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
  • C08G18/10—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
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S528/00—Synthetic resins or natural rubbers -- part of the class 520 series
  • Y10S528/904—Isocyanate polymer having stated hydrophilic or hydrophobic property

Definitions

• the present invention relates to a new process for the preparation of new isocyanate polyaddition products having pendant hydroxyl groups and to the compounds obtainable by this process.
• the process according to the invention is based on the principle of reacting reactive systems containing isocyanate groups and oxazolidine groups with water, the chain extension reaction essentially taking place with formation of urea groups from the isocyanate groups and the amino groups released hydrolytically from the oxazolidines, while the hydrolytic cleavage of the oxazolidine groups also takes place comparatively inert hydroxyl groups do not participate in the reaction and are present laterally in the process products.
• the present invention in particular also relates to an embodiment of this process in which chemically incorporated hydrophilic groups and / or prepolymers containing external emulsifiers are used as prepolymers and the water is used in such an excess that immediately aqueous dispersions or solutions of the polyadducts are formed .
• the present invention finally also relates to the isocyanate polyaddition products obtainable by the process according to the invention.
• the process according to the invention for the first time opens up a possibility of producing predominantly linear polyurethanes which are therefore soluble in common solvents and which have pendant hydroxyl groups and are therefore accessible to a subsequent crosslinking reaction, for example with organic polyisocyanates. Because of their linear structure, the process products according to the invention, with the simultaneous incorporation of hydrophilic groups and / or the use of external emulsifiers, can also be converted without difficulty into aqueous dispersions or solutions, from which simple, crosslinkable fabrics can then also be subsequently produced.
• Starting materials for the process according to the invention are essentially linear prepolymers, which have a statistical average of 1.8 to 2.2, preferably 2, terminal isocyanate groups and generally have an average molecular weight of 500 to 10,000, preferably 800 to 4000.
• the NCO prepolymers are prepared by known methods in polyurethane chemistry by reacting excess amounts of organic polyisocyanates, preferably diisocyanates, with suitable, preferably difunctional, compounds having groups which are reactive toward isocyanate groups. Starting materials for the preparation of the NCO prepolymers are accordingly
• any organic polyisocyanates preferably diisocyanates of the formula where Q represents an aliphatic hydrocarbon radical having 4 to 12 carbon atoms, a cycloaliphatic hydrocarbon radical having 6 to 15 carbon atoms, an aromatic hydrocarbon radical having 6 to 15 carbon atoms or an araliphatic hydrocarbon radical having 7 to 15 carbon atoms.
• diisocyanates examples include tetramethyl diisocyanate, liexamethylene diisocyanate, dodecamethylene diisocyanate, 1,4-diisocyanato-cyclohexane, 1-isoyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane, 4,4'-diisocyanatodicyclohexylmethane, 4,4'-diisocyanate dicyclohexylpropane- (2,2), 1,4-diisocyanatobenzene, 2,4-diiaocyanatotoluene, 2,6-diisocyanatotoluene, 4,4'-diisocyanatodiphenylmethane, 4,4'-diiaocyanato-diphenylpropane- (2,2), p- Xylylene diiaocyanate or ⁇ , ⁇ , ⁇ ', ⁇ '-t
• polyfunctional polyisocyanates known per se in polyurethane chemistry, or else modified polyisocyanates containing, for example, carbodiimide groups, allophanate groups, isocyanurate groups, urethane groups and / or biuret groups.
• Any organic compounds with at least two groups which are reactive towards isocyanate groups in particular a total of two amino compounds, thiol groups, carboxyl groups and / or hydroxyl groups containing organic compounds of the molecular weight range 62-10,000, preferably 1,000 to 6,000.
• the corresponding dihydroxy compounds are preferably used.
• trifunctional or higher-functional compounds in the sense of the isocyanate rolyaddition reaction in small proportions to achieve a certain degree of branching is possible, as is the possible use of trifunctional or higher-functional rolyisocyanates mentioned above 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 obtained, for example, by polymerization 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 adding these epoxides, optionally in a mixture or in succession, to starting components with reactive water atoms such as alcohols and amines, for example water, ethylene 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 water 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 polyethers to be used, if appropriate, are formed in an analogous manner by known alkoxylation of higher-functionality starter molecules, e.g. Ammonia, ethanolamine, ethylenediamine or sucrose.
• the condensation products of thiodiglycol with itself and / or with other glycols, dicarboxylic acids, formaldehyde, aminocarboxylic acids or amiroalcohols should be mentioned in particular.
• Je nacl. the CO components, the products are polythio ether, tolythio ether, polythio ether anude.
• polyacetals e.g. the compounds which can be prepared from glycols, such as diethylene glycol, triethylene glycol, 4,4'-diethoxy-diphenyldimethylmethane, hexanediol and formaldehyde.
• glycols such as diethylene glycol, triethylene glycol, 4,4'-diethoxy-diphenyldimethylmethane, hexanediol and formaldehyde.
• Polyacetals suitable according to the invention can also be prepared by polymerizing cyclic acetals.
• Suitable polycarbonates having 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, rropanediol-1,2 and -1,3, butanediol-1,4 and -1,3, pentanediols, hexardiols, trimethylolpropane, hexanetriols, glycerol and fentaerythritol.
• Representatives of the poly (cyanate) and hydroxyl compounds to be used in the process according to the invention are e.g. in High Polymers, Vol. XVI, "Polyurethanes, Chemistry and Technology", written by Saunders-Frisch, Interacience Méahers, New York, London, Volume I, 1962, pages 32-42 and pages 44-54 and Volume II, 1964, Pages 5-6 and 198-199, as well as in the plastics manual, volume VII, Vieweg-Höchtlen, Carl-Hanser-Verlag, Kunststoff, 1966, e.g. on pages 45 to 71.
• hydrophilically modified prepolymers are to be used in the process according to the invention in accordance with the above-mentioned special embodiment, their preparation takes place according to known processes of the prior art, for example according to those in DT-OSs 1 495 745, 1 495 847, 2 446 440, 2 340 512, U S-PS 3 479 310, GB-PS'en 1 158 088 or 1 076 688 described methods.
• the preferred hydrophilically modified structural components include in particular the sulfonate group-containing aliphatic diols according to DT - O S 2 446 440, the cationic or also anionic internal emulsifiers which can be incorporated according to German patent application P 26 51 506.0 and also the monofunctional incorporable polyethers described in this patent application.
• the reactants are generally used in such proportions that a ratio of isocyanate groups to hydrogen atoms reactive towards NCO, preferably from hydroxyl groups, from 1.05 to 10, preferably from 1.1 to 3 correspond.
• the order in which the individual reaction partners 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 to 190 ° C., preferably at 50 to 120 ° C.
• the prepolymers could also be produced in the presence of organic 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.
• NCO prepolymers in the process according to the invention, in the production of which none of the hydrophilic structural components mentioned under 3, were used, in which the content of the groups mentioned under b) or c) is therefore 0.
• NCO prepolymers which moreover have the properties mentioned under a) and d) above, the preparation of aqueous dispersions or solutions of the process products according to the invention is only possible when carrying out the process according to the invention if external emulsifiers are also used .
• Suitable such emulsifiers are described, for example, by R. Heusch in "Emulsions", Ullmann, Volume 10, pages 449-473, Weinheim 1975.
• ionic emulsifiers such as e.g. Alkali and ammonium salts of long-chain pet acids or long-chain aryl (alkyl) sulfonic acids, as well as non-ionic emulsifiers such as e.g. ethoxylated alkylbenzenes with an average molecular weight of 500 to 10,000.
• These external emulsifiers are thoroughly mixed with the NCO-Pril polymers before the process according to the invention is carried out. They are generally used in amounts of 1 to 30, preferably 5 to 20 parts by weight, based on the weight of the NCO prepolymer. It is also possible to increase the hydrophilicity of the hydrophilic modified NCO prepolymers by using such external emulsifiers, although this is generally not necessary.
• the reactant partners are preferably used in proportions such that 0.37-0.53, preferably 0.4-0.51 mol, hydroxyl groups of the hydroxyoxyzolidine are accounted for per mole of isocyanate groups of the NCO prepolymer.
• the reaction products are therefore also just like the NCO prepolymers used as starting materials essentially linear connections.
• hydroxyoxazolidines and the bisoxazolidines mentioned are compounds known from the literature (see, for example, the references mentioned at the beginning with regard to the moisture-curing oxazolidine compositions of the prior art).
• Bisoxazolidines or hydroxyoxazolidines to be used with particular preference are the corresponding compounds mentioned in US Pat. No. 4,002,601 or DT-OS 2,446,438.
• N-hydroxyalkyl oxazolidines are prepared by methods known from the literature, a ketone or an aldehyde being condensed with a bis- (hydroxyalkyl) amine with cyclizing dehydration and the water of reaction being removed azeotropically by an inert entrainer or by the excess carbonyl compound becomes.
• Bis- (2-hydroxyethyl) amine and bis- (2-hydroxypropyl) amine are particularly suitable. In principle, however, bis- (2-hydroxybutyl) amine, bis (2-hydroxyhexyl) amine, bis (3-hydroxyhexyl) amine, or N- (2-hydroxypropyl) -N- ( 6-hydroxyhexyl) amine.
• the bisoxazolidines to be used according to the invention can be reacted with diisocyanates of the formula (in which Z has the meaning given above), for example hexamethylene diisocyanate, 3,3,5-trimethyl-5-isocyanatomethylcyclohexyl isocyanate (IPDI), 4,4'-diisocyanatodicyclohexylmethane, 2,4- and 2,6-diisocyanatotoluene or Prepare 4,4'-diisocyanatodiphenylmethane.
• diisocyanates of the formula for example hexamethylene diisocyanate, 3,3,5-trimethyl-5-isocyanatomethylcyclohexyl isocyanate (IPDI), 4,4'-diisocyanatodicyclohexylmethane, 2,4- and 2,6-diisocyanatotoluene or Prepare 4,4'-diisocyanatodiphenylme
• dicarboxylic acids their bischlorides can also be used with the elimination of HCl or the bisesters with the elimination of alcohol.
• OH- To implement group with stoichiometric amounts of hydroxycarboxylic acids or the corresponding lactones.
• a decisive advantage over the previously known methods of the prior art for the solvent-free or low-solvent production of aqueous polyurethane dispersions is that intimate mixing with the chain extender takes place before the prepolymers are brought into contact with the water, or even before they are brought into contact with water
• the chain-extending group (oxazolidine group) is chemically fixed, so that the chain extension leads to particularly homogeneous products.
• the process according to the invention is particularly suitable for the production of aqueous dispersions or solutions which have a solids content of 10 to 70, preferably 30 to 65,% by weight.
• the particles of the discontinuous phase in the dispersions generally have a diameter of 50 to 1000 nm.
• the production of sols with an average particle diameter of the discontinuous phase of about 1-50 nm or clear, aqueous solutions in which the solid is present in molecularly disperse form or at most in the form of associates is also possible according to the invention.
• solutions or dispersions of the polyurethanes in water are obtained in the process according to the invention depends above all on the molecular weight and the hydrophilicity of the dissolved or dispersed particles, which in turn depends on the suitable choice of type and quantitative ratios of the starting materials, in particular in the preparation of the NCO prepolymers , can be adjusted according to the known principles of polyurethane chemistry.
• the use of an NCO prepolymer with a mean NCO functionality slightly below 2 leads to the polyaddition reaction being terminated before excessively high molecular weights are reached.
• 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.
• pendant hydroxyl groups built into the process products according to the invention can be shaped after shaping, for example by evaporation of the solvent or water after the solution or the dispersion a chemically or thermally activated crosslinking agent was added to cross-link l.
• Suitable crosslinking agents are, for example, polyisocyanates with blocked isocyanate groups or melamine resins which are reactive towards hydroxyl groups. Even if the process products according to the invention are not chemically crosslinked via the pendant hydroxyl groups, these can be advantageous since they often increase the physical affinity of the process products according to the invention for substrates which are coated with the compounds according to the invention
• the film was not sticky after moistening with toluene and acetone and did not dissolve in hot DMF.
• the NCO prepolymer from Example 1 was at 60 ° C with 361.8 parts of a bisoxazolidine of the formula transferred. 5100 parts of deionized water were added with vigorous stirring. The resulting dispersion had a solids content of 30% and a viscosity of 18 seconds. den (Ford cup, 4 mm). It showed a Tyndall effect in the translucent light.
• the dispersion dries to a clear, colorless and tack-free film which, after the water has been completely removed, has a Shore A hardness of 78. After heating to 130 ° C. for 20 minutes, the hardness had risen to 85 (Shore-A) and the film was only swellable in hot DMF, but no longer soluble.
• the resulting aqueous dispersion had a solids content of 30% and a viscosity of 15 seconds (Ford cup, 4 mm).
• the dispersion showed a Tyndall effect in the translucent light.
• the dispersion After pouring, the dispersion dried into a clear, hard film, which was easy to scratch with a fingernail.
• the pencil hardness was HB-H. After heating at 130 ° C. for 20 minutes, the temperature had risen to 3 hours.

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• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Polyurethanes Or Polyureas (AREA)

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• 1977
  • 1977-07-15 DE DE19772732131 patent/DE2732131A1/de not_active Withdrawn
• 1978
  • 1978-07-03 US US05/921,285 patent/US4192937A/en not_active Expired - Lifetime
  • 1978-07-07 EP EP78100323A patent/EP0000381B1/fr not_active Expired
  • 1978-07-07 DE DE7878100323T patent/DE2860113D1/de not_active Expired
  • 1978-07-12 IT IT50255/78A patent/IT1105095B/it active
  • 1978-07-13 JP JP8461778A patent/JPS5420098A/ja active Granted
  • 1978-07-14 ES ES471750A patent/ES471750A1/es not_active Expired

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