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
  • C08G18/08—Processes
  • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
• • 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
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]

Definitions

• High-quality polyurethane films that, for example, achieve the level of value necessary for textile coating, have so far been obtained from dispersions that are produced using organic solvents in the polyaddition.
• the polyaddition in solution makes it possible to build up a high molecular weight polyurethane in a homogeneous phase before it is dispersed in water. As a result, the solid of the disperse particles is also highly homogeneous.
• This chain extension reaction can take place in the presence of water, so that an aqueous dispersion of a polyurethane is formed immediately.
• This method is particularly suitable for the production of cationically modified polyurethanes or Production of polyurethanes containing anionic carboxylate groups.
• DT-CS 2 446 440 describes a further process which relates to the solvent-free production of polyurethanes in aqueous dispersion.
• a sulfonate and NCO group-containing prepolymer is then reacted without the use of solvents with a compound which is difunctional in the sense of the isocyanate polyaddition reaction and has hydrogen atoms which are reactive toward isocyanate groups.
• the NCO prepolymer is reacted with the NCO group reactive compound during the dispersing process, i.e. after the previous solution of the chain extender in the dispersing water, or after the prepolymer has been dispersed in water.
• the process mentioned enables the production of high-quality, sulfonate-containing polyurethanes in aqueous dispersion.
• it has the disadvantage that it is limited to polyurethanes bearing sulfonate groups and only water or water-soluble polyamines can be used as chain extenders.
• Another characteristic of this process is that the chain extension. i.e. it builds up to a high molecular weight polyurethane urea in a heterogeneous phase.
• the chain extender - diamine, water - is in the liquid phase and only reaches the center of the dispersed particle over a certain period of time.
• the chain extender i.e. the diamine dissolved in water initially reacts in the outer regions of the dispersed particle.
• the concentration of the chain extender decreases steadily towards the center of the particle.
• Dispersions whose solid particles are not homogeneous are therefore obtained by this process. This results in polyurethane ureas which, compared to products made in homogeneous solution, have lower mechanical strength and in some cases poorer resistance to hydrolysis.
• the object of the awarded invention was therefore to provide a solvent-free or low-solvent process which allows the production of polyurethanes in the aqueous phase with improved properties, the improvement being achieved in particular by the high molecular weight solids distributed in the liquid aqueous medium should be obtained by polyaddition in the most homogeneous phase possible.
• polyurethanes can be produced in aqueous dispersion or solution by using NCO-terminated prepolymers. which contain a hydrophilic radical or / and an external emulsifier, are mixed with a polyarin chain extender in at least partially blocked form before being dispersed in water and then dispersed in water.
• the present invention therefore relates to a process for the preparation of aqueous solutions or dispersions of polyurethane-polyureas by reacting chemically incorporated hydrophilic groups and / or external prepolymers containing at least 2 free isocyanate groups and not containing chemically bound emulsifiers and having at least 2 primary and / or or secondary amino group-containing organic compounds in the aqueous phase, characterized in that the hydrophilically modified and / or an external emulsifier-containing isocyanate group-containing prepolymer is mixed in the absence of water with compounds which contain at most one free primary or secondary amino group and at least one blocked, among the influence of water has a free primary or secondary amino group and a total of at least two at least partially blocked primary and / or secondary amino groups, and then mixing this mixture with Wa mixed.
• the present invention also relates to the dispersions or solutions obtainable by this process.
• the present invention also relates to the use of the dispersions or solutions obtainable by this process for coating flexible substrates.
• Starting materials for the process according to the invention are at least 2 terminal NCO prepolymers containing isocyanate groups.
• Difunctional NCO prepolymers are preferably used.
• the NCO prepolymers to be used in the process according to the invention are preferably those which have one or more hydrophilic group (s) which determine their solubility or dispersibility in water.
• hydrophilic group s
• hydrophobic NCO protipolywers per se in the process according to the invention if their solubility or dispersibility in water is ensured by the use of external emulsifiers.
• NCO prepolymers which have already been used in the preparation of aqueous polyurethane dispersions or solutions are suitable for carrying out the process according to the invention. They are produced using known methods of the prior art and are described, for example, in DT-OSen 1 495 745, 1 495 847, 2 446 440 2 340 512, US Pat. No. 3,479,310, GB-PS 1 15.3 088 or 1,076,688.
• Any organic compounds with at least two groups which are reactive toward isocyanate groups in particular a total of two amino groups, thiol groups, carboxyl groups and / or hydroxyl group-containing organic compounds of the molecular weight range 62-10,000, preferably 1,000 to 6,000.
• the corresponding dihydroxy compounds are preferably used.
• the use of tri or higher functional compounds in the sense of the isocyanate polyodition reaction, in small proportions to achieve a certain degree of branching, is also possible, as is the previously mentioned possible use of tri- or higher functional rolyisocyanates for the same purpose.
• the polyethers which are preferred according to the invention and preferably have two hydroxyl groups are those of the type known per se and are, for example, polymerized by themselves with epoxides such as ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide or epichlorohydrin, for example in the presence of BF 3 , or by adding these epoxides, optionally in a mixture or in succession, to starting components with reactive hydrogen atoms such as alcohols and amines, for example water, ethylene glycol, propylene glycol (1,3) or - (1,2), 4,4'-dihydroxy-diphenylpropane, Aniline.
• epoxides such as ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide or epichlorohydrin
• reactive hydrogen atoms such as alcohols and amines
• 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 polyether to be used is formed in an analogous manner by alkoxylation of starter molecules which are known per se, e.g. Ammonia, ethanolamine, ethylenediamine or sucrose.
• Folio ethers include, in particular, the condensation products of thiodiglycol with itself and / or with other glycols, dicarboxylic acids, formaldehyde, amino carboxylic acids or amino alcohols. Je naci. the CO components, the products are polythio ether, polythio ether ester, polythio ether ester amide.
• polyacetals e.g. the compounds which can be prepared from glycols, such as diethylene glycol, triethylene glycol, 4,4'-diethoxy-diphcnyldimethylmethane, hexanediol and formaldehyde.
• glycols such as diethylene glycol, triethylene glycol, 4,4'-diethoxy-diphcnyldimethylmethane, 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. 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 diaryloarbonates, 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. Polyhydroxyl compounds already containing urethane or urea groups can also be used.
• Low molecular weight polyols can also be used, e.g. Ethanediol, tropanediol 1,2 and 1,3, butanediol 1,4 and 1,3, pentanediols, hexanediols, trimethylolpropane, hexanetriols, glycerol and pentaerythritol.
• hydrophilic groups preferably mono- and in particular difunctional structural components in the sense of the isocyanate addition reaction, of the type described by way of example in the above-mentioned references with regard to the preparation of aqueous polyurethane dispersions or solutions, ie for example diisocyanates containing ionic or potential ionic groups, Diisocyanates or glycols containing diamines or dihydroxy compounds or polyethylene oxide units.
• the preferred hydrophilically modified structural components include, in particular, the sulfonate group-containing aliphatic diols according to DT-OS 2 446 440, the cationic or also anionic internal emulsifiers which can be incorporated according to German patent application P 26 51 506.
• the reactants are generally used in such proportions that the ratio of isocyanate groups to hydrogen atoms which are reactive towards NCO, preferably from hydroxyl groups, is from 1.05 to 10. preferably correspond to from 1.1 to 3.
• the order in which the individual reactants are added is largely arbitrary. You can either mix the hydroxyl compounds and add the polyisocyanate, or you can gradually add the mixture of hydroxyl compounds or the individual hydroxyl compounds to the polyisocyanate component.
• the NCO prepolymers are preferably produced in the melt at 30-190 ° C., preferably at 50-120 ° C.
• the prepolymers could of course also be produced in the presence of organic solvents, although one of the main advantages of the process according to the invention can be seen precisely in the possible avoidance of such solvents.
• Suitable solvents e.g. in an amount up to 25% by weight, based on the solid, could be used e.g. Acetone, methyl ethyl ketone, ethyl acetate, dimethylformamide or cyclohexanone.
• These external emulsifiers are thoroughly mixed with the NCO prepolymers before the process according to the invention is carried out. They are generally obtained in amounts of 1 to 30, preferably 5 to 20,% by weight. on the weight of the NCO prepolymer. It's all over possible to increase their hydrophilicity by additionally using such external emulsifiers even when using hydrophilically modified NCO test polymers, although this is generally not necessary.
• At least 2 organic compounds having primary and / or secondary amino groups are used in the process according to the invention. These compounds are preferably aliphatic or cycloaliphatic diamines with only primary and / or secondary amino groups.
• araliphatic diamines are also to be regarded as aliphatic diamines.
• Diprimary diamines are particularly preferably used, with particular preference being given to those diprimary diamines which have at least one cycloaliphatic ring in their molecule with in particular 6 ring carbon atoms, it being irrelevant whether the amino groups are linked directly to this cycloaliphatic ring or to an alkyl Substituents, especially methyl substituents of this aliphatic ring are linked.
• the diamines to be used in the process according to the invention generally have a molecular weight of 60-5 0 0, preferably 100-250.
• Suitable polyamines to be used in the process according to the invention are ethylene diamine, trimethylene diamine, tetramethylene diamine, hexamethylene diamine, propylene diamine-1,2, the isomerone mixture of 2,2,4- and 2,4,4-trimethylhexamethylene diamine, 1,3- and 1,4-xylylenediamine , Bis (2-aminoethyl) amine and methyl bis (3-aminopropyl) amine.
• the preferred diamines include, for example:
• blocked amino groups are to be understood in particular to mean those primary or secondary amino groups which have been converted into the corresponding ketimine, aldimine or enamine group by reaction with an aldehyde or ketone.
• Such ketimine, aldimine or enamine groups are largely inert to isocyanate groups at room temperature in the absence of moisture (see, for example, DT-OS 2 125 247, US Pat. No. 3,420,800, US Pat. No.
• ketimine, Aldimine or enamine groups which have at least partially blocked polyamines are known in the art and are described, for example, in Houben-Weyl, Methods of Organic Chemistry, Volume XI / 2, pages 73 ff. Or in DT-OS 2 125 247. Since the amino groups of the amine component to be used according to the invention need not be blocked quantitatively, there is also no need for the condensation reaction to be carried out quantitatively in the production of the partially blocked polyamines.
• Aldehydes or ketones suitable for producing the at least partially blocked polyamines to be used according to the invention are any organic compounds which have at least one ketone or aldehyde group and are otherwise inert under the reaction conditions.
• aliphatic or cycloaliphatic aldehydes or ketones with a total of 2 to 18, or in the case of the cycloaliphatic compounds 5 to 18, preferably 3 to 6, or in the case of the cycloaliphatic compounds 5 to 6 carbon atoms are preferably used.
• aldehydes or ketones examples include acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, acetone, methyl ethyl ketone, methyl isobutyl ketone, diisopropyl ketone, cyclohexanone or cyclopentanone.
• Aromatic aldehydes or ketones such as Benzaldehyde, acetophenone or benzophenone are also suitable, but less preferred.
• the NCO prepolymers which may contain external emulsifiers are mixed with the at least partially blocked polyamines mentioned.
• the quantitative ratio between NCO prepolymer and at least partially blocked polyamine is generally chosen so that the equivalent ratio (NCO groups of the prepolymer): (free + blocked amino groups of the amine component) is between 4: 1 and 1: 1, 5, preferably between 2: 1 and 1: 1.25 and in particular between 1.2: 1 and 1: 1.2.
• the two components are mixed in a temperature range from -20 to 100 ° C., preferably from 20 to 60 ° C.
• the subsequent step of the process according to the invention consists in mixing the mixture with water to produce the aqueous dispersion with simultaneous hydrolysis of the blocked polyamine. So much water is used for this step that the dispersion has as high a solids content as possible. Dispersions with 40 to 70% solids can preferably be prepared very well. Further dilution with water is easily possible. The water is preferably added in one pour or gradually as desired. However, the mixture of prepolymer with capped polyamine can be mixed with water in such a way that the mixture is introduced into the aqueous phase or that, after a continuous process in suitable mixing units, first prepolymer and capped polyamine and then water are mixed together. Water from 0 to 90 ° C is used, preferably from 20 to 60 ° C.
• the resulting dispersions are very fine, the particles preferably have a size of 20-200 nm, but can of course also be larger.
• the dispersions produced by the process according to the invention can of course be further modified in a known manner.
• polyurethanes produced by the process according to the invention and present in aqueous dispersion or solution are on a par with the known polyurethanes produced in organic solvents. Films made from them have excellent mechanical strength and hydrolysis resistance and can be used for a wide variety of applications.
• a particularly preferred area of use of the dispersions or solutions according to the invention is the coating of flexible substrates.
• the dispersions are particularly suitable for textile finishing, for glass fiber sizing or as adhesives.
• a dispersion is formed with a solids content of 40% and a Ford cup viscosity (4 mm nozzle) of 14 seconds.
• the dispersion shows a Tyndall effect in the translucent light.
• the dispersion dries to clear, elastic films and is suitable for textile coating.
• a prepolymer according to Example 1 is produced. After cooling to 60 ° C., 250.2 g of a ketimine composed of isophoronediamine and methyl ethyl ketone (87% blocked amino groups) are stirred and then dispersed as described in Example 1. The resulting dispersion is thin and shows a Tyndall effect.
• a prepolymer according to Example 1 is produced. After cooling to 60 ° C., 225 g of a ketimiris composed of isophoronediamine and acetone (amino groups blocked to 80%) are stirred in and then dispersed as described in Example 1. The resulting dispersion is thin and shows a Tyndall effect.
• a prepolymer according to Example 1 is produced. After cooling to 60 ° C., 250.2 g of an aldimine composed of isophoronediamine and isobutyraldehyde (99% blocked amino groups) are stirred in and then dispersed as described in Example 1. The resulting dispersion is thin and shows a Tyndall effect.
• a prepolymer according to Example 1 is produced. After cooling to 60 ° C., 297 g of a ketimine composed of isophoronediamine and cyclohexanone (99% blocked amino groups) are stirred in and then dispersed as described in Example 1. The resulting dispersion is thin and shows a Tyndall effect.
• a prepolymer according to Example 1 is produced. After cooling to 50 ° C., 25.3 g of a condensation product of diethylene triamine and methyl ethyl ketone of the formula are added to, whereupon a temperature rise of 10 ° C occurs. The amount of free NH groups used corresponds to a conversion of 5% of the available NCO groups. 200.1 g of a ketimine composed of isophoronediamine (90% blocked amino groups) and methyl ethyl ketone are then stirred in and the mixture is dispersed as described in Example 1.
• the resulting dispersion is thin and shows a Tyndall effect.
• a dispersion is formed with a solids content of 30% and a Ford viscosity (4 mm nozzle) of 15 seconds.
• the dispersion shows a Tyndall effect in the translucent light.
• the dispersion dries to clear, colorless, elastic films. It is suitable for coating paper and leather.
• a dispersion is formed with a solids content of 30% and a Ford cup viscosity (4 mm nozzle) of 15 seconds.
• the dispersion shows a Tyndall effect in the translucent light.
• the dispersion is suitable as a binder in leather finishing. It dries to clear, colorless, elastic films.
• the result is a dispersion with a content of 30% and a Ford cup viscosity (4 mm nozzle) of 13 seconds.
• the dispersion shows a Tydall effect in the translucent light.

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• 1977
  • 1977-06-07 DE DE19772725589 patent/DE2725589A1/de not_active Withdrawn
• 1978
  • 1978-05-24 CA CA303,927A patent/CA1129128A/fr not_active Expired
  • 1978-06-01 DE DE7878100046T patent/DE2860037D1/de not_active Expired
  • 1978-06-01 EP EP19780100046 patent/EP0000029B1/fr not_active Expired
  • 1978-06-05 JP JP6684378A patent/JPS543196A/ja active Granted
  • 1978-06-05 AT AT406278A patent/AT371487B/de not_active IP Right Cessation
  • 1978-06-05 IT IT4970078A patent/IT1104711B/it active
  • 1978-06-06 ES ES470537A patent/ES470537A1/es not_active Expired
  • 1978-06-06 BR BR7803624A patent/BR7803624A/pt unknown
  • 1978-06-07 AU AU36902/78A patent/AU516678B2/en not_active Expired
• 1987
  • 1987-02-27 US US07/019,902 patent/US4829122A/en not_active Expired - Fee Related

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