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  • C07H3/00—Compounds containing only hydrogen atoms and saccharide radicals having only carbon, hydrogen, and oxygen atoms
  • C07H3/04—Disaccharides
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  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
  • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
  • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
  • C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
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  • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
  • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
  • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
  • C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
  • C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
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  • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
  • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
  • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
  • C07C29/143—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones
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  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
  • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
  • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
  • C07C29/143—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones
  • C07C29/145—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones with hydrogen or hydrogen-containing gases
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  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
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  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
  • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
  • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
  • C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
  • C07C45/70—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction with functional groups containing oxygen only in singly bound form
  • C07C45/71—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction with functional groups containing oxygen only in singly bound form being hydroxy groups
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
  • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
  • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
  • C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
  • C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
  • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
  • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
  • C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
  • C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
  • C07C45/75—Reactions with formaldehyde
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
  • C07H3/00—Compounds containing only hydrogen atoms and saccharide radicals having only carbon, hydrogen, and oxygen atoms
  • C07H3/02—Monosaccharides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/30—Low-molecular-weight compounds
  • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
  • C08G18/3203—Polyhydroxy compounds
  • C08G18/3206—Polyhydroxy compounds aliphatic
  • C08G18/3209—Aliphatic aldehyde condensates and hydrogenation products thereof
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  • 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
  • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
  • C08G18/4297—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from polyester forming components containing aliphatic aldehyde condensates or hydrogenation products thereof having at least two hydroxy groups
• • 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
  • C08G18/4829—Polyethers containing at least three hydroxy groups

Definitions

• the present invention relates to an improved method for producing a mixture of low molecular weight, polyhydric alcohols, hydroxyaldehydes and hydroxyketones by condensation of formaldehyde hydrate. Such mixtures are referred to below as "molds”.
• Polyhydroxyl compounds have gained great technical importance in a wide variety of fields. They are used, for example, for the production of non-ionic surface-active compounds, as antifreezes, moisturizers and softeners, and as starting components for plastics, such as Large-scale use of polyester and polyether resins.
• the present invention is therefore based on the object of providing a process by which mixtures of polyhydroxyl compounds can be synthesized which are as free as possible from decomposition products and which can be hydrogenated to polyhydric alcohols in a simple manner using small amounts of hydrogenation catalysts.
• the mixtures of polyhydroxyl compounds obtained should be colorless and require no further purification.
• Another object of the present invention was to control the formaldehyde self-condensation in such a way that the product distribution of the resulting mixtures of low molecular weight polyhydroxyl compounds can be varied and adjusted in a reproducible manner, depending on the desired application.
• the present invention thus relates to a process for the preparation of low molecular weight polyhydroxyl compounds by condensation of formaldehyde hydrate in the presence of calcium hydroxide as a catalyst and of compounds capable of forming endiol as cocatalyst, which is characterized in that a solution of the cocatalyst containing formaldehyde in water and if appropriate, brings low molecular weight monohydric or polyhydric alcohols and / or higher molecular weight polyhydroxyl compounds at a temperature of 80 to 110 ° C, preferably 90 to 105 ° C, by adding calcium hydroxide to a pH of 9 to 12, preferably 9 to 10 , so that the condensation of the formaldehyde hydrate is started, then an aqueous formalin solution and / or paraformaldehyde dispersion containing 20 to 65% by weight of formaldehyde and calcium hydroxide are metered in such that the reaction mixture is at a temperature of 80 to 110 ° C., preferably 90 to 105
• the claimed pH control is also critical: during the start of the reaction preferably at pH values between 9 and 10 (pH ranges above 12 should be avoided, since the small amount of formaldehyde used at the start will then be consumed too quickly and therefore the condensation reaction becomes difficult to control), the condensation reaction is then continued by suitable dosing of the calcium hydroxide in a pH range between 7.5 and 9.5, preferably between 8 and 9, the reaction mixture preferably being kept constantly at boiling temperature.
• the reaction is difficult to control at pH values above 9.5; at pH values below 7.5, not only is the reaction time greatly prolonged, surprisingly there is also a higher consumption of calcium hydroxide.
• the condensation reaction is terminated in a manner known per se by cooling or adding acid (preferably using sulfuric acid or oxalic acid, since this causes the calcium ions to precipitate out at the same time). If necessary, however, the condensation reaction can also be continued at pH values below 7 until the formaldehyde is completely consumed. It is also possible to remove the remaining amount of at least 0.5% by weight of formaldehyde, based on the reaction mixture, at the end of the reaction according to the invention by reaction with methylolatable compounds such as e.g.
• glycolaldehyde is first formed from two molecules of formaldehyde in a primary step. Further accumulation of formaldehyde gives rise to glyceraldehyde according to the following scheme:
• the process according to the invention can be used to vary the product distribution on the one hand if the reaction is terminated at different levels of residual formaldehyde, on the other hand. adjust the product distribution completely reproducible both in the area of the compounds with 2 to 4 carbon atoms and in the area with 5 and more carbon atoms. This was not to be expected due to the number of reactions only partially mentioned above, which can take place simultaneously and next to one another in the process according to the invention.
• the formaldehyde is preferably condensed from aqueous formaldehyde solutions of a commercially available concentration (30-50% by weight of formaldehyde) which are stabilized by methanol or other known stabilizing agents.
• aqueous formaldehyde solutions of a commercially available concentration (30-50% by weight of formaldehyde) which are stabilized by methanol or other known stabilizing agents.
• non-stabilized formaldehyde solutions which contain proportions of solid, polymerized formaldehyde and / or paraformaldehyde dispersions, since in the course of the process according to the invention these solids are dissolved by depolymerization and are likewise condensed to give hydroxyaldehydes and hydroxyketones.
• Condensation from even more highly concentrated formaldehyde solutions which can be produced, for example, by depolymerizing paraformaldehyde or by concentrating low-concentration formaldehyde solutions in vacuo, is also possible.
• hydroxy aldehydes and hydroxy ketones can be obtained in very good yields by condensing a 65% formaldehyde solution obtained by concentrating a 37% formaldehyde solution in vacuo.
• the process according to the invention can of course also be applied to less concentrated formaldehyde solutions, but the use of these low-concentration formaldehyde solutions is less preferred from an economic point of view because of the additional energy costs required for the evaporation of the solvent.
• the starter mixture can also contain mono- or polyhydric alcohols with a molecular weight of up to approx. 400 or higher molecular weight polyhydroxyl compounds.
• the low molecular alcohols include, for example, methanol, ethanol, isopropanol, n-butanol, t-butanol, neopentyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol, 1,2- and 1,3-propylene glycol, 1,4- and 2,3-butylene glycol, 1,6- and 2,3-hexanediol, 2-methyl-1,2-propanediol, 1,2,4-butanetriol, 1,2,6-hexanetriol, glycerin, erythritol, quinite, mannitol , Sorbitol and methyl glycoside or adducts of ethylene
• Polyhydric alcohols with at least 2 adjacent hydroxyl groups are preferred.
• Suitable higher molecular weight polyhydroxyl compounds are e.g. those that can be used as starting components for the production of polyurethane plastics.
• all of these polyhydroxyl compounds can only be used during the process according to the invention, i.e. be added to the reaction mixture simultaneously with the formaldehyde and the calcium hydroxide.
• reaction according to the invention can also be started in the absence of compounds capable of forming endiol if the starter mixture contains polyols which contain at least 2 adjacent hydroxyl groups. This procedure is analogous to that of DOS 2714104.
• the resulting product mixture contains only a few compounds with 6 or more carbon atoms .
• the proportion of compounds with 2 to 4 carbon atoms is markedly increased.
• the most varied product distributions can be obtained by allowing the self-condensation of the formaldehyde to proceed at different formaldehyde concentrations or by leading to different residual formaldehyde contents. Any desired product distribution can be made; which is necessary for a specific area of application.
• Mixtures with predominantly high molecular weight products are also obtained by subsequently adding hydroxyaldehyde and hydroxyketone mixtures, which predominantly contain low molecular weight fractions, with excess formaldehyde and in the presence of an inorganic or organic base at a pH of 9 to 13, preferably 10 to 11, approx. 10 minutes to 12 hours at 10-100 ° C, preferably at 30--60 ° C, aftertreated.
• hydroxyaldehyde and hydroxyketone mixtures which predominantly contain low molecular weight fractions
• an inorganic or organic base at a pH of 9 to 13, preferably 10 to 11, approx. 10 minutes to 12 hours at 10-100 ° C, preferably at 30--60 ° C, aftertreated.
• tertiary amines such as e.g. Triethylamine, tripropylamine or dimethylbenzylamine are suitable.
• polyhydric alcohols can optionally be obtained in a simple manner by reduction by methods known per se.
• the reduction directly from the aqueous solution obtained is achieved at room temperature with sodium borohydride; however, it can also be done electrolytically, for example.
• Catalytic hydrogenation with hydrogen is also possible.
• all methods which are state of the art in the reduction of sugars to sugar alcohols can be used for this.
• Hydrogenation with Raney nickel in amounts of 5-20% by weight, based on the hydroxyaldehyde and hydroxyketone mixture to be reduced, is particularly favorable at hydrogen pressures of 50-200 kgg / cm 2 and temperatures of 20-200 ° C, however Catalysts containing nickel, cobalt, copper, platinum, rhodium or palladium on inert supports are used with similar success. These reduced formoses are called "forite" in the following.
• the reaction solution is mixed with excess formaldehyde and an inorganic base and for 30 minutes to 12 hours at 10 to 100 ° C., preferably 30 to 60 ° C., while maintaining a pH of 9 to 13, preferably 10 to 11, touched. It is possible not only to reduce the carbonyl function, but also, as explained above, to synthesize higher molecular weight and branched products.
• Preferred inorganic bases which accelerate the crossed Cannizzaro reaction are sodium hydroxide, potassium hydroxide, calcium and barium hydroxide and "crown ether" complexes of alkali atoms.
• the reduction reaction can be further accelerated by co-catalysts.
• Oxalates of transition metals in particular nickel, cobalt, iron, cadmium, zinc, chromium and manganese oxalate, as well as transition metals in elemental form, e.g. Nickel, cobalt, iron, copper, cadmium, zinc, chrome and manganese.
• Activated nickel which is used in the form of so-called Raney nickel, and elemental zinc in powder form are very particularly preferred.
• amides of organic acids such as formamide, dimethylformamide and acetamide
• tetraalkylammonium salts in particular tetramethylammonium chloride and tetraethylammonium chloride.
• the residual formaldehyde still present in the formose at the end of the process according to the invention can be removed not only by further condensation in the neutral or weakly basic pH range but also by adding methylolatable compounds.
• aldehydes and ketones which have a hydrogen atom in the ⁇ -position to the carbonyl group such as acetaldehyde, butyraldehyde, isobutyraldehyde, methyl ethyl ketone, acetone, cyclopentanone, cyclohexanone, mesityl oxide, isophorone, acetophenone and acetoacetic acid ester.
• butyraldehyde, isobutyraldehyde, acetone and cyclohexanone are preferred.
• aninoplast monomers are described, for example, in DOS 2 324 134.
• urea, thiourea, E- caprolactam, bisurethanes, oxamide, pyrrolidone, dicyandiamide, melamine, phenols, naphthols, bisphenol A, phenol and naphtholsulfonates are preferred.
• the residual formaldehyde can also be removed by adding dialkyl phosphites, in particular dimethyl phosphite and diethyl phosphite, the corresponding hydroxymethylphosphonic acid esters being formed.
• methylolatable compounds mentioned has the advantage that they significantly reduce the viscosity of the formoses obtained according to the invention. It is of course also possible according to the invention to achieve this effect, the methylolatable compounds mentioned (or their methylolation products already) at the start of the condensation reaction or at any time during the process according to the invention.
• polyhydroxyl compounds obtained by reduction are very suitable as chain extenders or crosslinking agents in the production of polyurethane plastics from polyisocyanates, low molecular weight polyhydroxyl compounds and optionally higher molecular weight polyhydroxyl compounds, further chain extenders, blowing agents, catalysts and other additives known per se.
• Suitable polyisocyanates in this context are, for example, the aliphatic, cycloaliphatic, araliphatic, aromatic and heterocyclic polyisocyanates as described, for example, by W.
• ethylene diisocyanate 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1.12 dodecane diisocyanate, cyclobutane-1,3-diisocyanate, cyclohexane-1,3- and -1,4-diisocyanate and any mixtures of these isomers, 1-isocyanato-3,3,5- trimethyl-5-isocyanatomethyl-cyclohexane (DAS 1 202 785, American patent specification 3401 190), 2,4- and 2,6-hexahydrotolylene diisocyanate and any mixtures of these isomers, hexahydro-1,3-and / or 1,4-phenytes diisocyanate, perhydro-2,4'- and / or -4,4'-diphenylmethane diisocyanate
• polyisocyanates containing ester groups such as are described, for example, in British Patents 965 474 and 1 072 956, in American Patent 3,567,763 and in German Patent 1,231,688 are mentioned, reaction products of the above-mentioned isocyanates with acetals according to German patent 1,072,385 and polyisocyanates containing polymeric fatty acid residues according to American patent 3,455,883.
• distillation residues obtained from industrial isocyanate production and containing isocyanate groups optionally dissolved in one or more of the aforementioned polyisocyanates. It is also possible to use any mixtures of the aforementioned polyisocyanates.
• polyisocyanates e.g. 2,4- and 2,6-tolylene diisocyanate as well as any mixtures of these isomers (“TDI”), polyphenyl-polymethylene polyisocyanates, such as those produced by aniline-formaldehyde condensation and subsequent phosgenation (“crude MDI”) and carbodiimide groups, Polyisocyanates containing urethane groups, allophenate groups, isocyanurate groups, urea groups or biuret groups (“modified polyisocyanates").
• TDI polyisocyanates
• polyphenyl-polymethylene polyisocyanates such as those produced by aniline-formaldehyde condensation and subsequent phosgenation
• CAMDI aniline-formaldehyde condensation and subsequent phosgenation
• carbodiimide groups Polyisocyanates containing urethane groups, allophenate groups, isocyanurate groups, urea groups or biuret groups
• Suitable higher molecular weight polyhydroxyl compounds are e.g. at least two, generally 2 to 8, but preferably 2 to 4, hydroxyl-containing polyesters, polyethers, polythioethers, polyacetals, polycarbonates and polyesteramides, as are known per se for the production of homogeneous and cellular polyurethanes.
• the hydroxyl group-containing polyesters are e.g. Reaction products of polyhydric, preferably dihydric and optionally additionally trihydric alcohols with polyhydric, preferably dihydric, carboxylic acids.
• polyhydric preferably dihydric and optionally additionally trihydric alcohols
• polyhydric preferably dihydric, carboxylic acids.
• the corresponding polycarboxylic anhydrides or corresponding polycarboxylic esters of lower alcohols or mixtures thereof can also be used to produce the polyesters.
• the polycarboxylic acids can be aliphatic, cycloaliphatic, aromatic and / or heterocyclic in nature and optionally, e.g. by halogen atoms, substituted and / or unsaturated.
• Examples include: succinic acid, adipic acid, suberic acid, azeiaic acid, sebacic acid, phthalic acid, isophthalic acid, trimellitic acid, phthalic anhydride, tetrahydrophthalic acid anhydride, hexahydrophthalic anhydride, tetrachlorophthalic acid, fumaric acid, maleic acid, malefic acid, malefic acid, malefic acid, malefic acid, malefic acid, trimethylsulfane, malefic acid, fumaric acid, malefic acid, malefic acid, malefic acid, malefic acid, malefic acid, malefic acid, malefic acid, malefic acid, malefic acid, malefic acid, malefic acid, fumaric acid, fumaric acid, fumaric acid, fumaric acid, fumaric acid mixture, monomeric fatty acids, dimethyl terephthalate and bis-glycol terephthalate.
• Polyhydric alcohols include, for example, ethylene glycol, propylene glycol (1,2) and - (1,3), butylene glycol (1,4) and - (2,3), hexanediol (1,6), octanediol (1, 8), neopentyl glycol, cyclohexanedimethanol (1,4-bis-hydroxymethylcyclohexane), 2-methyl-1,3-propanediol, glycerin, trimethylolpropane, hexanetriol (1,2,6), butanetriol (1,2,4) trimethylolethane , Pentaerythritol, quinite, mannitol and sorbitol, methyl glycoside, also diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycols, dipropylene glycol, polypropylene glycols, dibutylene glycol and polybutylene glycols in question.
• the polyesters
• the polyethers in question which have at least two, generally two to eight, preferably two to three, hydroxyl groups are those of the type known per se and are obtained, for example, by polymerizing epoxides such as ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide or epichlorohydrin with itself, for example in the presence of BF 3 , or by addition of these epoxides, optionally in a mixture or in succession, to starting components with reactive hydrogen atoms such as water, alcohols, ammonia or amines, for example ethylene glycol, propylene glycol (1,3) or - ( 1,2), trimethylolpropane 4,4'-dihydroxy-diphenylpropane, aniline, ethanolamine or ethylenediamine.
• epoxides such as ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide or epichloro
• Sucrose polyethers such as those described in German publications 1 176 358 and 1 064 938, are also suitable for this purpose. In many cases, those polyethers are preferred which have primary OH groups (up to 90% by weight, based on all the OH groups present in the polyether).
• Polyethers modified by vinyl polymers such as those formed, for example, by polymerizing styrene and acrylonitrile in the presence of polyethers (American patents 3,383,351, 3,304,273, 3,523,093, 3,110,695, German patent 1,152,536), are also suitable, as is OH -Group polybutadienes.
• the condensation products of thiodiglycol with itself and / or with other glycols, dicarboxylic acids, formaldehyde, aminocarboxylic acids or amino alcohols should be mentioned in particular.
• the products are polythio ether, polythio ether ester or polythio ether ester amide.
• polyacetals e.g. the compounds which can be prepared from glycols, such as diethylene glycol, triethylene glycol, triethylene glycol, 4,4'-dioxethoxydiphenyldimethylmethane, hexanediol and formaldehyde.
• glycols such as diethylene glycol, triethylene glycol, triethylene glycol, 4,4'-dioxethoxydiphenyldimethylmethane, hexanediol and formaldehyde.
• Suitable polyacetals can also be produced by polymerizing cyclic acetals.
• Suitable polycarbonates containing hydroxyl groups are those of the type known per se, for example by reacting dilene such as propanediol (1,3), butanediol (1,4) and / or hexanediol (1,6), diethylene glycol, triethylene glycol or tetraethylene glycol with diaryl carbonates, for example Diphenyl carbonate, or phosgene can be produced.
• dilene such as propanediol (1,3), butanediol (1,4) and / or hexanediol (1,6)
• diethylene glycol triethylene glycol or tetraethylene glycol
• diaryl carbonates for example Diphenyl carbonate, or phosgene
• polyester amides and polyamides include e.g. the predominantly linear condensates obtained from polyvalent saturated and unsaturated carboxylic acids or their anhydrides and polyvalent saturated and unsaturated amino alcohols, diamines, polyamines and their mixtures.
• Polyhydroxyl compounds already containing urethane or urea groups and optionally modified natural polyols such as castor oil, carbohydrates or starch can also be used. Addition products of alkylene oxides with phenol-formaldehyde resins or with urea-formaldehyde resins can also be used for this.
• mixtures of the above compounds with at least two isocyanate-reactive hydrogen atoms with a molecular weight of 800-10000 e.g. Mixtures of polyethers and polyesters can be used.
• Compounds with at least two isocyanate-reactive hydrogen atoms with a molecular weight of 32-400 can also be used as starting components which may be used.
• These compounds generally have 2 to 8 isocyanate-reactive hydrogen atoms, preferably 2 or 3 reactive hydrogen atoms.
• Examples of such compounds are: ethylene glycol, (1,2) and - (1,3) propylene glycol, (1,4) and - (2,3) butylene glycol, (1,5) pentanediol, hexanediol (1,6), octanediol- (1,8), neopentyl glycol, 1,4-bis-hydroxymethyl-cyclohexane, 2-methyl-1,3-propanediol, glycerin, trimethylolpropane, hexanetriol- (1,2,6), Trimethylolethane, pentaerythritol, quinite, mannitol and sorbitol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycols with a molecular weight up to 400, dipropylene glycol, polypropylene glycols with a molecular weight up to 400, dibutylene glycol, polybutylene glycols 4,4'
• mixtures of different compounds with at least two isocyanate-reactive hydrogen atoms with a molecular weight of 32-400 can be used.
• polyhydroxyl compounds can also be used for this purpose, in which high molecular weight polyadducts or polycondensates are contained in finely dispersed or dissolved form.
• modified polyhydroxyl compounds are obtained if polyaddition reactions (e.g. reactions between polyisocyanates and amino-functional compounds) or polycondensation reactions (e.g. between formaldehyde and phenols and / or amines) are carried out directly in situ in the above-mentioned compounds containing hydroxyl groups.
• polyhydric carboxylic acids of the type mentioned above, e.g. Phthalic acid, isophthalic acid, terephthalic acid, tetra- and hexahydrophthalic acid, adipic acid or maleic acid
• polyhydric carboxylic acids e.g. Phthalic acid, isophthalic acid, terephthalic acid, tetra- and hexahydrophthalic acid, adipic acid or maleic acid
• polyester condensation as described for example in Houben-Weyl, Methods of Organic Chemistry, Vol. XIV 12, p. 40
• the hydroxyl group-containing polyesters which are synthesized from the hydroxyl compounds prepared according to the invention can of course also be used as a starting component for the production of polyurethane plastics.
• polyhydric alcohols produced according to the invention as well as the hydroxy aldehydes and hydroxy ketones can also be very easily mixed with long-chain, aliphatic monocarboxylic acids, such as caprylic, capric, lauric, myristic, palmitic, stearic, oil, linoleic, arachidonic or Behenic acid, and its derivatives, such as convert the methyl or ethyl esters or the anhydrides or mixed anhydrides to hydroxyl-containing esters.
• aliphatic monocarboxylic acids such as caprylic, capric, lauric, myristic, palmitic, stearic, oil, linoleic, arachidonic or Behenic acid, and its derivatives, such as convert the methyl or ethyl esters or the anhydrides or mixed anhydrides to hydroxyl-containing esters.
• the compounds according to the invention can also be used as humectants in cosmetics and plastics. However, you can e.g. also serve as antifreeze.
• the Ca (OH) 2 metered goes into solution, the reaction mixture turns green to yellowish and begins to boil moderately without an additional heating source. After the reaction has started, Ca (OH) 2 suspension and formalin solution are metered in at the same time, so that the mixture boils continuously moderately, the pH of the reaction solution remains in the range between 8 and 9 and the formaldehyde concentration is approximately 4-5% .
• the Ca is precipitated from the mixture by adding 199 g of 20% strength sulfuric acid. After filtering and concentrating in vacuo, 419 g (89% of theory) of a light-colored formose are obtained, which contains 5.4% of water and has a sugar content of 57.1%, calculated as glucose.
• the mixture is cooled and desalted using an ion exchanger. After concentration on a rotary evaporator, 317 g of a formose with a water content of 7.2% and a sugar content of 10.5%, calculated as glucose, are obtained.
• the comparative example shows the significantly longer reaction time and lower sugar yield with a pH control which deviates from the process according to the invention.
• the Ca is precipitated from the mixture by adding 149 g of 20% sulfuric acid. After filtering and concentrating in vacuo, a light colored formose is obtained.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Biochemistry (AREA)
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• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Phenolic Resins Or Amino Resins (AREA)
• Polyurethanes Or Polyureas (AREA)
• Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

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• 1977
  • 1977-08-26 DE DE19772738512 patent/DE2738512A1/de not_active Withdrawn
• 1978
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  • 1978-08-14 EP EP78100659A patent/EP0000912B1/de not_active Expired
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