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
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/30—Low-molecular-weight compounds
  • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
  • C08G18/3203—Polyhydroxy compounds
  • C08G18/3206—Polyhydroxy compounds aliphatic
  • C08G18/3209—Aliphatic aldehyde condensates and hydrogenation products thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • 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
  • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
  • C08G18/3878—Low-molecular-weight compounds having heteroatoms other than oxygen having phosphorus

Definitions

• the present invention is directed to a process for lowering the viscosity of formose (or mixtures of formose with mono- or disaccharides and / or aminoplast monomers and / or water) by adding dialkyl phosphites and optionally trialkyl phosphites and / or ⁇ -hydroxyphosphonic acid esters.
• the invention further relates to mixtures of formose, dialkyl phosphites and optionally water and / or mono- or disaccharides and / or aminoplast monomers and / or trialkyl phosphites and / or ⁇ -hydroxyalkylphosphonic esters and / or ⁇ -hydroxyalkylphosphonic esters and / or ⁇ -aminoalkylphosphonic esters which are liquid and have a low viscosity and areocyanate-reactive mixtures of formose, dialkyl phosphites and optionally the use of such reactive organic materials for the production of polyurethane plastics, in particular foams.
• Form is understood according to the invention to mean the mixtures of low molecular weight polyhydroxyl compounds (polyhydric alcohols, hydroxyaldehydes and hydroxyketones) known per se, which result from the condensation of formaldehyde hydrate.
• the reaction temperature is generally between 70 and 110 ° C, preferably between 80 and 100 ° C, and the pH of the reaction solution is controlled by adding an inorganic or organic base up to a conversion of 10-60%, preferably 30- 50 1, to a value of 6.0-8.0, preferably 6.5-7.0 and then to a value of 4.0-6.0, preferably 5.0-6.0.
• the product distribution of the corresponding polyol, hydroxyaldehyde and hydroxyketone mixtures can be reproduced in a reproducible manner by this special pH control and by subsequent cooling at different levels of residual formaldehyde (0 to 10% by weight, preferably 0.5 to 6% by weight) Ways vary.
• a further possibility of producing highly concentrated colorless formoses in a high space-time yield consists in aqueous formalin solutions and / or paraformaldehyde dispersions in the presence of a soluble or insoluble metal catalyst and one by partial oxidation of a di- or polyvalent, having at least two adjacent hydroxyl groups
• a soluble or insoluble metal catalyst having at least two adjacent hydroxyl groups
• the pH of the reaction solution being controlled by controlled addition of a base up to a conversion of 5 to 40% between 6.0 and 9, Holds 0 and then adjusts to 4.5 to 8.0 until the condensation reaction is terminated, so that it is now 1.0 to 2.0 units lower than in the first reaction phase, then the reaction with a residual content of 0-10 %
• formaldehyde is interrupted by deactivating the catalyst and the catalyst is removed. This procedure is described in detail in DOS 2 714 084.
• High-quality formoses can also be produced by condensation of formaldehyde in the presence of a metal catalyst and more than 10% by weight, based on formaldehyde, of one or more dihydric or polyhydric low molecular weight alcohols and / or higher molecular weight polyhydroxyl compounds.
• Formose-polyol mixtures of this type are the subject of DOS 2,714,104.
• the formoses prepared in this way can also subsequently be converted into their hemiacetals by excess formaldehyde or ⁇ -methylolated by reaction with formaldehyde in the presence of bases. Modified forms of this type are also described in more detail in DOS 2 721 186.
• the properties of the formose can be varied within wide limits.
• the average molecular weight and thus the hydroxyl functionality of the formoses the higher the further Condensation reaction is carried out, ie the less residual formaldehyde is present when the condensation reaction is terminated.
• the condensation reaction is carried out up to a residual formaldehyde content of 0 to 1.5% by weight, a formose is obtained which contains approx. 25% by weight of 5-carbon atoms and 45% by weight Contains compounds with 6 carbon atoms and about 20 wt .-% of compounds with 7 and more carbon atoms.
• only about 10% of polyols, hydroxyketones and hydroxyaldehydes with 2.3 and 4 carbon atoms are obtained. This corresponds to an average hydroxyl functionality of approx. 5.
• the functionality of the products can optionally be varied further in the desired manner if certain application effects are to be achieved.
• low molecular weight polyhydric alcohols molecular weights up to approx.
• 300 are ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, diethylene glycol, dipropylene glycol, triethylene Glycol, tetraethylene glycol, D ibutylene glycol, glycerol, trimethylolpropane, pentaerythritol, sorbitol, butane triols and hexane triols as well as oxyethylation products of these alcohols or also hydrogenated formose (formite) in question.
• the use of amines and / or ethanolamines as a blending component is also possible.
• Examples include M ONO, D i and triethanolamine, mono-, di- and triisopropanolamine, N-alkanolamines, such as N-ethanolamine and N-Methyldi- ⁇ thyldiäthanolamin and lower aliphatic mono- and polyamines, such as ethylamine, ethylenediamine, diethylenetriamine and Triethylene tetramine.
• N-alkanolamines such as N-ethanolamine and N-Methyldi- ⁇ thyldiäthanolamin
• lower aliphatic mono- and polyamines such as ethylamine, ethylenediamine, diethylenetriamine and Triethylene tetramine.
• formoses can be used as a polyol component in the polyisocyanate polyaddition process for the production of polyurethane plastics. It has now been found that polyurethane plastics, in particular foams, can be produced in this way with extremely high flame resistance if a mixture of formose and dialkylphosphites is used as the starting component instead of the pure formose. Compared to pure formose, mixtures of this type have a surprisingly low viscosity, which is of great advantage in terms of application technology; because the mixtures are easy to dose.
• the mixtures of formose and dialkyl phosphites also surprisingly have the ability to dissolve large amounts of crystallized sugars (mono- and / or disaccharides).
• compounds capable of aminoplast formation can also be added to the mixtures according to the invention.
• the invention thus relates to a process for reducing the viscosity of formoses by adding a viscosity-reducing agent, which is characterized in that dialkyl phosphites, optionally in a mixture with trialkyl phosphites and / or ⁇ -hydroxyalkylphosphonic acid esters and / or ⁇ -aminoalkylphosphonic acid esters and / or or compounds capable of aminoplast formation.
• a viscosity-reducing agent which is characterized in that dialkyl phosphites, optionally in a mixture with trialkyl phosphites and / or ⁇ -hydroxyalkylphosphonic acid esters and / or ⁇ -aminoalkylphosphonic acid esters and / or or compounds capable of aminoplast formation.
• the mixtures according to the invention are preferably 0.2 to 20 mol per mole of component A, particularly preferably 0.7 to 5 moles of component B and 0 to 3 moles, particularly preferably 0 to 1.5 moles, of water.
• the mixtures according to the invention can furthermore optionally also up to 100 G ew. parts, preferably 10 to 50 parts by weight, based on 100 parts by weight of the mixture of A, B and C, contain at aminoplast.
• any formoses are suitable for the mixtures according to the invention; for the preferred use according to the invention (production of polyurethane plastics), however, it is advantageous to use the formoses produced by the applicant's more recent processes described above, since they are generally colorless and free of disruptive by-products.
• Formoses are preferably used which have an average molecular weight between 92 and 360, particularly preferably between 100 and 240, and a sugar content (calculated as glucose with a molecular weight of 180) of 4 to 85% by weight, particularly preferably 6-72% by weight. %, exhibit.
• formoses are preferred for some applications which, as described above, have been ⁇ -aldolized by subsequent treatment with formaldehyde in basic pH ranges.
• Formoses can of course also be used according to the invention, which have been converted into hemiacetals after their production by reaction with formaldehyde, or by subsequent treatment with acids with inter- or intramolecularly acetalized or ketalized formoses, or also by adding carbonyl compounds which have no hydroxyl group at the 4-position carbon atom, or by Maillard reaction, be used by acyloin condensation in the presence of cyanides or formoses modified by phenoplast formers. All of these modified formoses also fall under the term "formose" within the meaning of the present invention.
• crystallized mono- and disaccharides such as glucose, maltose or cane sugar are soluble in the mixtures according to the invention, as are natural invert sugars (e.g. bee honey) or artificial invert sugars, e.g. Hydrolysates of cane sugar, but also degradation products of corn and potato starch and pectin substances (amylose and amylopectins) or hydrolysates of any other di- and / or polysaccharides, e.g. of trehalose, galactose, raffinose, cellulose and dextrins.
• This is of particular technical interest because such crystallized mono- or disaccharides are difficult to react with polyisocyanates in pure form.
• All of these sugars can be present in component A in proportions of up to 70% by weight, preferably up to 50% by weight (based on component A).
• dialkyl phosphites which contain alkyl groups having 1 to 3 carbon atoms; dimethyl phosphite and diethyl phosphite are particularly preferred.
• phosphites with benzyl, cycloalkyl or alkyl groups with 4 to 8 carbon atoms can also be used.
• Suitable aldehydes and ketones are, for example, those with 1 to 15, particularly preferably 1 to 9, carbon atoms, for example formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, mesityl oxide, isophorone, acetophenone and their methylol derivatives, as they are obtainable by base-catalyzed partial or complete aldolization with formaldehyde on the C atoms ⁇ to the carbanyl group.
• ⁇ -hydroxyalkylphosphonic acid esters or x-aminoalkylphosphonic acid esters are also compounds which are reactive toward isocyanates and which are incorporated into the resulting polyurethane plastics when the mixtures according to the invention are reacted with polyisocyanates.
• aminoplast monomers can also be added to the mixtures according to the invention for further modification. All substances known per se which are capable of forming aminoplast are suitable for this purpose, as are described, for example, in German Offenlegungsschriften 2,324,134 and 2,713,198. In general, it is preferred to use the N-methylolation products of these compounds since they can be more easily incorporated into the polyurethane plastics in the reaction with polyisocyanates.
• Aminplast monomers preferred according to the invention are urea, symmetrically or asymmetrically substituted ureas such as N, N-dimethyl (or -diethyl or -dibutyl) urea, thiourea, dicyandiamide, melamine, oxamide, ethylene urea, F-caprolactam, pyrrolidone (2) , Aniline, acetylene diurein and the N-methylol compounds of all these monomers.
• urea, symmetrically or asymmetrically substituted ureas such as N, N-dimethyl (or -diethyl or -dibutyl) urea, thiourea, dicyandiamide, melamine, oxamide, ethylene urea, F-caprolactam, pyrrolidone (2) , Aniline, acetylene diurein and the N-methylol compounds of all these monomers.
• urea N-monomethylolurea, N, N-dimethylolurea, thiourea, N-monomethylolthiourea, N, N-dimethylolthiourea, ⁇ -caprolactam and N-methylol-f-caprolactam are particularly preferred.
• natural sugars such as D-glucose, D-fructose, D-galactose, maltose, lactose and cane sugar only dissolve very little or are completely insoluble in polar organic solvents, both at room temperature and when heated to approx. 100 ° C.
• Most mono- and disaccharides such as glucose, galactose, fructose and lactose are practically insoluble at room temperature in methanol or ethanol; Cane sugar only slightly dissolves in methanol or ethanol at room temperature after long dissolving times by 1% by weight.
• dialkyl phosphites and optionally also aminoplast monomers to formose or formose / mono- and / or disaccharide mixtures according to the invention also improves their emulsifiability or miscibility with the various low and high molecular weight polyhydroxyl compounds used in the production of polyurethane plastics .
• the modification reactions mentioned are explained in more detail in the examples.
• fillers such as, for example, can be incorporated into the mixtures according to the invention wise alumina hydrate are stirred in, forming stable, non-sedimenting, paste-like dispersions. These dispersions are ideal for the production of filler-containing polyurethane foams.
• the mixtures according to the invention can also be used as flame retardants for plastics and textiles; they are also antifreeze agents with an anti-corrosive effect.
• the mixtures according to the invention can be prepared by simply mixing the various starting components in any order. It is preferable to start with an optionally water-containing formose, to mix it with the aminoplast monomers and then to add any ⁇ -aldolized formoses, mono- and / or disaccharides that may be used, and to dewater the mixtures to a water content of 0.5-10%. , eg at reduced pressure and 30 - 60 ° C, and mixed with the dialkyl phosphite to clear solutions.
• the mixtures according to the invention can of course contain the aforementioned aldehydes and ketones, mono- or polyaldimines or ketimines, but also aldehydes and ketones together with mono- or polyamines, are subsequently admixed, hydroxyalkylphosphonic acid esters or alkyl- or polyamino-phosphonic acid alkyl esters being prepared in situ in the mixture according to the invention.
• the main use of the mixtures according to the invention is in the production of particularly flame-resistant polyurethane plastics, in particular polyurethane foams.
• the mixtures according to the invention generally contain more or less large amounts of water (the water can only be completely removed from molding mixtures with a great deal of technical effort), are suitable the mixtures according to the invention in particular for the production of polyurethane foams.
• both open-cell and closed-cell rigid polyurethane foams and open-cell flexible foams can be produced according to the invention.
• formulations which contain between 4 and 25 percent by weight, particularly preferably between 8 and 20%, water.
• suspensions of aluminum oxide hydrate or other mineral fillers described above can also be used in the mixtures according to the invention.
• up to 100 parts by weight, preferably 10 to 50% by weight, based on the total polyol component, of a higher molecular weight polyhydroxy compound (molecular weight approx. 400-10,000) can also be used as an elasticizing component.
• the amount of polyisocyanate in the formulation can vary within wide limits; it is possible to use both an excess of polyisocyanate (up to 120 of the calculated equivalent amount) and a less than equivalent amount of polyisocyanate, calculated on the sum of the isocyanate-reactive components present.
• the lower the characteristic number of the formulation (equivalent ratio of polyisocyanates and compounds reactive toward isocyanates), the higher the flame resistance of the foams obtained in this way. It is therefore preferable to work in the range between 20 and 70, particularly preferably between 30 and 60, in particular between 35 and 55.
• the mixtures according to the invention can to 3 0 percent, in proportions of 5 -%, preferably 5 to 20 wt .-%, based on total polyol component, also be used as crosslinkers in the preparation of open-cell foams.
• the rest of the polyol component in this case consists of polyhydroxyl compounds with a molecular weight of 400 to 10,000, preferably of polyether polyols.
• Aliphatic, cycloaliphatic, araliphatic, aromatic and heterocyclic polyisocyanates are suitable as isocyanate components for the production of the optionally cellular polyurethane plastics.
• 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 3 401 190), 2,4- and 2,6-hexahydrotoluenediisocyanate and any mixtures of these isomers, hexahydro-1, 3- and / or -1,4-phenylene diisocyanate, perhydro-2,4'-and / or -4,4'-diphenylmethane diisocyanate, 1,3- and 1,4-phenylene diisocyanate, 2,4--
• distillation residues obtained in the industrial production of isocyanates 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 polyisocyanates
• polyphenyJ-polymethylene polylsocyanates such as those produced by aniline-formaldehyde condensation and subsequent phosgenation ("crude MDI") and carbodiimide groups
• Urethane groups allophanate groups
• isocyanurate groups urea groups of the polyisocyanates containing biuret groups
• modified polyisocyanates modified polyisocyanates
• Suitable higher molecular weight polyhydroxyl compounds are e.g. at least two, usually 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 polyesters containing hydroxyl groups are, for example, 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 acid can also be used anhydrides or corresponding polycarboxylic acid esters of lower alcohols or mixtures thereof can be used to produce the polyesters.
• the polycarboxylic acids can be aliphatic, cycloaliphatic, aromatic and / or heterocyclic in nature and optionally substituted, for example by halogen atoms, and / or unsaturated.
• succinic acid examples include succinic acid, adipic acid, azelaic acid, phthalic acid, trimellitic acid, Phthal Acidrcanhydrid, tetrahydrophthalic anhydride, tetrachlorophthalic endomethylenetetrahydrophthalic, glutaric anhydride, maleic anhydride, fumaric acid, dimeric and trimeric fatty acids such as oleic acid, optionally mixed with 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, quinitol, mannitol and sorbitol, methyl glycoside, also diethylene glycol, triethylene glycol, T etraäthylenglykol, polyethylene glycols, dipropylene glycol, polypropylene glycols, dibutylene glycol and polybutylene glyco
• At least two, generally two to eight, preferably two to three, hydroxyl-containing polyethers are those of the type known per se and are, for example, by P oly- merization of epoxides such as ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide or epichlorohydrin with themselves, 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 epichlor
• Sucrose polyethers such as are described, for example, in German publications 1 176 358 and 1 064 938, are also suitable according to the invention. In many cases, those polyethers are preferred which predominantly (up to 90% by weight, based on all the OH groups present in the polyether) have primary OH groups.
• 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 Polybutadienes containing OH groups.
• polythioethers the condensation products of thiodiglycol with itself and / or with other glycols, dicarboxylic acids, formaldehyde, aminocarboxylic acids or amino alcohols may be mentioned.
• the products are either polythio ether, polythioether or polythioether amide.
• polyacetals e.g. the compounds which can be prepared from glycols, such as diethylene glycol, triethylene glycol, 4,4'-dioxethoxydiphenyldimethylmethane, hexanediol and formaldehyde, are suitable.
• glycols such as diethylene glycol, triethylene glycol, 4,4'-dioxethoxydiphenyldimethylmethane, hexanediol and formaldehyde
• Polyacetals suitable according to the invention can also be prepared by polymerizing cyclic acetals.
• Suitable polycarbonates containing hydroxyl groups are those of the type known per se, which e.g. by reacting diols such as propanediol (1,3), butanediol (1,4) and / or hexanediol (1,6), diethylene glycol, triethylene glycol or tetraethylene glycol with diaryl carbonates, e.g. Diphenyl carbonate, or phosgene can be produced.
• diols such as propanediol (1,3), butanediol (1,4) and / or hexanediol (1,6)
• diethylene glycol triethylene glycol or tetraethylene glycol
• diaryl carbonates e.g. 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 on phenol-formaldehyde resin or also on urea-formaldehyde resins can also be used according to the invention.
• 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 according to the invention.
• 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-bishydroxymethyl-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 of up to 400, dipropylene glycol, polypropylene glycols with a molecular weight of up to 400, dibutylene glycol, polybutylene glycols with
• 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 in which high molecular weight polyadducts or polycondensates are contained in finely diaphanous 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.
• the flame resistance of the plastics obtained is substantially increased by the phosphorus built into the polyurethane in this way or by reaction of polyisocyanates with ⁇ -hydroxyalkylphosphonic acid esters or ⁇ -aminoalkylphosphonic acid esters. Another improvement in Flame resistance is achieved by the additional use of aminoplast monomers in the mixtures according to the invention.
• the mixtures a) and b) according to the invention are stable on storage, as is shown by the constant viscosity.
• acids or bases eg triethylamine, dimethylbenzylamine or endoethylene piperazine
• the dimethyl phosphite or diethyl phosphite is added to the carbonyl groups of the formose to form the corresponding ⁇ -hydroxyphosphonic acid esters and transesterification reactions occur with Ab cleavage of methyl or ethyl alcohol, through which phosphites form the sugar.
• the transesterification reactions can be completed quantitatively by applying a vacuum and heating (for example 14 Torr and 55 ° C).
• This example shows that an increased supply of dialkyl phosphite can be used to obtain almost water-thin solutions which, if desired, can later be converted at any time into formose phosphite esters with a defined degree of esterification.
• the hydroxyl groups present can be esterified almost quantitatively, essentially asymmetric formose phosphite esters, e.g.
• the targeted ⁇ -aldolization formoses be obtained which contain primary per molecule on average at least two hydroxyl groups and, therefore, isocyanates over P oly- have a higher reactivity than the Facebookformosen.
• the viscosity of the aldolized formose thus produced which was concentrated to a water content of 5.2 in a rotary evaporator, is not measurable either at 25 ° C. or 35 ° C. and is above 570,000 mPas. At 50 ° C the viscosity of the formose is 25 736 mPas. The average molecular weight of this ⁇ -aldolized formose is approximately 198.
• Mixtures a), b) and c) are reactive solutions which are not at 50 to 70 ° C in a vacuum of 1 to 15 torr easy only ethanol elimination respond to Formose phosphite esters but also with the aminoplast on dehydration A midophosphon Anlagenreestern such as condense.
• Example 1 The formose described in Example 1 is dissolved in diethyl phosphite in various concentrations at 50 ° C. The following viscosity concentration dependency is found:
• This example shows the technically particularly interesting possible use of the mixtures according to the invention for the production of extremely flame-retardant, open-pore, strongly carbonizing rigid polyurea-polyurethane foams in the range 45 to 50, i.e. with insufficient amounts of polyisocyanates.
• the intensely stirred mixture is mixed with 3 parts by weight of water, 1.2 parts by weight of a commercially available silicone stabilizer (stabilizer OS 610 from Bayer AG), 0.2 part by weight of endoethylene piperazine and 0.25 part by weight of tin -II-octoate was added and then 184 parts by weight of a phosgenation product of an industrial aniline-formaldehyde condensate were stirred in.
• the polyisocyanate used has an NCO content of 29%. Foam formation is complete after 6 minutes and with a very even rise time without any signs of shrinkage. An open-cell rigid foam with a built-in flame retardant is obtained, which has a density of 30 kg / m.
• Example 6 b) If the mixture according to the invention described in Example 6 b) is used for impregnation reactions or matrix reactions in flexible polyurethane foams, even before the modification, flammable flexible polyurethane foams become so flame-retardant that they self-extinguish after ignition with a Bunsen flame.

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