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
  • C08G18/40—High-molecular-weight compounds
  • C08G18/48—Polyethers
  • C08G18/4833—Polyethers containing oxyethylene units
• • 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
• • 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
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
  • C08G18/78—Nitrogen
  • C08G18/7806—Nitrogen containing -N-C=0 groups
  • C08G18/7818—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative 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
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/80—Masked polyisocyanates
  • C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen

Definitions

• Aqueous solutions of polyurethanes or polyurethane ureas have been known for a long time (see, for example, Angewandte Chemie, 82, (197 0 ) pages 53 to 55, there ref. Cit. 4-8, 10a).
• hydrophilic centers built into the known water-soluble polyurethanes or polyurethane ureas can be both salt-like, i.e. represent ionic groups as well as hydrophilic nonionic groups.
• polyurethane ionomers include both chemically fixed cations, i.e. in particular chemically incorporated polyurethanes containing ammonium ions as well as chemically fixed anions, i.e. in particular chemically incorporated polyurethanes containing sulfonate or carboxylate groups.
• non-ionic, water-soluble polyurethanes or polyurethane ureas in particular include chains of polyethylene oxide.
• solutions of these polyurethanes have different, characteristic properties depending on the type of the hydrophilic center. So are polyurethane ionomer solutions because the the salt groups contained in them are practically not temperature-dependent in their solubility, stable against heating to boiling, non-ionic solutions, on the other hand, coagulate when heated (at approx. 60 ° C), since the polyethylene oxide chains gradually lose their solubility in water at higher temperatures. In contrast to ionomers, these solutions are resistant to the addition of practically unlimited amounts of electrolytes and are stable even after freezing and thawing.
• the sensitivity to electrolytes is particularly high in solutions of cationic polyurethanes, but solutions of polyurethane polycarboxylates are also sensitive. Small amounts of aqueous electrolyte solutions cause turbidity, larger amounts lead to slimy or cheesy deposits. Even if flocculation does not occur, the colloidal chemical state changes, which is noticeable, for example, in the changed viscosity and rheology.
• the present invention now provides new water-soluble polyurethanes, which are in the form their aqueous solution have both the advantage of excellent frost and electrolyte resistance and the advantage of very good temperature resistance.
• it is possible to produce such water-soluble polyurethanes if both hydrophilic segments containing ethylene oxide units and ionic groups are incorporated into the polyurethane. This is quite surprising since it turned out that mixtures of aqueous solutions of ionic and nonionic polyurethanes in no way have such a combination of desirable properties. Rather, such mixtures primarily have the disadvantages of the individual components.
• hydrophilic polyether segments either within the polymer main chain or at its ends or in the form of side chains, provides surprisingly effective protection for polyurethanes or have COO G groups, achieved with respect to the action of electrolytes. Even with a high content of cationic centers, for example more than 20 milliequivalents per 100 g of polyurethane the solutions are no longer precipitated by dilute sodium chloride solution.
• Organic diisocyanates suitable for the preferred process mentioned above for the preparation of the polyurethane elastomers according to the invention are those of the general formula R (NCO) 2 ' where R is an organic radical, as is preferred by removing the isocyanate groups from an organic diisocyanate of the molecular weight range 112-1000 140-400.
• Particularly preferred diisocyanates suitable for the process according to the invention are those of the general formula given, in which R represents a divalent aliphatic hydrocarbon radical having 4-18 carbon atoms, a divalent cycloaliphatic hydrocarbon radical having 5-15 carbon atoms, a divalent aromatic hydrocarbon radical having 6-15 carbon atoms or one araliphatic hydrocarbon radical having 7-15 carbon atoms.
• Typical representatives of organic diisocyanates which are preferably suitable for the process according to the invention are, for example, tetramethylene diisocyanate, hexamethylene diisocyanate and dodeca methylene diisocyanate, cyclohexane-1,3- and -1,4-diisocyanate, 1-isocyanato-3-isocyanatomethyl-3,5,5-trimethylcyclohexane, 4,4'-diisocyanatodicyclohexylmethane or also aromatic diisocyanates, such as 2,4-diisocyanatotoluene, 2,6-diisocyanatotoluene, mixtures consisting of these isomers, 4,4'-diisocyanatodiphenylmethane, 1,5-diisocyanatonaphthalene, etc.
• aromatic diisocyanates such as 2,4-diisocyanatotoluene, 2,6-di
• dihydroxy polyesters dihydroxy polylactones, Dihydroxypolyvonher and D are preferably used ihydroxypolycarbonate.
• the compounds according to the invention could also be used without the use of higher molecular weight polyhydroxyl compounds, i.e. can only be produced using diisocyanates and low molecular weight reactants (molecular weight ⁇ 300).
• the chain extenders of a molecular weight below 300 which are to be also used in the process according to the invention for the preparation of the water-soluble polyurethanes are, for example, the low molecular weight diols described in the preparation of the dihydroxy polyesters, or else diamines, such as diaminoethane, 1,6-diaminohexane, piperazine, 2,5-dimethylpiperazine, 1- Amino-3-aminomethyl-3,5,5-trimethylcyclohexane, 4,4'-diaminodicyclohexylmethane, 1,4-diaminocyclohexane, 1,2-propylenediamine or hydrazine, amino acid hydrazides, hydrazides of semicarbazidocarboxylic acids, bis-hydrazides and bis-semicarbazides in Consider.
• diamines such as diaminoethane, 1,6-diaminohexane, pipe
• Suitable structural components are also e.g. Oleyl diethanolamine, stearyl diethanolamine, adducts of long-chain alkyl isocyanates with diethanolamine or other amino alcohols, esterification products of long-chain fatty acids with glycerol or trimethylolpropane, adducts of amines having 6-24 C atoms or phenols with glycide or 3-ethyl-3-hydroxymethyl-ox.
• the tri-functional and higher functional structural components known per se in polyurethane chemistry can also be used in small proportions.
• the starting components are preferably selected so that the functionality does not exceed an average of 2.1.
• hydrophilic structural components with hydrophilic chains having pendant ethylene oxide units include both compounds of the formula and / or compounds of the formula
• Particularly preferred structural components a) are those of the first-mentioned formula (I).
• the compounds of the formulas (I) and (II) mentioned above can be prepared in accordance with the procedures of DT-OS 2 314 512 or 2 314 513, the addition of Disclosure made there is pointed out that, instead of the polyether alcohols mentioned there as starting material, it is also possible to use those whose polyether segment, in addition to ethylene oxide units, is also preferably up to 60% by weight, based on polyether segment, of propylene oxide, butylene oxide or styrene oxide Have propylene oxide units. The proportion of such "mixed polyether segments" can bring specific advantages in special cases.
• Dihydroxy polyethers having a molecular weight of 300-6000, preferably 500-3000, also containing ethylene oxide units can also be used as a hydrophilic structural component in the process according to the invention.
• hydrophilic ether groups i.e. Dihydroxypolycarbonates containing polyethylene oxide units are suitable as a hydrophilic structural component.
• Structural components b) essential to the invention are, for example in the sense of the isocyanate polyaddition reaction, monofunctional or difunctional representatives of the compounds mentioned by way of example in US Pat. No. 3,479,310, column 4, line 11 to column 5, line 46, or the corresponding compounds accessible by simple neutralization or quaternization with salt-like groups.
• Suitable neutralizing or quaternizing agents are, for example, the compounds mentioned in the US patent mentioned in column 6, lines 14 to 39.
• tertiary sulfonium groups for example, the compounds listed in US Pat. No. 3,419,533, column 3, line 75 to column 4, line 51 are used as synthesis components.
• the type and amount of components a) are chosen such that 2 to 50, preferably 11 to 20,% by weight of -CH 2 -CH 2 -O- ethylene oxide units built into the ether segments are present in the polyurethanes according to the invention.
• the sum of the number of milliequivalents of incorporated ionic groups per 100 g of polyurethane and the number of “pseudomillie equivalents” of incorporated ethylene oxide units per 100 g of polyurethane is 40 to 300 and particularly preferably between 60 and 200.
• a “pseudomilli equivalent” of built-in ethylene oxide units is to be understood here as the amount of ethylene oxide units built into a polyalkylene oxide chain, which makes the same contribution to the solubility of the polyurethane in water as one milliequivalent of built-in ionic groups.
• the effectiveness of the above-mentioned ionic groups with regard to their contribution to the solubility of the polyurethane depends exclusively on the number of milliequivalents of ionic groups and not on the type of the ionic groups.
• the solubility depends on the concentration of the hydrophilic centers built into the polyurethane from.
• the ionic groups can always be replaced by a certain amount of ethylene oxide arranged within a polyether chain, so that a corresponding one is exclusively non-ionic modified polyurethane is obtained, which has the same solubility in water, (with an analogous preparation of the polyurethane solutions is assumed) if the milliequivalents of ionic groups present in the ionically modified polyurethane are replaced by the same number of "pseudomilliequivalents" of nonionic groups.
• One milliequivalent of built-in ionic groups corresponds to 0.5 g of ethylene oxide units built into a polyether chain.
• a “pseudomilli equivalent” of nonionic groups is therefore to be understood as meaning 0.5 g of ethylene oxide units incorporated within a polyether chain.
• an exclusively ionically modified polyurethane with a content of 40 milliequivalents per 100 g of one of the above-mentioned ionic groups has the same water solubility as an analogue constructed and produced exclusively nonionically modified polyurethane with a content of 20 g per 100 g of that incorporated within a polyether chain Ethylene oxide.
• the process according to the invention for the preparation of the water-soluble polyurethanes can be carried out according to the methods of polyurethane chemistry known per se, both according to the one-step and the two-step process (prepolymer process).
• the reactants are used in an equivalent ratio of isocyanate groups to isocyanate-reactive groups of 0.8: 1 to 2.5: 1, preferably 0.95: 1 to 1.5: 1.
• an excess of NCO is used, this naturally results in compounds having NCO groups which, when converted into an aqueous solution, react further with the water with chain extension to the end product.
• any carboxyl groups (component b)) which may be present in the reaction mixture are not regarded as groups which are reactive towards isocyanate groups, which is justified in view of the inertness of these groups towards isocyanate groups.
• Both the one-step and two-step processes can be carried out in the presence or absence of solvents.
• Suitable solvents are, for example, water-miscible solvents which are indifferent to isocyanate groups and have a boiling point below 100 ° C, e.g. Acetone or methyl ethyl ketone.
• difunctional terminal compounds of molecular weight range 500 to 6000 mentioned above under 1 to 7 and having groups which are reactive toward isocyanate groups, with the hydrophilic chain extenders a) and b) and the chain extender which may also be used a molecular weight below 500 mixed.
• the diisocyanate component is then added to the mixture thus obtained in the absence of solvents, after which the reaction mixture is preferably brought to reaction at temperatures of from 50 to 150 ° C., optionally after addition of the catalysts known per se in polyurethane chemistry.
• the amount of the diisocyanate components is chosen so that there is an NCO / OH ratio of 0.8 to 1.05.
• component b) which have groups which can be converted into ionic groups
• this conversion by neutralization or quaternization known per se following the polyaddition reaction is recommended either in organic solution or in such a way that the polyurethane present in organic solution during its conversion is neutralized in an aqueous solution by neutralizing agents present in the water.
• the polyurethanes are advantageously converted into an aqueous solution by adding water to the stirred solution or melt. After removal of any solvent present by distillation, a purely aqueous solution remains.
• the first step is preferably in the melt of excess diisocyanate, higher molecular weight compound with groups of the type mentioned above under 1 to 7 which are reactive towards isocyanate groups, and hydrophilic chain extender a) and optionally b) while maintaining an NCO / OH ratio from 1.1: 1 to 3.5: 1, preferably 1.2: 1 to 2.5: 1, in the absence of solvents or even in the presence of solvents, an NCO prepolymer is prepared, which is then used in the absence of solvents, for example, is taken up in a suitable solvent.
• the solution of the prepolymer thus obtained can then be reacted in a manner known per se with the chain extender of the type exemplified above having a molecular weight below 300.
• the chain extender of the type exemplified above having a molecular weight below 300.
• the diamines or hydrazine derivatives mentioned are preferably used as chain extenders - in small amounts of water or a water / solvent mixture so offset that the NCO / NH ratio is between 2.5 and 1.05. This reaction can take place at room temperature or preferably at 25-60 ° C.
• the aqueous polyurethane solution is finally obtained.
• the chain extender in the total amount of water finally present in the solution (50-200% by weight, based on solid polyurethane) to solve.
• the two-stage process described is preferably carried out without solvent without major difficulties, namely in such a way that the NCO prepolymer described is prepared solvent-free and stirred into the water as a melt, the ionic or nonionic chain extenders containing amino groups mentioned here also being able to be present in water-soluble form .
• thermoplastics it is also possible, as is usual with solid thermoplastics, to build up the melt from the components, e.g. in a form, on a steel belt or in a screw, to crush the solid product and then to dissolve it in water.
• hydrophilic monoisocyanates are produced in analogy to the procedure described in German Offenlegungsschrift No. 2,314,512, but here too in addition to those made there Disclosure is pointed out that instead of the monofunctional polyether alcohols mentioned there as the starting material, it is also possible to use those whose polyether segment in addition to ethyl hydroxide units also contains up to 60, preferably up to 35% by weight, based on polyether segment, of propylene oxide, butyl oxide or styrene oxide , preferably have propylene oxide units.
• a linear polyurethane is preferably produced from the starting materials mentioned using an equivalent ratio of isocyanate groups: preferably 1: 1 groups which are reactive towards isocyanate groups, but which still contain ionic groups or groups which can be converted into ionic groups has no hydrophilic polyether segments.
• This linear polyurethane elastomer is then reacted in the melt or in a suitable solvent, for example of the type mentioned above, at 50 to 150 ° C. with the hydrophilic monoisocyanates, in particular an addition of the isocyanate group of the hydrophilic monoisocyanate to the active hydrogen atoms of the urethane present in the linear polyurethane.
• any groups that can be converted into ionic groups are then at least partially converted into the corresponding ionic groups by neutinelization or quaternization known per se.
• a procedure is particularly preferred according to which a prepolymer with terminal NCO groups is reacted with a monofunctional hydrophilic polyether, so that a polymeric polyurethane with terminal hydrophilic polyether segments is formed.
• a product can also be obtained by a one-step process in that a corresponding hydrophilic monofunctional polyether is also used as a structural component in the construction of the polyurethane.
• a prepolymer with terminal OH, SH, NH 2 , NHR or COOH groups with a hydrophilic monoisocyanate of the formula implement.
• R, X, Y, R "have the meaning given above.
• polyurethanes with terminal monofunctional hydrophilic polyethers are produced, preference is given to at least little branching of these products, e.g. through partial use of trifunctional or polyfunctional structural components or through partial allophanatization, trimerization or biuretization.
• the polyurethane according to the invention obtained in this way as a melt or as a solution can then be converted into an aqueous solution by mixing with water and, if appropriate, then distilling off the auxiliary solvent.
• aqueous polyurethane solutions according to the invention are clear and also show a solids content of e.g. 5-10% no Tyndall effect. At room temperature, layers that have dried out of the solutions dissolve smoothly and sparingly in water.
• the solutions of the polyurethane masses in water are stable, can be stored and shipped and can be used at any later time, e.g. B. proactive, processed. They generally dry directly to form stable plastic coatings, but the process products can also be shaped in the presence of crosslinking agents known per se.
• crosslinking agents known per se.
• polyurethanes with different properties are obtained. This means that soft, sticky tills, thermoplastic and rubber-elastic products from the various degrees of hardness up to glass-hard thermosets can be obtained.
• the hydrophilicity of the products can also fluctuate within certain limits.
• the elastic products can be used at higher temperatures, e.g. 1 00 - 180 ° C. process thermoplastic, provided that they are not chemically cross-linked.
• the process products are used for coating or for covering and impregnating woven and non-woven textiles, leather, paper, wood, metals, ceramics, stone, concrete, bitumen, hard fiber, straw, glass, porcelain, all kinds of plastics, glass fibers antistatic and wrinkle-free finish, as a binder for nonwovens, adhesives, adhesion promoters, laminating agents, water repellents, plasticizers, binders, e.g. B. for cork or wood flour. Glass fibers, asbestos, paper-like materials, plastic or rubber wastes, ceramic materials, as aids ic stuff printing and in the paper industry, as an additive to polymers, as sizing agents, for example for glass fibers. and suitable for leather finishing.
• vinyl polymers or active or inactive fillers you can modify the properties of the process products.
• up to 70%, based on the total amount of cesamite, of such fillers can be present in the end product.
• dyes, fillers, pigments, plasticizers or additives influencing the rheological properties can also be added, likewise e.g. Polymer dispersions, soot and cresolic acid brines.
• the products obtained by various application techniques can be dried at room temperature or at elevated temperature.
• a polyether diol started on propylene glycol according to Example 1 and 175 g (0. 100 mol) of a polyester diol consisting of adipic acid, phthalic anhydride and ethylene glycol and 107.5 g (0.050 mol) of the nonionically hydrophilic chain extender according to Example 1 were dewatered for one hour at 120 ° C., 15 torr, cooled to 80 ° C. and mixed with 109 g (0.650 mol) of hexane diisocyanate. The mixture is stirred at 120 ° C. for 2 hours, resulting in a prepolymer with an NCO content of 2.19%.
• the solution contains 17 milliequivalents of N + and 68 pseudo milliequivalents of ethylene oxide units.
• Example 2 As a comparative example to Example 2, a similar polyurethane solution was prepared without hydrophilic ethylene oxide units, the proportion of quaternary nitrogen being increased so that it corresponded to the sum of milliequivalents of quaternary nitrogen and pseudomilliequivalents of ethylene oxide according to Example 2.
• the aqueous polyurethane solution was prepared according to Example 2.
• the resulting cationic polyurethane solution has a solids content of 31% by weight, a viscosity of 600 cP at 22 ° C. and a pH of 1.8. Based on 100 g of solid, the solution contains 85 milliequivalents of quaternary nitrogen. 50 ml of the solution adjusted to 10% solids coagulate when less than 1 ml of a 10% saline solution is added.
• 133 g (0.074 mol) of a polyester diol from adipic acid and tetraethylene glycol with an average molecular weight of 1800 and 125 g (0.058 mol) of the nonionic-hydrophilic chain extenders according to Example 1 are dewatered at 15 Rorr and 120 ° C. for 30 minutes, cooled to 80 ° C. and 61.3 g of 1,6-hexane diisocyanate are added. After stirring for 2 hours at 120 ° C., a prepolymer with an NCO content of 5.35% by weight is obtained.
• the mixture is diluted with 100 ml of acetone, at 60 ° C (bath temperature), 23.8 g (0, 200 mol) of N-methyldiethanolamine are diluted with 50 ml of acetone, stirred for one hour at 60 ° C, 0.25 g ( 0, 003 mol) 1,2-diaminoproo pan added and quaternized one hour later at the same temperature with 23, 8 g (0, 189 mol) of dimethyl sulfate. 30 minutes after the dimethyl sulfate. 20 ml of water are added, the mixture is then stirred at a bath temperature of 60 ° C. until NCO can no longer be detected by IR spectroscopy.
• aqueous polyurethane solution has a solids content of 30% by weight, a viscosity of 67 cP at 22 ° C. and a pH of 2.3.
• 100 g of solid contain 53 milliequivalents of quaternary nitrogen and 50 pseudomilliequivalents of ethylene oxide units. 50 ml of a sample of this solution adjusted to 10% solids tolerate the addition of 100 ml of a 10% saline solution without coagulation occurring.
• 230 g of a technical polyethylene glycol mixture with an average molecular weight of 230 (as is the case in the distillation of tetraethylene glycol as a residue) and 119 g of N-methyldiethanolamine mixed together and at 80 ° C 262 g of a technical polyisocyanate mixture as it is obtained as a distillation residue in the production of hexane diisocyanate 1,6 (NCO content approx. 32% by weight) are slowly added dropwise. 30 minutes after the end of the dropping, NCO can no longer be detected by IR spectroscopy. 173 g of phosphoric acid (85% strength) and 1769 g of water are now added simultaneously with cooling.
• the resulting thin-bodied polyurethane solution has a pH of 1.6 at a solids content of 30% by weight. 50 ml of a sample of this dispersion adjusted to 10% solids tolerate 100 ml of a 10% saline solution without coagulation.

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• 1977
  • 1977-07-06 DE DE19772730514 patent/DE2730514A1/de active Pending
• 1978
  • 1978-06-28 EP EP78100254A patent/EP0000347A1/fr not_active Withdrawn
  • 1978-07-04 IT IT7850152A patent/IT7850152A0/it unknown

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