) | JP4173101B2 (en) |
KR (1) | KR100940290B1 (en) |
CN (1) | CN100424115C (en) |
AT (1) | ATE535560T1 (en) |
CA (1) | CA2464352A1 (en) |
ES (1) | ES2376050T3 (en) |
MX (1) | MXPA04003467A (en) |
PL (1) | PL370429A1 (en) |
RU (1) | RU2308465C2 (en) |
TW (1) | TWI300072B (en) |
WO (1) | WO2003035717A1 (en) |
Families Citing this family (77)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
ATE334992T1 (en) * | 2001-04-30 | 2006-08-15 | Univ Michigan | ISORETICULAR ORGANOMETALLIC BASIC STRUCTURES, METHOD FOR THEIR FORMATION AND SYSTEMATIC DEVELOPMENT OF THEIR PORE SIZE AND FUNCTIONALITY, WITH APPLICATION FOR GAS STORAGE |
US6893564B2 (en) * | 2002-05-30 | 2005-05-17 | Basf Aktiengesellschaft | Shaped bodies containing metal-organic frameworks |
US7008607B2 (en) * | 2002-10-25 | 2006-03-07 | Basf Aktiengesellschaft | Process for preparing hydrogen peroxide from the elements |
CA2524903A1 (en) * | 2003-05-09 | 2004-11-25 | The Regents Of The University Of Michigan | Implementation of a strategy for achieving extraordinary levels of surface and porosity in crystals |
US7309380B2 (en) * | 2003-06-30 | 2007-12-18 | Basf Aktiengesellschaft | Gas storage system |
US20050004404A1 (en) * | 2003-07-03 | 2005-01-06 | Basf Akiengesellschaft | Process for the alkoxylation of monools in the presence of metallo-organic framework materials |
DE10355087A1 (en) * | 2003-11-24 | 2005-06-09 | Basf Ag | Process for the electrochemical preparation of a crystalline porous organometallic framework |
EP1689762A4 (en) * | 2003-12-05 | 2009-08-05 | Univ Michigan | Metal-organic polyhedra |
JP4659356B2 (en) * | 2003-12-26 | 2011-03-30 | 株式会社イノアックコーポレーション | Method for producing recycled polyurethane foam |
EP1802732B1 (en) | 2004-10-22 | 2012-07-11 | The Regents of The University of Michigan | Covalently linked organic frameworks and polyhedra |
US7524444B2 (en) * | 2004-11-09 | 2009-04-28 | Basf Aktiengesellschaft | Shaped bodies containing metal-organic frameworks |
US7343747B2 (en) * | 2005-02-23 | 2008-03-18 | Basf Aktiengesellschaft | Metal-organic framework materials for gaseous hydrocarbon storage |
US7662746B2 (en) * | 2005-04-07 | 2010-02-16 | The Regents Of The University Of Michigan | High gas adsorption metal-organic framework |
US8628055B2 (en) * | 2005-07-27 | 2014-01-14 | The Board Of Trustees Of The University Of Illinois | Bi-direction rapid action electrostatically actuated microvalve |
WO2007038508A2 (en) * | 2005-09-26 | 2007-04-05 | The Regents Of The University Of Michigan | Metal-organic frameworks with exceptionally high capacity for storage of carbon dioxide at room-temperature |
US8123834B2 (en) * | 2005-10-06 | 2012-02-28 | The Board Of Trustees Of The University Of Illinois | High gain selective metal organic framework preconcentrators |
DE102005054523A1 (en) | 2005-11-14 | 2007-05-16 | Basf Ag | Porous organometallic framework containing another polymer |
DK1988996T3 (en) * | 2006-02-28 | 2017-09-11 | Univ Michigan Regents | Production of functionalized zeolite skeletons |
US7880026B2 (en) * | 2006-04-14 | 2011-02-01 | The Board Of Trustees Of The University Of Illinois | MOF synthesis method |
KR101493529B1 (en) | 2006-04-18 | 2015-02-13 | 바스프 에스이 | Metal organic framework based on aluminum fumarate |
US7441574B2 (en) * | 2006-08-17 | 2008-10-28 | The Goodyear Tire & Rubber Company | Pneumatic tire |
US20080111114A1 (en) * | 2006-10-30 | 2008-05-15 | Gilbert Alan M | Flame-retardant materials and systems |
US9719019B1 (en) | 2006-10-30 | 2017-08-01 | Alan M. Gilbert | Flame-retardant materials and systems |
RU2009120403A (en) | 2006-10-30 | 2010-12-10 | Басф Се (De) | ALUMINUM NAPHTHALINDICARBOXYLATE AS A POROUS METALLORGANIC MATERIAL WITH A SKELETON STRUCTURE |
US9017584B2 (en) * | 2006-10-30 | 2015-04-28 | Alan M. Gilbert | Flame-retardant materials and systems |
JP5559545B2 (en) * | 2007-01-24 | 2014-07-23 | ザ レジェンツ オブ ザ ユニヴァースティ オブ カリフォルニア | Crystalline 3D- and 2D-covalent organic frameworks |
ES2397231T3 (en) | 2007-04-24 | 2013-03-05 | Basf Se | Organometallic structural materials, with a hexagonal and trigonal structure, based on aluminum, iron or chromium, as well as a dicarboxylic acid |
US8540802B2 (en) * | 2007-05-11 | 2013-09-24 | The Regents Of The University Of California | Adsorptive gas separation of multi-component gases |
EP2167511A4 (en) * | 2007-07-17 | 2010-12-22 | Univ California | Preparation of functionalized zeolitic frameworks |
US8222179B2 (en) * | 2007-08-30 | 2012-07-17 | The Regents Of The University Of Michigan | Porous coordination copolymers and methods for their production |
US9132411B2 (en) | 2007-08-30 | 2015-09-15 | The Regents Of The University Of Michigan | Strategies, linkers and coordination polymers for high-performance sorbents |
US8383545B2 (en) * | 2007-08-30 | 2013-02-26 | The Regents Of The University Of Michigan | Strategies, linkers and coordination polymers for high-performance sorbents |
WO2009042802A1 (en) * | 2007-09-25 | 2009-04-02 | The Regents Of The University Of California | Edible and biocompatible metal-organic frameworks |
WO2009074742A2 (en) * | 2007-09-28 | 2009-06-18 | Ifp | Method for producing alcohol esters from triglycerides and alcohols using heterogeneous catalysts containing a hybrid solid with an organic-inorganic mixed matrix |
FR2921661B1 (en) * | 2007-10-01 | 2013-05-31 | Centre Nat Rech Scient | INORGANIC ORGANIC HYBRID SOLID WITH MODIFIED SURFACE. |
FR2921660B1 (en) | 2007-10-01 | 2015-09-25 | Centre Nat Rech Scient | INORGANIC ORGANIC HYBRID NANOPARTICLES BASED ON IRON CARBOXYLATES. |
US8034952B2 (en) * | 2007-11-15 | 2011-10-11 | University Of South Florida | Supramolecular assemblies and building blocks |
US8123841B2 (en) * | 2008-01-16 | 2012-02-28 | The Board Of Trustees Of The University Of Illinois | Column design for micro gas chromatograph |
US8071063B2 (en) | 2008-02-21 | 2011-12-06 | Exxonmobile Research And Engineering Company | Separation of hydrogen from hydrocarbons utilizing zeolitic imidazolate framework materials |
US8142746B2 (en) * | 2008-02-21 | 2012-03-27 | Exxonmobil Research And Engineering Company | Separation of carbon dioxide from methane utilizing zeolitic imidazolate framework materials |
US8142745B2 (en) * | 2008-02-21 | 2012-03-27 | Exxonmobil Research And Engineering Company | Separation of carbon dioxide from nitrogen utilizing zeolitic imidazolate framework materials |
FR2929278A1 (en) * | 2008-04-01 | 2009-10-02 | Centre Nat Rech Scient | POROUS CRYSTALLINE HYBRID SOLID FOR THE ADSORPTION AND RELEASE OF GASES OF BIOLOGICAL INTEREST. |
US8269029B2 (en) * | 2008-04-08 | 2012-09-18 | The Board Of Trustees Of The University Of Illinois | Water repellent metal-organic frameworks, process for making and uses regarding same |
US8946454B2 (en) * | 2008-06-05 | 2015-02-03 | The Regents Of The University Of California | Chemical framework compositions and methods of use |
EP2358726B1 (en) | 2008-12-18 | 2017-08-02 | The Regents of the University of California | Porous reactive frameworks |
WO2010078337A1 (en) | 2008-12-29 | 2010-07-08 | The Regents Of The University Of California | A gas sensor incorporating a porous framework |
US8674128B2 (en) | 2009-01-15 | 2014-03-18 | The Regents Of The University Of California | Conductive organometallic framework |
WO2010088629A1 (en) | 2009-02-02 | 2010-08-05 | The Regents Of The University Of California | Reversible ethylene oxide capture in porous frameworks |
FR2942229B1 (en) | 2009-02-18 | 2011-02-25 | Univ Paris Curie | TITANIUM-BASED POLYCARBOXYLATE INORGANIC-ORGANIC HYBRID SOLID MATERIAL, PROCESS FOR PREPARING THE SAME AND USES THEREOF |
US8876953B2 (en) | 2009-06-19 | 2014-11-04 | The Regents Of The University Of California | Carbon dioxide capture and storage using open frameworks |
JP5698229B2 (en) | 2009-06-19 | 2015-04-08 | ザ リージェンツ オブ ザ ユニバーシティ オブ カリフォルニアThe Regents Of The University Of California | Complex mixed ligand open skeleton materials |
KR20120084662A (en) | 2009-07-27 | 2012-07-30 | 바스프 에스이 | Oxidative homo-coupling reactions of aryl boronic acids using a porous copper metal-organic framework as a highly efficient heterogeneous catalyst |
WO2011038208A2 (en) | 2009-09-25 | 2011-03-31 | The Regents Of The University Of California | Open metal organic frameworks with exceptional surface area and high gas strorage capacity |
ES2547729T3 (en) | 2009-11-30 | 2015-10-08 | Basf Se | Organometallic structure materials based on 2,5-furandicarboxylic acid or 2,5-thiophenedicarboxylic acid |
US8716359B2 (en) * | 2010-03-18 | 2014-05-06 | Vanderbilt Chemicals, Llc | Polyurethane foam scorch inhibitor |
WO2011123795A1 (en) | 2010-04-02 | 2011-10-06 | Battelle Memorial Institute | Methods for associating or dissociating guest materials with a metal organic framework, systems for associating or dissociating guest materials within a series of metal organic frameworks, and gas separation assemblies |
BR112013001263A2 (en) | 2010-07-20 | 2016-05-17 | Basf Se | method for replacing at least one atom of an organic molecule with another atom or group of atoms, and catalyst. |
RU2013119647A (en) | 2010-09-27 | 2014-11-10 | Те Риджентс Оф Те Юниверсити Оф Калифорния | CONDUCTING OPEN FRAME FRAME STRUCTURES |
MX2013008390A (en) | 2011-01-21 | 2013-08-12 | Univ California | Preparation of metal-triazolate frameworks. |
KR20140041445A (en) | 2011-02-04 | 2014-04-04 | 더 리젠츠 오브 더 유니버시티 오브 캘리포니아 | Preparation of metal-catecholate frameworks |
ES2645260T3 (en) | 2011-10-13 | 2017-12-04 | The Regents Of The University Of California | Organometallic structure with exceptionally large pore opening |
EP2839525B1 (en) | 2012-04-18 | 2020-06-03 | King Abdullah University Of Science And Technology | Electrode separator |
CN103333182A (en) * | 2013-06-04 | 2013-10-02 | 中南大学 | Method for preparing MOF-5 |
WO2015066693A1 (en) | 2013-11-04 | 2015-05-07 | The Regents Of Thd University Of California | Metal-organic frameworks with a high density of highly charged exposed metal cation sites |
ES2768680T3 (en) | 2014-02-19 | 2020-06-23 | Univ California | Organometallic frames that have resistance to acids, solvents, and thermal |
JP2017512637A (en) | 2014-03-18 | 2017-05-25 | ザ リージェンツ オブ ザ ユニバーシティ オブ カリフォルニア | Mesoscopic materials containing ordered superlattices of microporous metal-organic framework |
PL3311913T3 (en) | 2014-03-27 | 2021-01-11 | Basf Se | Porous films comprising metal-organic framework materials |
WO2015195179A2 (en) | 2014-03-28 | 2015-12-23 | 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. |
EP2985075A1 (en) | 2014-08-15 | 2016-02-17 | Basf Se | Shaped body made of a porous material |
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 |
KR20180088679A (en) | 2015-11-27 | 2018-08-06 | 바스프 에스이 | High-speed time-space synthesis of metal-organic framework |
WO2017091779A1 (en) | 2015-11-27 | 2017-06-01 | The Regents Of The University Of California | Zeolitic imidazolate frameworks |
EP3380228A1 (en) | 2015-11-27 | 2018-10-03 | The Regents of The University of California | Covalent organic frameworks with a woven structure |
US11452967B2 (en) | 2017-07-17 | 2022-09-27 | Zymergen Inc. | Metal-organic framework materials |
US20230178848A1 (en) | 2020-04-28 | 2023-06-08 | King Abdullah University Of Science And Technology | Electrode separators |
CN113828281B (en) * | 2021-09-18 | 2023-07-14 | 集美大学 | Preparation method, product and application of polyurethane composite material |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3144418A (en) | 1959-08-17 | 1964-08-11 | Union Carbide Corp | Polymerization of epoxides |
DE4408772B4 (en) | 1993-03-16 | 2006-09-07 | Mitsubishi Chemical Corp. | Process for the preparation of a polyoxyalkylene glycol and new metal aluminosilicate |
US5601437A (en) | 1994-10-17 | 1997-02-11 | Methode Electronics, Inc. | Clockspring with centering display device |
US5648508A (en) | 1995-11-22 | 1997-07-15 | Nalco Chemical Company | Crystalline metal-organic microporous materials |
DE19928156A1 (en) | 1999-06-19 | 2000-12-28 | Bayer Ag | Polyetherpolyols for preparation of soft polyurethane foams avoid increase in monofunctional polyethers and decrease in functionality with increased chain length and difficulty in alkoxylation of conventional starting compounds |
DE60041200D1 (en) | 1999-07-21 | 2009-02-05 | Black & Decker Inc | DRIVEN FOOD |
DE19941242A1 (en) * | 1999-08-31 | 2001-03-08 | Basf Ag | Polyether alcohols |
DE19949092A1 (en) | 1999-10-12 | 2001-04-19 | Basf Ag | Process for the preparation of polyether alcohols |
DE10111230A1 (en) | 2001-03-08 | 2002-09-19 | Basf Ag | Organometallic framework materials and processes for their production |
DE10143195A1 (en) | 2001-09-04 | 2003-03-20 | Basf Ag | Integrated process for the production of polyurethane foams |
-
2001
- 2001-10-19 US US10/039,733 patent/US20030078311A1/en not_active Abandoned
-
2002
- 2002-10-18 RU RU2004115338/04A patent/RU2308465C2/en not_active IP Right Cessation
- 2002-10-18 US US10/492,192 patent/US7279517B2/en not_active Expired - Fee Related
- 2002-10-18 WO PCT/EP2002/011700 patent/WO2003035717A1/en active Application Filing
- 2002-10-18 EP EP02781271A patent/EP1440106B1/en not_active Expired - Lifetime
- 2002-10-18 CA CA002464352A patent/CA2464352A1/en not_active Abandoned
- 2002-10-18 MX MXPA04003467A patent/MXPA04003467A/en active IP Right Grant
- 2002-10-18 PL PL02370429A patent/PL370429A1/en not_active Application Discontinuation
- 2002-10-18 ES ES02781271T patent/ES2376050T3/en not_active Expired - Lifetime
- 2002-10-18 TW TW091124078A patent/TWI300072B/en active
- 2002-10-18 AT AT02781271T patent/ATE535560T1/en active
- 2002-10-18 CN CNB028207831A patent/CN100424115C/en not_active Expired - Fee Related
- 2002-10-18 KR KR1020047005723A patent/KR100940290B1/en not_active IP Right Cessation
- 2002-10-18 JP JP2003538229A patent/JP4173101B2/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
PL370429A1 (en) | 2005-05-30 |
TWI300072B (en) | 2008-08-21 |
JP4173101B2 (en) | 2008-10-29 |
US20040249189A1 (en) | 2004-12-09 |
ES2376050T3 (en) | 2012-03-08 |
JP2005506421A (en) | 2005-03-03 |
MXPA04003467A (en) | 2004-07-30 |
CN1571803A (en) | 2005-01-26 |
KR100940290B1 (en) | 2010-02-05 |
RU2004115338A (en) | 2005-10-27 |
CN100424115C (en) | 2008-10-08 |
US20030078311A1 (en) | 2003-04-24 |
RU2308465C2 (en) | 2007-10-20 |
WO2003035717A9 (en) | 2004-12-29 |
EP1440106B1 (en) | 2011-11-30 |
US7279517B2 (en) | 2007-10-09 |
KR20040083413A (en) | 2004-10-01 |
EP1440106A1 (en) | 2004-07-28 |
ATE535560T1 (en) | 2011-12-15 |
WO2003035717A1 (en) | 2003-05-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US7279517B2 (en) | Process for the alkoxylation of organic compounds in the presence of novel framework materials | |
EP1658257B1 (en) | Process for the alkoxylation of monools in the presence of metallo-organic framework materials | |
CA2161064C (en) | Production of low-fogging polyurethane foams, and specific polyoxyalkylene-polyols which can be used for this purpose | |
US9896542B2 (en) | Dual catalyst system for high primary hydroxyl polyols | |
EP3538588B1 (en) | Polycarbonate based polyols | |
AU2007301112A1 (en) | Method for producing soft polyurethane foam | |
ES2319973T3 (en) | INTEGRATED PROCEDURE FOR OBTAINING POLYURETHANE FOAMS. | |
KR20120095338A (en) | Method for the production of polyether polyols comprising terminal primary hydroxyl groups | |
KR20140007822A (en) | Method for producing polyether ester polyols | |
KR102529691B1 (en) | Polyether-acetal polyol compositons | |
US6906110B1 (en) | Method for the production of polyurethanes | |
MXPA02005086A (en) | Method for producing polyether polyols. | |
KR20060120012A (en) | Process for the preparation of a polyether polyol | |
KR20210137478A (en) | Lewis Acid Polymerization Catalyst | |
JPH05305629A (en) | Manufacture of polyurethane foam molded aritcle | |
MXPA97005754A (en) | Copolymers of polyeteros and polisiloxano manufactured with double me cyanide catalysts |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
EEER | Examination request | ||
FZDE | Discontinued |