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
  • C08G18/16—Catalysts
  • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
  • C08G18/1808—Catalysts containing secondary or tertiary amines or salts thereof having alkylene polyamine 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
  • C08G18/08—Processes
  • C08G18/16—Catalysts
  • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
  • C08G18/1825—Catalysts containing secondary or tertiary amines or salts thereof having hydroxy or primary amino 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
  • C08G18/2805—Compounds having only one group containing active hydrogen
  • C08G18/285—Nitrogen containing compounds
  • C08G18/2865—Compounds having only one primary or secondary amino group; Ammonia
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/30—Low-molecular-weight compounds
  • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
  • C08G18/3225—Polyamines
  • C08G18/3228—Polyamines acyclic
• • 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
  • Y10T428/249921—Web or sheet containing structurally defined element or component
  • Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
  • Y10T428/249987—With nonvoid component of specified composition
  • Y10T428/249991—Synthetic resin or natural rubbers
  • Y10T428/249992—Linear or thermoplastic
• • 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.]
  • Y10T428/31573—Next to addition polymer of ethylenically unsaturated monomer
  • Y10T428/3158—Halide monomer type [polyvinyl chloride, etc.]

Definitions

• the present invention relates to a process for the production of polyurethane plastics, preferably foams, using novel catalysts having tertiary nitrogen atoms which are incorporated into the polyurethane and at the same time act as aging and light stabilizers.
• Polyurethane foams with a wide variety of physical properties are made by the known isocyanate polyaddition process from compounds with several active hydrogen atoms, in particular compounds containing hydroxyl and / or carboxyl groups, and polyisocyanates, with the use of water and / or blowing agents and, if appropriate, catalysts, emulsifiers and other additives, has long been produced on an industrial scale (Angew. Chem. A, 59 (1948), p. 257). With a suitable choice of components, either elastic or rigid foams or all products lying between these extremes are obtained.
• Polyurethane foams are preferably produced from liquid starting components, the starting materials to be reacted with one another either in one step process are mixed together or an NCO group-containing pre-adduct is first prepared from a polyol and an excess of polyisocyanate, which is then foamed, for example by reaction with water.
• Tertiary amines have proven themselves as catalysts in the production of polyurethane foams primarily because they accelerate both the reaction between hydroxyl or carboxyl groups and NCO groups (urethane reaction) and the reaction between water and isocyanates (blowing reaction), also in the case of One-step process (“one-shot”) the speeds of the two reactions running side by side can be coordinated.
• catalysts which, on their own or in a mixture with known amine catalysts, prevent discoloration of foam-backed plastic films (e.g. PVC films) under thermal stress and / or exposure to light, as well as aging effects in the case of free-foamed polyurethane plastics.
• foam-backed plastic films e.g. PVC films
• preferred catalysts (A) are compounds of the general formulas (1) and (2).
• the catalysts characterized by the general formulas (1) to (4) have a special position compared to the tertiary amines previously used due to their stabilizing action against thermal and photochemical aging. This is probably due to the fact that despite their content of active hydrogen atoms - due to steric hindrance - they are only very slowly incorporated into the polyurethane during the foaming process. As a result, they can surprisingly develop their stabilizing effect at the phase interfaces.
• amine catalysts (B) known per se in an amount of 3 to 97 mol%, preferably 10 to 90 mol%, particularly preferably 30 up to 70 mol%, based on the total amount of catalyst can also be used, for example tertiary amines containing ether groups according to US Pat. No. 3,330,782, DAS 1 030 558 or DOS 1 804 361 or the ether-free catalysts from DOS having at least 4 tertiary nitrogen atoms 2,624,527 and DOS 2,624,528.
• preferred co-catalysts (B) are compounds which, in addition to at least one tertiary nitrogen atom, contain at least one amide group, in particular one formamide group.
• acylated amines are described in detail in DOS 2 523 633.
• the formylation products of the compounds (A) of the general formulas (1) to (4) and the compounds are particularly preferred in this context and where R and n have the meaning given above.
• catalysts or co-catalysts to be used according to the invention are the following tertiary amines:
• the catalysts to be used according to the invention can be prepared in a manner known per se, for example in DAS 1 154 269, DOS 2 523 633 and in "Die Angewandte Makromolekulare Chemie” 34, pp. 111-132 (1973), and from F Möller in Houben-Weyl, XI / 2 (pp. 27-29).
• a total of 0.01-5% by weight, preferably 0.1-3% by weight, based on the entire reaction mixture, of catalyst is generally used.
• aliphatic, cycloaliphatic, araliphatic, aromatic and heterocyclic polyisocyanates come into consideration, as described, for. B. by W. Siefken in Justus Liebigs Annalen der Chemie, 562, pages 75 to 136, for example ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,12-dodecane diisocyanate, cyclobutane-1, 3-diisocyanate, cyclohexane-1,3- and -1,4-diiaocyanate and any mixtures of these isomers, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane (DAS 1 202 785, American patent specification 3 401 190), 2,4- and 2,6-hexahydrotoluiene diisocyanate and any mixtures of these iso
• distillation residues obtained in the industrial production of isocyanate and containing isocyanate groups optionally dissolved in one or more of the aforementioned polyisocyanates. It is also possible to use any mixtures of the aforementioned polyisocyanates.
• polyisocyanates e.g. 2,4- and 2,6-tolylene diisocyanate as well as any mixtures of these isomers
• TDI polyisocyanates
• polyphenyl-polymethylene polyisocyanates such as those produced by aniline-formaldehyde condensation and subsequent phosgenation ("crude MDI") and carbodiimide groups
• Urethane groups allophanate groups
• isocyanurate groups urea groups
• polyisocyanates containing biuret groups modified polyisocyanates
• Starting components to be used according to the invention are furthermore compounds having at least two isocyanate-reactive hydrogen atoms with a molecular weight of generally 400-10,000.
• These include compounds containing amino groups, thiol groups or carboxyl groups, preferably polyhydroxyl compounds, in particular two to eight compounds containing hydroxyl groups, especially those of Molecular weight 800 to 10,000, preferably 1000 to 6000, e.g. at least two, usually 2 to 8, but preferably 2 to 4, hydroxyl-containing polyesters, polyethers, polythioethers, polyacetals, polycarbonates and polyesteramides, as are known per se for the production of homogeneous and cellular polyurethanes.
• the hydroxyl group-containing polyesters are e.g. 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 anhydrides or corresponding polycarboxylic esters of lower alcohols or mixtures thereof can also be used to produce the polyesters.
• the polycarboxylic acids can be aliphatic, cycloaliphatic, aromatic and / or heterocyclic in nature and optionally, e.g. by halogen atoms, substituted and / or unsaturated.
• succinic acid adipic acid, azelaic acid, phthalic acid, trimellitic anhydride, phthalic anhydride, hexahydrophthalic anhydride, tetrachlorophthalic endomethylenetetrahydrophthalic, glutaric anhydride, maleic anhydride, Fumärklare, dimeric and trimeric fatty acids such as oleic acid, optionally mixed with monomeric fatty acids, dimethyl terephthalate and bis-glycol terephthalate.
• polyhydric alcohols are e.g.
• the polyesters can have
• the at least two, usually two to eight, preferably two to three, hydroxyl groups-containing polyethers which are suitable according to the invention are also of the type known to aich and are, for example, by poly merization of epoxides such as ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide or epichlorohydrin with themselves, for example in the presence of BF 3 , or by addition of these epoxides, optionally in a mixture or in succession, to starting components with reactive hydrogen atoms such as water, alcohols, ammonia or Amines, for example ethylene glycol, propylene glycol (1,3) or - (1,2), trimethylolpropane, 4,4'-dihydroxy-diphenylpropane, aniline, ethanolamine or ethylenediamine.
• epoxides such as ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, sty
• Sucrose polyethers such as are described, for example, in German publications 1 176 358 and 1 064 938, are also suitable according to the invention. In many cases, those polyethers are preferred which predominantly (up to 90% by weight, based on all the OH groups present in the polyether) have primary OH groups.
• Polyethers modified by vinyl polymers such as those formed, for example, by polymerizing styrene and acrylonitrile in the presence of polyethers (American patents 3,383,351, 3,304,273, 3,523,093, 3,110,695, German patent 1,152,536), are also suitable Polybutadienes containing OH groups.
• the condensation products of thiodiglycol with themselves and / or with other glycols, dicarboxylic acids, formaldehyde, aminocarboxylic acids or amino alcohols should be mentioned in particular.
• the products are polythio ether, polythio ether ester or polythio ether ester amide.
• polyacetals e.g. the compounds which can be prepared from glycols, such as diethylene glycol, triethylene glycol, 4,4'-dioxethoxydiphenyldimethylmethane, hexanediol and formaldehyde, are suitable.
• glycols such as diethylene glycol, triethylene glycol, 4,4'-dioxethoxydiphenyldimethylmethane, hexanediol and formaldehyde
• Polyacetals suitable according to the invention can also be prepared by polymerizing cyclic acetals.
• Suitable polycarbonates containing hydroxyl groups are those of the type known per se, which e.g. by reacting diols such as propanediol (1,3), butanediol (1,4) and / or hexanediol (1,6), diethylene glycol, triethylene glycol or tetraethylene glycol with diaryl carbonates, e.g. Diphenyl carbonate, or phosgene can be produced.
• diols such as propanediol (1,3), butanediol (1,4) and / or hexanediol (1,6)
• diethylene glycol triethylene glycol or tetraethylene glycol
• diaryl carbonates e.g. Diphenyl carbonate, or phosgene
• polyester amides and polyamides include e.g. the predominantly linear condensates obtained from polyvalent saturated and unsaturated carboxylic acids or their anhydrides and polyvalent saturated and unsaturated amino alcohols, diamines, polyamines and their mixtures.
• Polyhydroxyl compounds already containing urethane or urea groups and optionally modified natural polyols such as castor oil, carbohydrates or starch can also be used.
• Addition products of alkylene oxides on phenol-formaldehyde resins or also on urea-formaldehyde resins can also be used according to the invention.
• Compounds with at least two isocyanate-reactive hydrogen atoms with a molecular weight of 32-400 are also suitable as starting components to be used according to the invention, if appropriate in a mixture with the higher molecular weight compounds mentioned.
• These compounds generally have 2 to 8 isocyanate-reactive hydrogen atoms, preferably 2 or 3 reactive hydrogen atoms.
• Examples of such compounds are: ethylene glycol, (1,2) and - (1,3) propylene glycol, (1,4) and - (2,3) butylene glycol, (1,5) pentanediol, hexanediol (1,6), octanediol- (1,8), neopentyl glycol, 1,4-bishydroxymethyl-cyclohexane, 2-methyl-1,3-propanediol, glycerin, trimethylolpropane, hexanetriol- (1,2,6), trimethylolethane, Pentaerythritol, quinite, mannitol and sorbitol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycols with a molecular weight of up to 400, dipropylene glycol, polypropylene glycols with a molecular weight of up to 400, dibutylene glycol, polybutylene glycols with
• mixtures of different compounds with at least two isocyanate-reactive hydrogen atoms with a molecular weight of 32-400 can be used.
• polyhydroxyl compounds can also be used in which high molecular weight polyadducts or polycondensates are contained in finely dispersed or dissolved form.
• modified polyhydroxyl compounds are obtained if polyaddition reactions (for example reactions between polyisocyanates and amino-functional compounds) or polycondensation reactions (for example between formaldehyde and phenols and / or amines) are carried out directly in situ in the above-mentioned compounds containing hydroxyl groups.
• water and / or volatile organic substances can also be used as blowing agents.
• Acetone, ethyl acetate, halogen-substituted alkanes such as methylene chloride, chloroform, ethylidene chloride, vinylidene chloride, monofluorotrichloromethane, chlorodifluoromethane, dichlorodifluoromethane, butane, hexane, heptane or diethyl ether are also suitable.
• a blowing effect can also be achieved by adding compounds which decompose at temperatures above room temperature with the elimination of gases, for example nitrogen.
• Azo compounds such as azoisobutyronitrile can be achieved.
• propellants as well as details on the use of propellants can be found in the Kunststoff-Handbuch, Volume VII, published by Vieweg and Höchtlen, Carl-Hanser-Verlag, Kunststoff 1966, e.g. on pages 108 and 109, 453 to 455 and 507 to 510.
• tertiary amines such as triethylamine, tributylamine, N-methyl-morpholine, N-ethyl-morpholine, N-cocomorpholine, N, N, N ', N'-tetramethyl-ethylenediamine, 1,4-diaza-bicyclo- (2.2 , 2) octane, N-methyl-N'-dimethylaminoethyl-piperazine, N, N-dimethylbenzylamine, bis (N, N-di-ethylaminoethyl) adipate, N, N-diethylbenzylamine, pentamethyldiethylenetriamine, N, N -Dimethylcyclohexylamine, N, N, N ', N'-tetramethyl-1,3-butanediamine, N, N-dimethyl- ⁇ -phenylethy
• tertiary amines such as triethylamine, tribut
• Mannich bases known per se from secondary amines such as dimethylamine and aldehydes, preferably formaldehyde, or ketones such as acetone, methyl ethyl ketone or cyclohexanone and phenols such as phenol, nonylphenol or bisphenol are also suitable as additional catalysts.
• Tertiary amines which have hydrogen atoms active against isocyanate groups as catalysts are e.g. Triethanolamine, triisopropanolamine, N-methyldiethanolamine, N-ethyl-diethanolamine, N, N-dimethyl-ethanolamine, and their reaction products with alkylene oxides, such as propylene oxide and / or ethylene oxide.
• Silaamines with carbon-silicon bonds such as those e.g. in German Patent 1,229,290 (corresponding to American Patent 3,620,984) are in question, e.g. 2,2,4-trimethyl-2-silamorpholine and 1,3-diethylaminomethyltetramethyl-disiloxane.
• Suitable additional catalysts are also nitrogenous bases such as tetraalkylammonium hydroxides, alkali metal hydroxides such as sodium hydroxide, alkali phenolates such as sodium phenolate or alkali metal alcoholates such as sodium methylate. Hexahydrotriazines can also be used as catalysts.
• organic metal compounds in particular organic tin compounds, can also be used as catalysts.
• Preferred organic tin compounds are tin (II) salts of carboxylic acids such as tin (II) acetate, tin (II) octoate, tin (II) ethylhexoate and tin (II) laurate and the tin (IV) compounds,
• tin (II) salts of carboxylic acids such as tin (II) acetate, tin (II) octoate, tin (II) ethylhexoate and tin (II) laurate and the tin (IV) compounds
• tin oxide dibutyltin dichloride
• dibutyltin diacetate dibutyltin dilaurate
• dibutyltin maleate or dioctyltin diacetate can be considered.
• all of the above catalysts can be used as mixtures.
• surface-active additives such as emulsifiers and foam stabilizers, can also be used.
• the emulsifiers are e.g. the sodium salts of castor oil sulfonates or salts of fatty acids with amines such as oleic acid diethylamine or stearic acid diethanolamine.
• Alkali or ammonium salts of sulfonic acids such as dodecylbenzenesulfonic acid or dinaphthylmethane disulfonic acid or of fatty acids such as ricinoleic acid or of polymeric fatty acids can also be used as surface-active additives.
• Polyether siloxanes are particularly suitable as foam stabilizers. These compounds are generally constructed in such a way that a copolymer of ethylene oxide and propylene oxide is linked to a polydimethylsiloxane radical.
• foam stabilizers are e.g. in U.S. Patents 2,834,748, 2,917,480, and 3,629,308.
• reaction retarders e.g. acid-reacting substances such as hydrochloric acid or organic acid halides, furthermore cell regulators of the type known per se such as paraffins or fatty alcohols or dimethylpolysiloxanes as well as pigments or dyes and flame retardants of the type known per se, e.g. Tris-chloroethyl phosphate, tricresyl phosphate or ammonium phosphate and polyphosphate, also stabilizers against aging and weather influences, plasticizers and fungistatic and bacteriostatic substances, and fillers such as barium sulfate, diatomaceous earth, carbon black or sludge chalk are also used.
• acid-reacting substances such as hydrochloric acid or organic acid halides
• cell regulators of the type known per se
• pigments or dyes and flame retardants e.g. Tris-chloroethyl phosphate, tricresyl phosphate or ammonium phosphate and
• the reaction components are reacted according to the one-step process, the prepolymer process or the semi-prepolymer process, which are known per se, machine equipment often being used, e.g. those described in U.S. Patent 2,764,565. Details of processing devices that are also suitable according to the invention are given in the plastics manual, volume VI, published by Vieweg and Höchtlen, Carl-Hanser-Verlag, Kunststoff 1966, e.g. described on pages 121 to 205.
• foaming is often carried out in molds according to the invention.
• the reaction mixture is introduced into a mold.
• Metal for example aluminum, or plastic, for example epoxy resin, can be used as the molding material.
• the foamable reaction mixture foams in the mold and forms the shaped body.
• the foaming of the mold can be carried out in such a way that the molded part has a cell structure on its surface, but it can also be carried out in such a way that the molded part has a compact skin and a cellular core. According to the invention, one can proceed in this connection in such a way that so much foamable reaction mixture is introduced into the mold that the foam formed just fills the mold.
• Cold-curing foams can also be produced according to the invention (cf. British patent specification 1 162 517, German patent application specification 2 153 086).
• foams can also be produced by block foaming or by the double conveyor belt process known per se.
• the process products are preferably flexible, semi-flexible or hard polyurethane foams. You will find the known use for such products, e.g. as mattresses and upholstery material in the furniture and automotive industry, also for the manufacture of fittings such as are used in the automotive industry and finally as insulation and means for heat or cold insulation, e.g. in the construction sector or in the refrigeration industry.
• Example 1 is repeated, but using 1.2 parts of tetramethylethylenediamine instead of the catalyst mixture according to the invention.
• Example 1 is repeated, but using 1.2 parts of N-dimethylamino-N '- (2-dimethylamino-propionyl) aminal instead of the catalyst mixture according to the invention.

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• Chemical & Material Sciences (AREA)
• 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
  • 1977-07-16 DE DE19772732292 patent/DE2732292A1/de not_active Withdrawn
• 1978
  • 1978-07-11 DE DE7878100346T patent/DE2860114D1/de not_active Expired
  • 1978-07-11 EP EP78100346A patent/EP0000389B1/fr not_active Expired
  • 1978-07-14 IT IT50306/78A patent/IT1106265B/it active
  • 1978-07-14 AT AT0510778A patent/AT367779B/de not_active IP Right Cessation
  • 1978-07-14 BR BR7804545A patent/BR7804545A/pt unknown
  • 1978-07-14 JP JP8526578A patent/JPS5420099A/ja active Granted
• 1979
  • 1979-12-26 US US06/107,310 patent/US4248930A/en not_active Expired - Lifetime

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