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
  • C08G18/83—Chemically modified polymers
  • C08G18/84—Chemically modified polymers by aldehydes
• • 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
  • C08G18/08—Processes
  • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
  • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
  • C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
• • 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
  • C08G18/08—Processes
  • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
• • 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
  • C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
  • C08G18/343—Polycarboxylic acids having at least three carboxylic acid 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
  • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
  • C08G18/4263—Polycondensates having carboxylic or carbonic ester groups in the main chain containing carboxylic acid groups

Definitions

• dimethylolpropionic acid can be used as chain extender for the opening of polyurethanes, the free carboxyl group being predominantly retained and then being neutralized (see, for example, US Pat. No. 3,412,054, DT-OS 1,913,271).
• polyurethanes which contain free primary or secondary amino groups are mixed with ⁇ -propiolactone or the anhydride Dicarboxylic acid reacted, the polyurethane being modified with free carboxyl groups (see, for example, DT-AS 1 237 306).
• polyether ester or Pol y terminated O H groups and pendant sulfonate or carboxylate groups for the synthesis of anionic polyurethane dispersions use (see. For example, DT-AS 1,570,615).
• Esters which contain both hydroxyl groups and free carboxyl groups are known from the chemistry of dispersible ester resins (cf., for example, DT-OS 2,323,546, US Pat. No. 4,029-617, BE-PS 803,346 or US Pat. PS 3 876 582), but are in such products, the reactive groups are statistically distributed, so that it is not possible to build up structurally defined and, in particular, predominantly linear polyurethanes on the basis of these known products.
• the polyhydroxyl component used in the process according to the invention has an (average) OH functionality of 1.8 to 3, preferably 1.8 to 2.2. It is either glycols or glycol mixtures of an (average) molecular weight of 62 to 10,000 preferably 200 - 5 0 00 and especially 300-3000 or alcohol mixtures which monohydric alcohols of the molecular weight range 32 to 5000, preferably 500 to 4000 and / or glycols of already mentioned molecular weight ranges and / or higher functional alcohols in the molecular weight range 92-10,000, preferably 92-300.
• glycols are preferably polyester diols or polyether diols.
• the higher functional polyhydroxyl compounds are preferably simple alkane polyols, but trifunctional or higher functional polyether polyols or polyester polyols are also suitable.
• 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 anhydrides or corresponding polycarboxylic acid esters of lower alcohols or mixtures thereof can also be used to produce the polyesters.
• the polycarboxylic acids can be more aliphatic, cycloaliphatic, be aromatic and / or heterocyclic in nature and optionally substituted, for example by halogen atoms, and / or unsaturated.
• Examples of these are: 'succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, trimellitic acid, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, tetrachlorophthalic anhydride, malefic acid, anhydride, malefic acid malefic anhydride, malomic acid malefic acid, acid malefic acid, in a mixture with monomeric fatty acids, dimethyl terephthalate, 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, methylglycoside, also diethylene glycol,.
• Triethylene glycol Triethylene glycol, tetraethylene glycol, polyethylene glycols, dipropylene glycol, polypropylene glycols, dibutylene glycol and polybutylene glycols in question.
• the polyesters can have a proportion of terminal carboxyl groups.
• Polyesters of lactones, for example ⁇ -caprolactone or hydroxycarboxylic acids, for example ⁇ -hydroxycaproic acid, can also be used.
• the polyethers which are suitable according to the invention and preferably have two hydroxyl groups are those of the type known per se and are obtained, for example, by polymerizing epoxides such as ethylene glycol, propylene glycol, butylene glycol, tetrahydrofuran, styrene oxide or epichlorohydrin itself, e.g. in the presence of BF 3 , or by the addition of these epoxides, optionally in a mixture or in succession, to starting components with reactive hydrogen atoms such as water or alcohols such as ethylene glycol, propylene glycol (1,3) or - (1,2), 4 , 4'-dihydroxy-diphenylpropane.
• epoxides such as ethylene glycol, propylene glycol, butylene glycol, tetrahydrofuran, styrene oxide or epichlorohydrin itself, e.g. in the presence of BF 3 , or by the addition of these
• Polyethers modified by vinyl polymers e.g. by polymerization of styrene or 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.
• the proportionally higher-functionality polyethers which may optionally be used are formed in an analogous manner by alkoxylation of higher-functionality starter molecules, known per se, e.g. Ammonia, ethanolamine, ethylenediamine or sucrose.
• the condensation products of thiodiglycol with itself and / or with other glycols, dicarboxylic acids, formaldehyde, aminocabonic acids or amino alcohols should be mentioned in particular.
• the products are polythio ether, poly thio ether, poly thio ether ester amide.
• polyaetal e.g. the compounds which can be prepared from glycols, such as diethylene glycol, triethylene glycol, 4,4'-dioxethoxy-diphenyldimethylmethane, hexanediol and formaldehyde, are questionable.
• glycols such as diethylene glycol, triethylene glycol, 4,4'-dioxethoxy-diphenyldimethylmethane, 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, 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
• tetraethylene glycol 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. Also already containing urethane or urea groups. Polyhydroxyl compounds can be used.
• the polyhydroxyl component to be used according to the invention preferably consists exclusively of the glycols mentioned by way of example.
• mixtures of such glycols with higher-functionality polyhydroxyl compounds come into consideration insofar as the average hydroxyl functionality of the mixtures is within the above-mentioned range.
• monohydric alcohols in the polyhydroxyl component used according to the invention, although it is also conceivable that the polyhydroxyl component consists exclusively of a mixture of monohydric and higher than difunctional alcohols, provided the above-mentioned condition regarding the average OH functionality of the mixture is met is. In general, however, when using monohydric or higher than dihydric alcohols, a glycol component will always be used in the polyhydroxyl mixture at the same time.
• Suitable monohydric alcohols are e.g. simple aliphatic, cycloaliphatic or araliphatic monohydric alcohols such as methanol, ethanol, dodecanol, benzyl alcohol or cyclohexanol. However, the use of such simple monohydric alcohols is less preferred.
• hydrophilic nonionic structural components i.e. especially monohydric or dihydric alcohols containing ethylene oxide units built into polyether chains.
• hydrophilic structural components are either dihydroxy polyethers having polyethylene oxide segments and a molecular weight within the range mentioned above for the glycols, or polyether alcohols having monovalent ethylene oxide units and having a molecular weight within the range mentioned above for the monohydric alcohols.
• Such hydrophilic structural components are described, for example, in patent application P 26 37 690.9.
• Mixtures of the polyhydroxy compounds mentioned are frequently used as the polyhydroxy component, for example to adjust the hardness, elasticity and grip behavior of the coatings produced from the dispersions to the requirements.
• the low molecular weight mono- two and polyhydric alcohols if used at all, preferably in amounts up to 5 0 HydroxylvXquivalentprozent to the entire polyhydroxyl component.
• the polyhydroxyl component is reacted with one or more intramolecular tricarboxylic acid monoanhydride (s) or tetracarboxylic acid monoanhydride (s).
• s intramolecular tricarboxylic acid monoanhydride
• tetracarboxylic acid monoanhydride s
• Diisocyanates R 1 (NCO) 2 are preferably used, where R 1 has the meaning already mentioned and preferably for an aliphatic hydrocarbon radical with 4 to 12 carbon atoms, a cycloaliphatic hydrocarbon radical with 6 to 15 carbon atoms, an aromatic hydrocarbon radical with 6 to 15 carbon atoms or one araliphatic coals is hydrogen residue with 7 to 15 carbon atoms.
• diisocyanates examples include tetramethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, 1,4-diisocyanato-cyclohexane, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane, 4,4'-diisocyanatodicyclohexylmethane, 4,4'-diisocyanato- dicyclohexylpropane- (2,2), 1,4-diisocyanatobenzene, 2,4-diisocyanatotoluene, 2,6-diisocyanatotoluene, 4,4'-diisocyanatodiphenylmethane, 4,4'-diisocyanato-diphenylpropane- (2,2), p- Xylylene diisocyanate or ⁇ , ⁇ , ⁇ , ⁇ '-t
• polyfunctional polyisocyanates known per se in polyurethane chemistry or modified ones known in the art, for example carbodiimide groups, allophanate groups, isocyanurate groups, urethane groups and / or biuret groups, in the process according to the invention.
• monoisocyanates such as e.g. Phenyl isocyanate or dodecyl isocyanate or partially blocked polyisocyanates are possible in principle. However, care must always be taken to ensure that the average NCO functionality of the polyisocyanate component is between 1.8 and 3.0.
• Any inorganic or organic bases are suitable for the partial neutralization of the reaction product between the polyhydroxyl component and the anhydride having carboxyl groups.
• Preferred neutralizing agents are tert.
• Amines in the molecular weight range 59-200 such as trimethylamine, Triethylamine, triisopropylamine, tributylamine, N-methylpyrrolidine, N-methylpiperidine, dimethylaminoethanol, dimethylaminopropanol, dimethylaniline, pyridine.
• inorganic bases such as the hydroxides, oxides, carbonates, hydrogen carbonates of the alkali metals, in particular sodium hydroxide, potassium hydroxide, lithium hydroxide, potassium carbonate.
• inorganic compounds can be added either as such in finely powdered form or as aqueous or alcoholic solutions. If a solvent which is reactive towards isocyanates, such as methanol or water, is also used, this must then be removed again by distillation.
• the reactions of the first to third reaction stages can be carried out in the presence of organic solvents, in particular those of a polar type, such as acetone, methyl ethyl ketone, N-methylpyrrolidine, methylene chloride, the solvent being generally added to the extent that the increasing viscosity of the polymer melt requires it .
• the process is preferably carried out at elevated temperature and in the absence of solvents. If the presence of solvents is unavoidable for reasons of viability, preferably not more than about 10%. based on the reaction mixture used. If possible, those solvents are used which are also desirable from the point of view of later use and which, for example, bring about a lowering of the film-forming temperature, improvement of the flow, drying behavior, etc.
• paint solvents in particular are added, e.g. Methyl isobutyl ketone, glycol monomethyl ether acetate, glycol diethyl ether.
• the reaction of the polyhydroxyl component to the carboxy-anhydride the proportions of the reactants are chosen so as to be present in the reaction mixture for each hydroxyl group of the polyhydroxyl 0.05-1 preferably 0 1 to 0, 5 anhydride groups.
• This reaction is preferably carried out at 40-170 ° C., in particular at 50-150 ° C., until the characteristic anhydride bands at 1780 cm -1 and 1860 cm -1 have disappeared in the IR spectrum of a sample.
• the carboxyl groups of the reaction product from the polyhydroxyl component and carboxy anhydride which may be present in a mixture with excess, unmodified polyhydroxyl component, are partially neutralized with the bases mentioned by way of example so that 0.1 in one mole of the partially neutralized reaction product -4, preferably 0.2-1 mol of carboxylate groups, at least 0.1 mol of carboxyl groups and a total of 1.8-3.8, preferably 1.8-2.2 mol of carboxyl and optionally hydroxyl groups are present.
• Partial neutralization is easiest with tertiary amines, which are simply added to the reaction mixture in the required amount.
• amines with isocyanate-reactive groups preferred are those in which the reactivity of this group is poor, e.g. sec- or tert-hydroxy groups or amide or urethane groups, inorganic bases are preferably added in aqueous or alcoholic solution, the solvent then having to be removed by distillation.
• the next reaction stage of the process according to the invention consists in the reaction of the carboxylate and free carboxyl groups and, if appropriate, hydroxyl groups neutralized m feels.s U, as well as optionally present in the mixture, non-modified polyhydroxyl component with the polyisocyanates mentioned by way of example to the corresponding NCO prepolymers.
• urethane groups are formed from hydroxyl groups and amide groups are formed from carboxyl groups with elimination of CO 2 , so that an NCO prepolymer is formed which contains amide, carboxylate and optionally urethane groups.
• the proportions in this reaction are chosen such that for each equivalent of groups that are reactive towards isocyanate groups (carboxyl and optionally hydroxyl groups) 1.1 to 2, preferably 1.2 to 2 and in particular 1.3 to 1.8 equivalents of NCO groups omitted. It is also possible to use a large excess of polyisocyanate and, after the isocyanate addition reaction has ended, to remove the excess polyisocyanate, for example by distillation.
• the reaction is generally carried out at temperatures between 40 and 150 ° C., preferably 45 to 130 ° C.
• the isocyanate addition reaction ie until to calculate the predicted NCO content of the reaction products.
• This reaction can be terminated, for example, by immediately subjecting the reaction mixture which has not fully reacted to the chain extension reaction according to the fourth reaction stage, for example by introducing the reaction mixture into an aqueous diamine solution.
• NCO prepolymer partially neutralized reaction product with the exemplified polyisocvants to the corresponding NCO prepolymer.
• urethane groups are formed from hydroxyl groups and amide groups are formed from carboxyl groups with elimination of CO 2 , so that an NCO prepolymer is formed which contains amide, carboxylate and optionally urethane groups.
• the proportions in this reaction are selected so that for each equivalent of isocyanate reactive groups (carboxyl and optionally hydroxyl groups) 1, 1 to 2, preferably 1.2 to 2 and especially 1.3 to 1.8 equivalents of NCO groups omitted.
• reaction is generally carried out at temperatures between 40 and 150 ° C., preferably 45 to 130 ° C.
• branched reactants for the polyisocyanate component ie compounds which have a statistical average of more than two carboxyl and hydroxyl groups
• reaction mixture it is possible to terminate the reaction at a point in time in which free carboxyl and optionally hydroxyl groups are present in addition to free isocyanate groups in the reaction mixture.
• This termination of the reaction can take place, for example, by immediately subjecting the reaction mixture which has not fully reacted to the chain extension reaction according to the fourth reaction stage, for example by introducing the reaction mixture into an aqueous diamine solution.
• This procedure in which not all carboxyl or hydroxyl groups are reacted with the polyisocyanate component, is preferably carried out in an equivalent ratio between isocyanate groups and groups reactive to isocyanate groups of 0.8: 1 to 1.2: 1, i.e. it is also conceivable to use the polyisocyanate component in an amount which corresponds to an equivalent ratio of isocyanate groups to isocyanate-reactive groups of less than 1: 1, since the isocyanate addition reaction is not brought to an end in the formation of the prepolymers and only by this partial conversion of the isocyanate groups used is ensured even with a deficient amount of polyisocyanate component that the reaction product still has free isocyanate groups.
• an excessive increase in the viscosity of the NCO prepolymer and premature crosslinking can be avoided with certainty even when using compounds with more than two groups which are reactive toward isocyanate groups.
• partially blocked polyisocyanates or mixtures of mono-, di- and / or polyfunctional isocyanates with partially blocked polyisocyanates can also be used as the polyisocyanate component in the third process stage.
• a suitable choice of the functionality of the compounds having groups which are reactive toward isocyanate groups and / or the functionality of the polyisocyanate component (based on free isocyanate groups) can ensure that, on the one hand, an undesirable increase in viscosity or ver No wetting occurs and, on the other hand, intermediates with terminal isocyanate groups and also blocked isocyanate groups, as well as with incomplete reaction according to the above statements with free carboxyl or hydroxyl groups are obtained.
• Suitable partially blocked polyisocyanates are, in particular, partially blocked polyisocyanates which have a statistical average of 1.8-2.2 free isocyanate groups per molecule, ie for example triisocyanates with one blocked and two unblocked isocyanate groups.
• Suitable mixtures containing partially blocked polyisocyanates are, in particular, those which contain either the latter partially blocked polyisocyanates or else monoblocked diisocyanates in addition to moon-, di- and / or polyfunctional polyisocyanates, the individual components of these mixtures should be selected such that the average NCO functionality (based on free isocyanate groups) is between 1.8 and 2.2.
• Suitable blocking agents are the monofunctional blocking agents known per se in polyurethane chemistry for organic polyisocyanates such as, for example, ⁇ -caprolactam, phenols such as, for example, phenol or o-cresol, ketoximes such as, for example, methyl ethyl ketone ketoxime or CH-acidic compounds such as diethyl malonate.
• organic polyisocyanates such as, for example, ⁇ -caprolactam, phenols such as, for example, phenol or o-cresol, ketoximes such as, for example, methyl ethyl ketone ketoxime or CH-acidic compounds such as diethyl malonate.
• ketoximes such as, for example, methyl ethyl ketone ketoxime or CH-acidic compounds such as diethyl malonate.
• the production of the partially blocked Polyisocyanates are made using the organic polyisocyanates exemplified above by known methods of isocyan
• chain extension is to be understood both as a true chain extension without branching and as a branching or crosslinking of the prepolymers (use of higher than difunctional “chain extension agents”).
• this chain extension reaction is combined with the simultaneous conversion of the process product into an aqueous dispersion. The simplest way to do this is to use water only as a chain extender.
• liquid prepolymer which is present in a honey-like consistency
• Simple laboratory stirrers are sufficient for this mixing process, although it is of course also possible to use dispersing machines with high shear forces as well as the use of non-mechanical dispersing agents such as ultrasonic waves of extremely high frequency.
• the temperature during the mixing process is between 1 0 and 180 ° C, preferably between 20 ° C and 100 ° C. This process can also be carried out under pressure.
• the chain extension reaction can, however, also be carried out using mixtures of water and water-soluble chain extenders, chain extenders preferably being used which have a higher reactivity towards isocyanate groups than water. It is also possible to use the NCO prepolymer in To disperse water and to add the chain extender mentioned after the dispersion has taken place.
• chain extender are in particular exclusively hydrazines or polyamines containing primary or secondary amino groups, preferably hydrazines or diamines of a molecular weight above 31, preferably between 32 and 600.
• hydrazines or polyamines suitable as chain extenders are hydrazine, ethylenediamine, diethylenetriamine, 1,2-diaminopropane, 1,3-diaminopropane, 3,3,5-trimethyl-5-aminomethyl-eyclohexylamine or 1,4-diaminobutane.
• chain extenders are described in DT-OS 1 495 847 or in DT-AS 1 237 306.
• the water is used in a 0.2 to 10-fold amount by weight, based on NCO prepolymer.
• the chain extension reaction takes place using a mixture of water and polyamines of the type mentioned, which are additionally modified by chemically fixed ionic groups, preferably by chemically fixed sulfonate groups.
• an ionically modified chain extender is e.g. the N- (2-aminoethyl) -2-aminoethanesulfonic acid sodium.
• the chain extension reaction which takes place in the fourth reaction stage can also be carried out using solvents in which the prepolymer is present in solution, although it is one of the essential advantages of the process according to the invention that such Solvent can be dispensed with in principle.
• the solvents which may be used in the chain extension reaction correspond to the solvents which are also suitable for the preparation of the prepolymers.
• a further possibility of chain extension of the NCO prepolymers obtained in the third process step can also be carried out according to the principles of the process described in US Pat. No. 3,756,992 or the process described in German Patent Application P 26 37 690.9 in such a way that the NCO Prepolymer first by reaction with vzw.
• Ammonia or primary amines such as, for example, methylamine or n-butylamine, prepare prepolymers with terminal urea groups and extend them via the intermediate stage of prepolymers containing methylol groups by reaction with formaldehyde or crosslinked with compounds of the type described in US Pat. No. 3,756,992 containing methylol groups.
• the reaction of the NOO prepolymers with compounds containing methylol groups of the type mentioned in US Pat. No. 3,756,992 without prior conversion of the terminal NCO groups into the corresponding urea groups to give prepolymers containing methylol groups and their subsequent thermal treatment according to US Pat. No. 3,756,992 represents a viable way of chain extension or crosslinking of the NCO prepolymers obtained in the third stage of the process according to the invention.
• the chain extension according to these latter variants also involves the construction of the high molecular weight polyadducts or the preparation of the intermediate products containing terminal methylol groups with their dispersion Water.
• prepolymers containing terminal urea groups which are present as dispersions or solutions in water, are then reacted either in the aqueous phase with compounds which release formaldehyde or formaldehyde, for example paraformaldehyde, or with compounds containing methylol groups in the aqueous phase to form terminal prepolymers containing methylol groups, the final extension or Crosslinking takes place before and / or during and / or after the removal of the water, for example by evaporation or evaporation during the production of fabrics from the dispersions by a heat treatment at 25 to 180 ° C.
• this reaction step is preferably carried out in the absence of water, followed by dispersion of the prepolymers containing methylol groups in water and their further treatment as described above.
• a chain extension of the NCO prepolymers according to the principles of DT-OS 2 543 091 is also possible in principle.
• the type and proportions of the starting materials are therefore preferably selected so that the NCO prepolymers obtained meet the criteria mentioned.
• aqueous dispersions of the process products according to the invention can of course also be carried out with the use of external emulsifiers, although one of the main advantages of the process according to the invention is that the use of such emulsifiers can be dispensed with.
• the process according to the invention can of course also be carried out using the catalysts known per se which accelerate the NCO / OH reaction.
• the new method according to the invention brings with it a considerable increase in the space-time yield compared to the known solvent method, since on the one hand the solution medium volume and on the other hand, the energy and time-consuming distillation process is eliminated.
• the dispersions produced by the process according to the invention have a wide variety of fields of application. They can e.g. use for leather finishing or can be used for coating a wide variety of materials, especially for textile coating. Here you can use it as an adhesive or cover rope. Textile foam coatings are also possible. Significant areas of application also include use as an adhesive or as a lacquer.
• TMP Trimethylolpropane
• IPDI Isophorone diisocyanate
• the disentangled mixture of PE II, PE III, PA III and TMP is mixed with the TMA and stirred at 120-130 ° C until a clear melt is formed.
• the mixture is then cooled to 80 ° C., the T ⁇ A is added and stirring is continued for 15 minutes.
• a solution of the NH 3 in half of the dispersing water is stirred into the prepolymer thus obtained at 70-80 ° C. and, as soon as the product is homogeneous, the remaining water is added.
• pH 7.7.
• Expiry time (Ford D 4 ) 17 sec.

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• Polymers & Plastics (AREA)
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• Engineering & Computer Science (AREA)
• Manufacturing & Machinery (AREA)
• General Chemical & Material Sciences (AREA)
• Polyurethanes Or Polyureas (AREA)

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• 1977
  • 1977-06-29 DE DE19772729245 patent/DE2729245A1/de not_active Withdrawn
• 1978
  • 1978-06-12 CA CA305,257A patent/CA1094737A/fr not_active Expired
  • 1978-06-16 US US05/916,403 patent/US4172191A/en not_active Expired - Lifetime
  • 1978-06-20 EP EP78100198A patent/EP0000171B1/fr not_active Expired
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