DK141851B - PROCEDURE FOR MANUFACTURING POLYURETHANE FOOD SUBSTANCES WITH SELF-GRINDING PROPERTIES - Google Patents

Description

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(11) PUBLICATION NOTICE 141851 DENMARK '') mt ci.3 c 08 e 18 / u (21) Application No. 851M (22) Filed on 15 Feb. 1974 f (23) Onday 15 · Feb. 1974 (44) The application presented and. , Qon «the petition published on 'J1" 1 · • i? 0

DIRECTORATE OF

PATENT AND TRADEMARKET (3 °) Priority book from dm

Feb 16 1975s 2507589 »DE Apr 18 1975 »2519648, DE

(71) BAYER AKTIENGESELLSCHAFT, 5 DE9 Leverkusen, DE.

(72) Inventor: Helmut Kleimann, Mettlacher Strasse 6, Leverkusen, DE:

Wulf von Bonin, Goetheplafcz 9 »Leverkusen, DE: Heinz-Georg ^ Schneider, Gummersbach J> \, Dir inghaus en Strås se 65» DE: Herbert Ge = bauer, Albert-Schweizer-Strasse 14, Krefeld, DE.

(74) Plenipotentiary in the proceedings:

The engineering company Budde, Schou & Co.

(54) Process for producing polyurethane foam materials with self = release properties.

The invention relates to a process for producing polyurethane foams having excellent mold removal properties and, more particularly, to a polyurethane foams having self-releasing properties by reacting in closed forms of organic polyisocyanates, compounds having reactive hydrogen atoms of a molecular weight of 62, and and / or organic propellants and optionally additional additives and while using one internal release agent or several internal release agents.

Foams based on polyisocyanates, e.g. polyurethane foam fabrics with a thick outer skin and a cellular core, prepared by the molding foam method (cf. . for building furniture, vehicles and houses.

The polyurethane molding bodies are prepared as follows:

The foamable reaction mixture consisting of polyisocyanates, compounds containing at least two isocyanate-reacting hydrogen atoms, and additives, are filled into closed, temperable molding tools in which the reaction mixture is foamed and solidified in highly densified form. The molding completely fills the tool and accurately depicts the inner surfaces of the tool.

Preferably, tools are used consisting of a material with the greatest possible heat capacity and maximum possible thermal conductivity, preferably metal. However, it is also possible to use other materials, such as plastics, glass or wood. To prevent an adhesion of the plastic part to the tool surface at the mold removal (i.e. at the removal from the mold), the tool is provided with a mold release agent. As such release agents, e.g. waxes, soaps or oils. These release agents form a thin film between the tool surface and the fabric part, which neither adheres to the host bait nor to the plastic material and thus allows easy removal of the plastic material from the tool.

For serial production, this process exhibits various disadvantages. The abrasive must be applied at regular intervals and during this time the tool cannot be used for production. Fine engravings in the tool, e.g. an imitated wooden structure or leather tint, is covered over time with residue of abrasive. Removal of these retaining tools from the tools, which often have a strong contour, can only be accomplished with great difficulty. The plastic parts are coated with a thin film of abrasive on which varnish systems do not adhere. The parts must be sanded prior to coating or covered with solvents to provide sufficient adhesion of the paint to the resin.

From German Publication No. 1,953,637, it is already known that the application of an abrasive in the tool can be avoided when admixing certain additives which impart the finished resin with excellent abrasive in the foamable reaction mixture.

properties in metal molds with impeccable surfaces. As such additives, salts containing at least 25 carbon atoms of aliphatic carboxylic acids with preferably primary amines or I may be used.

amide or ester group-containing amines. However, the abrasive properties leave a lot to be desired, e.g. with respect to the force to be used for the removal from the mold.

i i 3 U1851

German Publication No. 2,121,670 discloses a process for the preparation of foams by foaming a reaction mixture consisting of polyisocyanates, compounds with reactive hydrogen atoms, water and / or organic propellants and additives in a closed form, wherein as additives e.g. . a mixture of a) salts having at least 20 aliphatic carbon atoms of aliphatic carboxylic acids and optionally amide and / or ester group-containing amines is used, and b) natural and / or synthetic oils, fats or waxes.

Since these additives cause an internal lubrication of the plastic composition, they at the same time give the plastic material excellent flow properties in the tool with reduced blistering on the plastic surface. In addition, these internal release agents exhibit an antistatic effect as well as excellent abrasive properties, even in metal structures with a highly textured surface.

Although this known process provides excellent release effects, it is often found in the practical application that the frequently used synthetic oils or waxes of higher fatty acids or mixtures esters thereof are insufficiently compatible with the starting components of the foam - either with isocyanate or with polyol components - that is, in many cases a mixture of these starting components with the fatty acid esters acting as abrasives is not stable to storage, but separates in single phases. While this separation process can be hindered by stirring in the storage containers, this is unsatisfactory from a technical point of view, since many such storage containers are not provided with a stirrer. Finally, phase separation may also occur during transport of the product.

Thus, there is a task in finding internal release agents which can be mixed with at least one of the foam starting components for a storage resistant mixture, ie. a mixture which does not exhibit a phase separation propensity and which allows the finished resin to be removed from the mold with very little force effect.

It has now surprisingly been found that reaction products of mono- or polyisocyanates with certain esters or polyesters of higher fatty acids having more than 8 carbon atoms and containing active hydrogen atoms (hereinafter referred to as "fatty acid esters"), mixed or in combination with additional release agents or abrasive cysts, provide excellent abrasive effects in foam molding by foam molding and are also soluble in the isocyanate starting components of the foams without phase separation. Fatty acid is understood to mean aliphatic mono-carboxylic acids present in or recoverable by fats.

141851 4

The present invention thus relates to a process of the kind already described, characterized in that a reaction product soluble in organic polyisocyanates soluble in organic polyisocyanates is prepared by reacting at temperatures between 30 and 200 ° C at least. an equivalent amount of an organic poly or mono-isocyanate and a fatty acid ester or a mixture of fatty acid esters wherein the fatty acid ester is made up of aliphatic fatty acids having more than 8 carbon atoms and mono or polyhydric aliphatic alcohols, or a fatty acid polyester having an average fatty acid polyester molecular weight between 500 and 5000 and is composed of at least one aliphatic fatty acid having more than 8 carbon atoms, aliphatic dicarboxylic acids, optionally aliphatic monocarboxylic acids, and polyvalent and optionally monovalent aliphatic alcohols, wherein the fatty acid ester or fatty acid polyester has an acid number between 100 and number of flour limbs 0 and 150, with at least one of these target numbers being greater than 0 and wherein the reaction product and the polyisocyanate used in the reaction may optionally be the same product.

As a measure of the grinding effect, the force, 2 measured in kp / cm, required to open the tool at the mold withdrawal stage can be used, but the grinding effect can also be subjectively assessed by manually opening a suitable mold and removing the foamed foam material. plate (20 x 20 x 1 cm). The forces to be used in extracting the polyurethane foams prepared with the reaction products used in the process of the invention are appreciably less than those to be used in the extraction of the same foams which have been foamed from a reaction mixture which is not mixed with the aforementioned abrasives, cf. more detailed below. The required withdrawal forces are usually between 0.02 and 0.16 kp / cm, measured as specific tearing force for opening the mold (cf. more detail below), and are also substantially smaller than those to be used in removing the mold. the same foams formed from a reaction mixture containing the aforementioned additives known from German Publication No. 1,953,637, wherein the specific tearing force for opening the mold is 0.8 and 1.0 kp / cm, cf. . Table I.

Within the scope of the present invention, polyurethane foams based on polyisocyanates mean foams prepared using compounds of reactive hydrogen atoms having a molecular weight of 62-10,000.

In view of the starting components of the foam preparation of the invention, aliphatic, cycloaliphatic, ar-aliphatic, aromatic and heterocyclic polyisocyanates, e.g. those described by W. Siefgen in Justus Liebigs' Annalen der Chemie, 562, pages 75-136, for example, ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,12-dodecanedisocyanate, cyclobutane 1,3-diisocyanate, cyclohexane-1,3- and -1,4-diisocyanate, and any mixtures of these isomers, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane (cf. German publication no. (1,202,785), 2,4- and 2,6-hexahydrotoluylene diisocyanate and any mixtures of these isomers, hexahydro-1,3- and / or -1,4-phenylene diisocyanate, perhydro-2,4'- and / or -4,4'-diphenylmethane diisocyanate, 1,3- and 1,4-phenylene diisocyanate, 2,4- and 2,6-toluylene diisocyanate and any mixtures of these isomers, diphenylmethane-2,4'- and / or -4,4'-diisocyanate, naphthylene-1,5-diisocyanate, triphenylmethane-4,4 ', 4 "triisocyanate, polyphenyl-polymethylene-polyisocyanates produced by aniline-formaldehyde condensation and subsequent phosgenation , such as described in the UK Patent Nos. 874,430 and 848,671, perchlorinated aryl polyisocyanates, e.g. are described in German Patent Specification No. 1,157,601, carbodiimide group-containing polyisocyanates, e.g. are described in German Patent No. 1,092,007, diisocyanates of the kind described in U.S. Patent No. 3,492,330, allophanate group-containing polyisocyanates, e.g. are described in British Patent No. 994,890, Belgian Patent No. 761,626 and published Dutch Patent Application No. 71.02524, isocyanurate group-containing polyisocyanates, e.g. is disclosed in German Patent Specification No. 1,022,789. 1,222,067 and 1,027,394, as well as in German Publication Nos. 1,929,034 and 2,004,048, urethane group-containing polyisocyanates, e.g. are described in Belgian Patent Specification No. 752,261 or in U.S. Patent No. 3,394,164, polyisocyanates containing acylated urea groups according to German Patent No. 1,230,778, biuret group-containing polyisocyanates, e.g. as described in German Patent No. 1,101,394 and British Patent No. 889,050, polyisocyanates prepared by the telomerization reaction, e.g. disclosed in Belgian Patent No. 723,640, ester group-containing polyisocyanates, e.g. disclosed in British Patent Nos. 965,474 and 1,072,956, in United States Patent No. 3,567,763 and in German Patent No. 1,231,688, as well as turnover products of the above isocyanates with acetals according to German Patent No. 1,072,385.

141851 6

It is also possible to use the isocyanate group-containing distillation residues resulting from the technical isocyanate preparation, optionally dissolved in one or more of the above polyisocyanates. Furthermore, it is possible to use any mixtures of the above polyisocyanates.

Particularly preferred are the readily available polyisocyanates, e.g. 2,4- and 2,6-toluylene diisocyanate and any mixtures of these isomers ("TDI"), polyphenyl-polymethylene-polyisocyanates prepared by aniline-formaldehyde condensation with subsequent phosgenation ("crude MDI") and carbodiimide group -, urethane group, allophanate group, isocyanurate group, urea group or biuret group containing polyisocyanates ("modified polyisocyanates").

In addition, the starting components used for the foam preparation herein are compounds having at least two reactive hydrogen atoms with a molecular weight of 62-10,000. This means, in addition to amino group, thiol group or carboxyl group containing compounds, is preferably polyhydroxyl compounds, especially compounds containing two to eight hydroxyl groups, especially those having a molecular weight of 800-10,000, preferably 1000-6000, e.g. polyesters, polyethers, polythioethers, polyacetals, polycarbonates and polyesteramides having at least two, usually 2-8, but preferably 2-4 hydroxyl groups known per se to produce homogeneous and cellular polyurethanes.

The present hydroxyl group-containing polyesters are e.g. reaction products of polyhydric, preferably divalent, and optionally also trivalent alcohols with polyhydric, preferably divalent carboxylic acids. Instead of the free polycarboxylic acids one can also use the corresponding polycarboxylic acid anhydrides or corresponding lower alcohol alcohol polycarboxylic acid esters or mixtures thereof to prepare the polyester. The polycarboxylic acids may be of aliphatic, cycloaliphatic, aromatic and / or heterocyclic nature and may be optionally substituted, e.g. with halogen atoms, and / or unsaturated. Examples which may be mentioned 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, endomethy-lentetrahydrophthalsyreanhydrid, glutaric anhydride, maleic acid, paint-insyreanhydrid, fumaric acid, dimeric and trimeric fatty acids , such as oleic acid, optionally mixed with monomeric fatty acids, terephthalic acid methyl ester and terephthalic acid bis-glycol ester. Speaking as polyhydric alcohols, for example, come 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, glycerol, trimethylolpropane, hexanetriol (1,2,6), butanetriol. (1,2,4), trimethylolethane, pentaerythritol, quinitol, mannitol and sorbitol, methyl glycoside, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycols, dipropylene glycol, polypropylene glycols, dibutylene glycols and polybutylene lycols. The polyesters may partly exhibit terminal carboxyl groups. Also polyesters of lactones, e.g. ε-caprolactone, or hydroxy-carboxylic acids, e.g. fcj-hydroxycaproic acid may be used. The above lower molecular weight polyhydric alcohols may also be used as such.

Also, the polyethers of at least 2, usually 2-8, preferably 2-3, which are present in the process according to the invention are of the type known per se and are prepared, for example, by polymerization of epoxides such as ethylene oxide, propylene oxide, butylene oxide. , tetrahydrofuran, styrene oxide or epichlorohydrin, by themselves, e.g. in the presence of BF 2, or by the addition of these epoxides, optionally mixed or in succession, to starting components with reaction-capable hydrogen atoms such as alcohols or amines, e.g. water, ethylene glycol, propylene glycol (1,3) or (1,2) trimethylolpropane, 4,4'-dihydroxy diphenylpropane, aniline, ammonia, ethanolamine or ethylenediamine. Also sucrose polyethers such as e.g. disclosed in German Patent Specification Nos. 1,176,358 and 1,064,938 can be used in the method of the invention. Particularly preferred are polyethers which predominantly (i.e. up to 90% by weight, based on all OH groups present in the polyether) exhibit primary QH groups.

Also, polyethers modified with vinyl polymerisates, e.g. prepared by polymerization of styrene and acrylonitrile in the presence of poly, ethers (cf. US Patent Nos. 3,383,351, 3,304,273, 3,523,093, 3,110,695 and German Patent No. 1,152,536) are suitable. The same applies to OH-group-containing polybutadiene.

Preferred polythioethers are in particular condensation products of thiodiglycol with themselves and / or with other glycols, dicarboxylic acids, formaldehyde, aminocarboxylic acids or amino alcohols. Depending on the co-components, these are polythio mixture ethers, polythioether esters and polythioether esters.

Speaking as polyacetals, for example, the compounds are derived from glycols such as diethylene glycol, triethylene glycol and 4,4'-dioxethoxy-diphenyldimethylmethane, hexanediol and formaldehyde.

The polyacetals suitable for the process according to the invention can also be prepared by the polymerization of cyclic acetals.

q 141851

ISLAND

In view of hydroxyl group-containing polycarbonates, polycarbonates of a kind known per se, e.g. can be prepared by reacting diols such as propanediol (1,3), butanediol (1,4) and / or hexanediol (1,6), diethylene glycol, triethylene glycol and tetraethylene glycol, with diaryl carbonates, e.g. diphenyl carbonate, or phosgene.

For example, polyester amides and polyamides belong to. those obtained from polyvalent, saturated and unsaturated carboxylic acids or their anhydrides and polyvalent, saturated and unsaturated amino alcohols, diamines, polyamines and mixtures thereof, preferably linear condensates.

Also polyhydroxyl compounds already containing urethane or urea groups, as well as any modified natural polyols such as castor oil, carbohydrates, starch, may be used. Also, adhesive products of alkylene oxides for phenol-formaldehyde resins or for urea-formaldehyde resins can be used in the process of the invention.

Representatives of these compounds useful in the process of the invention are e.g. described in High Polymers, Volume XVI, "Polyurethanes, Chemistry and Technology", by Saunders-Frisch, Inter-Science Publishers, 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 Kunststoff - Handbuch, Volume VII, Vieweg-Hochtlen, Carl-Hanser-Verlag, Miinchen, 1966, e.g. on pages 45-71.

In the process according to the invention, water and / or volatile organic substances are used as propellant. Speaking as an organic propellant come, for example, acetone, ethyl acetate, halogen-substituted alkanes, e.g. methylene chloride, chloroform, ethylidene chloride, vinylidene chloride, monofluorotrichloromethane, chlorodifluoromethane, dichlorodifluoromethane, trichlorotrifluoroethane, as well as butane, hexane, hepatlethane or diethyl ether. A driving action may also be provided by the addition of compounds which decompose at temperatures above room temperature during the decomposition of gases, e.g. of nitrogen, e.g. aso compounds such as azoisobutyric acid nitrile. Further examples of propellants and details of the use of propellants are described in Kunststoff-Handbuch, Volume VII, Viegweg and Hochtlen, Carl-Hanser-Verlag, Miinchen 1966, e.g. on pages 108 and 109, 453-455 and 507-510.

Furthermore, in the process of the invention, catalysts are often used together. Speaking as catalysts in this context, catalysts of a kind known per se, e.g. tertiary amines such as triethylamine, tributylamine, N-methyl-morpholine, N-ethyl-morpholine, N-cocomorpholine, Ν, Ν, Ν ', Ν'-tetramethyl-ethylenediamine, 1,4-diaza-bicyclo- ( 2,2,2) -octane, N-methyl-N'-dimethylaminoethyl-piperazine, 14, Ν-dimethylbenzylamine, bis- (N, N-diethylaminoethyl) adipate, N, N - diethylbenzylamine, pentamethyldiethylenetriamine, N , N-dimethylcyclohexylamine, Ν, Ν, Ν ', N'-tetramethyl-1,3-butanediamine, N, N-dimethyl-β-phenylethylamine, 1,2-dimethylimidazole, 2-methylimidazole and tetramethyl-guanidine .

Tertiary amines with hydrogen atoms active against cyanate groups are, for example, triethanolamine, triisopropanolamine, N-methyl-diethanolamine, N-ethyl-diethanolamine, N, N-dimethyl-ethanol-amine, and their reaction products with alkylene oxides such as propylene oxide. and / or ethylene oxide.

As catalysts one can also use silamines with carbon-silicon bonds which e.g. is described in German Patent No. 1,229,290. Examples of this are 2,2,4-trimethyl-2-silamorpholine and 1,3-diethylaminomethyl-tetramethyl-disiloxane.

Also considered as catalysts are nitrogen-containing bases such as tetraalkylammonium hydroxides, alkali metal hydroxides such as sodium hydroxide, alkali metal phenolates such as sodium phenolate, or alkali metal alcoholates such as sodium methylate. Hexahydrotriazines can also be used as catalysts.

Also, organic metal compounds, especially organic tin compounds, can be used as catalysts.

Considering sqm of organic tin compounds, preferably tin (II) salts of carboxylic acids such as tin (II) acetate, tin (II) octoate, tin (II) ethylhexoate and tin (II) laurate, and dialkyltin salts of carboxylic acids, e.g. dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate or dioctyltin diacetate.

Other catalyst representatives that can be used in the process of the invention, as well as details on the operation of the catalysts, are described in Kunststoff-Handbuch, Vol. VII, Vieweg and Hochtlen, Carl-Hanser-Verlag, Miinchen, 1966, e.g. on pages 96-102.

The catalysts are usually used in an amount of between approx. 0.001 and approx. 10% by weight, based on the amount of the compounds having at least two reactive hydrogen atoms with a molecular weight of 62-10,000.

The process according to the invention can also be used with surfactant additives (emulsifiers and foam stabilizers). Speaking as emulsifiers, for example, are sodium salts of castor oil sulfonates or of fatty acids or salts of fatty acids with amines such as diethylamine's oleic acid salt or diethanolamine's stearic acid salt. Also alkali metal or ammonium salts of sulfonic acids, e.g. of dodecylbenzenesulfonic acid or dinaphthylmethanedisulfonic acid, or of fatty acids, such as ricinolic acid, or of polymeric fatty acids, may be used as surfactant additives.

10 141851 Speaking as foam stabilizers come especially water-soluble polyethersiloxanes. These compounds are generally so constructed that a copolymer of ethylene oxide and propylene oxide is associated with a polydimethylsiloxane group. Such foam stabilizers are e.g. disclosed in U.S. Patent No. 2,764,565.

In addition, the process according to the invention allows the use of reaction delayers, e.g. acidic reactants such as hydrochloric acid, sulfuric acid, phosphoric acid or organic acid halides, as well as cell regulators of a known nature, such as paraffins or fatty alcohols or dimethylpolysiloxanes, and pigments or dyes and flame retardants of a kind known per se, such as tris-chloroethyl phosphate ammonium phosphate and polyphosphate, as well as stabilizers against aging and weathering, plasticizers and fungistatic and bacteriostatic active compounds as well as fillers such as barium sulfate, diatomaceous earth, soot or slime.

Further examples of the optionally used surface active additives and foam stabilizers, as well as cell regulators, reaction inhibitors, stabilizers, flame retardants, plasticizers, dyes and fillers, and fungistatic and bacteriostatic active compounds, as well as details of the present invention -Handbuch, Volume VI, Vieweg and Hochtlen, Carl-Hanser-Verlag, Miinchen 1966, e.g. on pages 103-113.

The foaming is carried out in closed molds, the reaction mixture being introduced into a mold. Speaking as mold material comes metal, e.g. aluminum, or plastic, e.g. epoxy resin. In the mold, the foamable reaction mixture foams and forms the mold body. The molding foam may be conducted so that the molding member exhibits cellular structure on its surface, but it may also be so made that the molding member exhibits a compact skin and a cellular core. In this context, it is possible to proceed in such a way as to introduce such a large amount of foamable reaction mixture that the foam material formed precisely fills the mold exactly. But one can also work to introduce more foamable reaction mixture into the mold than is necessary for filling the diminished with foam. In the latter case, thus, "overcrowding" is worked. Such a method is e.g. known from U.S. Patent Nos. 3,178,490 and 3,182,104.

In addition, in the mold foaming, the known release agents can also be used.

The process of the present invention can also produce cold-hardening foams (cf. British Patent Specification No. 1,162,517 and German Patent Publication No. 2,153,086).

In the process according to the invention, as mentioned, 1X 141851 uses reaction products of fatty acid esters or fatty acid polyesters and mono or polyisocyanates, since in the case of fatty acid esters, those containing at least one aliphatic fatty acid having more than 8 carbon atoms incorporated in the molecule have an acid number between 0 and 100, preferably between 0 and 40, and an OH number between 0 and 150, preferably between 0 and 75, at least one of the two measurement numbers having a value greater than 0.

The fatty acid esters used may have the character of polyesters or of mixed esters, since mono- and polyhydric carboxylic acids and / or alcohols may be used in the construction of the fatty acid ester. In the preparation of the considered fatty acid esters, various types of fatty acids or carboxylic acids and / or alcohols may be used at the same time, so that when mixed condensation arises complicated fatty acid ester types whose average molecular weight is between 500 and 5000, preferably between 800 and 3000.

In addition, with the use of amino alcohols, it is also possible to prepare basic or amide group-containing fatty acid mixture esters which can be used in the process of the invention. Such mixture ester types occur, for example, by the use of alkoxylation products with e.g. ethylene oxide, propylene oxide or higher epoxides of ammonia, monoalkylamines or dialkylamines, or by the use of alcohol group-containing acid amides, e.g. may be prepared by amidation of carboxylic acids with mono- or dialkanolamines such as ethanolamine or diethanolamine, propanolamine or dipropanolamine.

For the reaction with the mono- or polyisocyanates, fatty acid esters are preferably used which can be prepared by esterification of carboxylic acids with alcohols or which can be prepared from natural substrates. For example, carboxylic acids and alcohols include the following: butanol, hexanol, octanol isomers, dodecanol, oleyl alcohol, other fatty alcohols, natural or synthetic steroidal alcohols, castoric acid, ethylene glycol, propylene glycol, butanediols, hexanediols, trimethylol, trimethylol, trimethylol, trimethylol, trimethylol most diverse sugars or preparation products of alkylene oxides, such as ethylene oxide or propylene oxide, for these alcohols. Preferred compounds are glycerol, trimethylol propane, pentaerythritol and sorbitol.

Considering carboxylic acids, saturated and unsaturated aliphatic types such as octanecarboxylic acids, dodecanoic acids, natural fatty acids such as castoric acid, oleic acid, elaidic acid, stearic acid, palmitic acid, linoleic acid, linolenic acid, abietic acid, tartaric acid, trace fatty acids, coconut fatty acids, coco fatty acids, tallow oil fatty acids, succinic acid, maleic acid, citric acid, azelaic acid, adipic acid or higher di- and polycarboxylic acids, oligomerization products of unsaturated carboxylic acids, and preparation products of maleic acid for natural and synthetic oils. Preferred compounds are: oleic acid, linoleic acid, ricinolic acid and adipic acid.

The preparation of the fatty acid ester is most conveniently done by cocondensing the alcohols and acids used at temperatures above 100 ° C, preferably at 120-180 ° C, optionally under vacuum, whereby the water decomposition is carried out until the desired OH and acid numbers or average molecular weights are reached. Of course, catalytic esterification by means of acidic or basic catalysts or azeotropic dewatering is possible. Reaction products containing OH groups and / or COOH groups are prepared and these reaction products are used in the preparation of the reaction products for use in the process of the invention.

It has been found that cocondensates of oleic acid with a dicarboxylic acid, e.g. adipic acid, and a polyhydric alcohol, e.g. pentaerythritol, with molecular weight between 900 and 2500, as well as OH number between 30 and 70 and acid number between 3 and 30, are particularly well suited for use in the preparation.

A direct stoichiometric relationship between the measured target numbers and the molar ratio of the components used is not always given, since side reactions of unknown nature may occur parallel to the esterification.

Also of particular interest are ricinoleic acid polyesters whose molecular weight is between 800 and 2500.

For reaction with the fatty acid esters, in principle all known mono- or polyisocyanates, e.g. the polyisocyanates referred to above for the foam preparation.

Considering that monoisocyanates come aliphatic, araliphatic, aromatic or heterocyclic isocyanates or acyl isocyanates. In view of the modification, isocyanates having more than 5 carbon atoms are preferably present in the molecule, although one may also use e.g. methyl isocyanate, chlorocarbonyl isocyanate or methoxymethyl isocyanate.

As examples are the following isocyanates: benzyl isocyanate, benzoyl isocyanate, tosyl isocyanate, phenyl isocyanate, toluyl isocyanate, dimethylphenyl isocyanate, phenoxyphenyl isocyanate, tetradecyl isocyanate, isocyanone isocyanate, cyclohexyl isocylate may be derived from amines which can be prepared from resin acids or fatty acids, e.g. dihydroabethyl isocyanate, and oleyl or stearyl isocyanate. Also suitable are monoisocyanates which e.g. may be derived by reacting such compounds containing Zerewitinow active hydrogen atoms when these compounds are reacted with polyisocyanates, especially diisocyanates, in such a way that an addition compound containing an isocyanate group still exists in the molecule. This reaction is preferably realized by reaction in the molar ratio of 1: 1.

Of particular interest are complex monoisocyanates made from polyesters or polyethers which contain essentially only one OH, amino or carboxyl group per liter. molecule, by reaction with diisocyanates, e.g. diisocyanates prepared by phosgenation of aniline-formaldehyde condensates. In this context, for example, mention should be made of equimolar reaction products of polyaddition products of ethylene oxide and / or propylene oxide for monoalcohols and diphenyl methane diisocyanate, toluylene diisocyanate, l-isocyanato-3,5,5-trimethyl-5-isocyanatomethylcyclohexane or hexamethylene hexane or hexamethylene hexane or hexamethylene naphthylene-1,5-diisocyanate, or equimolar reaction products of these isocyanates with benzylamine, cyclohexylamine, oleylamine or monoaminopolyethers.

In principle, such monoisocyanates can also be prepared from molecules containing n isocyanate groups by reacting n-1 of these isocyanate groups with suitable acceptors, e.g. OH or NII groups.

However, in the process of the invention, preferably, reaction products of fatty acid esters and monoisocyanates containing 5-50 carbon atoms, especially 5-30 carbon atoms, are used, but the use of complexly constructed higher carbon monoisocyanates is also possible.

The reaction of the fatty acid ester or the mixture of the fatty acid esters with the polyisocyanates takes place in such a way that the fatty acid esters are mixed with the isocyanate and optionally stirred at temperatures between 30 and 200 ° C, preferably between 45 and 95 ° C. Acceleration of the reaction by means of catalysts is possible, but it should be avoided so that the reactivity of the isocyanate components in the later foam preparation is changed as little as possible in the undesirable direction.

When reacting the fatty acid ester with the polyisocyanate, a molar ratio of active hydrogen atoms to isocyanate groups is usually maintained at 1: 1-1: 25. The composition products are often prepared by reacting a mixture consisting of 0.5-50% by weight (preferably 1-35% by weight) of fatty acid ester and 99.5-50% by weight (preferably 99-65% by weight) of polyisocyanate at temperatures between 30 and 200 ° C.

The reaction of the fatty acid ester or the mixture of fatty acid esters with monoisocyanates takes place in such a way that the fatty acid esters are mixed with the isocyanate and optionally stirred to react at temperatures between 30 and 200 ° C, preferably between 45 and 110 ° C. Acceleration of the reaction by means of catalysts is possible, but it should be avoided so that the reactivity of the mixture in the later foam preparation is as undesirable as possible.

In the reaction of the fatty acid ester with the monoisocyanate, the reaction products are usually prepared by reacting a mixture of 0.5-70 wt.% (Preferably 1-55 wt.%) Of fatty acid ester and 99.5-30 wt.% (Preferably 99-45 wt.%) Of monoisocyanate. and 200 ° C. Of course, the compounds are also effective in the process of this invention when the reaction of isocyanate with fatty acid ester is carried out in stoichiometric weight ratio. Any excess isocyanate excess contained in the reaction products may be removed by distillation, but it may also remain in the reaction mixture if, e.g. the polyisocyanate is added or directly added to the foaming process.

The reaction products used in the process according to the invention can be added as such to the starting components used in the foam preparation, e.g. the polyisocyanate or polyol.

However, it is often advantageous to prepare the reaction products in situ in the polyisocyanate used as starting material in the preparation of the foams. As a rule, between 0.5 and 25% by weight, preferably between 2 and 18% by weight of fatty acid ester, based on the polyisocyanate is used. In-situ preparation of the reaction product in excess polyisocyanate provides a "modified" polyisocyanate product directly applicable to the foaming which results in foams having excellent abrasive properties.

Of course, as described above, it is also possible to prepare the reaction products of mono- or polyisocyanates and fatty acid esters first, and then later dilute them with more polyisocyanate, optionally of a different type, but the reaction product used in the process according to the invention can also be dosed separately in the foam preparation. .

Of course, additional release agents or release agents can also be used in the foam recipes, e.g. those disclosed in German Patent Specification No. 1,953,637 or Belgian Patent Specification No. 782,942, e.g. the oleic or tall oil fatty acid salt of amide group-containing amines which can be prepared by reacting N-dimethylamino-propylamine with oleic or tall oil fatty acid.

The reactor components are reacted by the process of the invention by known one-step methods, by the prepolymer process or by the semi-prepolymer process, often using mechanical apparatus, e.g. that disclosed in U.S. Patent No. 2,764,565. Details of processing apparatus which can also be used in the process of the invention are described in Kunststoff-Handbuch, Vol. VI, Vieweg and Hochtlen, Carl-Hanser-Verlag, Munich 1966, e.g. on pages 121-205.

The products made by the process according to the invention can be used in hard adjustment for the manufacture of furniture parts, body parts for vehicles, technical appliances and building elements.

In semi-hard to soft settings, they can be used for the production of safety upholstery for automobiles and elastic shoe soles.

In the following, the invention is further described by a number of examples. Unless otherwise stated, parts mean parts by weight.

Examples First, a number of examples of preparation of some fatty acid esters are described, in principle the preparation method described is applicable to almost all fatty acid ester types.

Fatty acid ester A

544 parts by weight of pentaerythritol, 3390 parts of oleic acid and 292 parts of adipic acid are stirred for 8 hours at 140 ° C. Then stir for 24 hours under vacuum at 140 ° C and then for 5 hours under water jet vacuum at 16 ° C. The final product is a clear, viscous liquid of average molecular weight 1100 (cryoscopic), OH number: 19.5; acid number: 25.0.

Fatty acid ester B

580 parts of pentaerythritol, 3390 parts of oleic acid and 292 parts of adipic acid are heated to 150 ° C over 20 hours under water jet vacuum. The mixture is then left for 3 hours at 150 ° C under vacuum. The condensation product thus produced has an OH number of 54.3 and an acid number of 25.5. The average molecular weight is 905.

Fatty acid ester C

This ester is prepared in the same way as fatty acid ester B, leaving the mixture for 10 hours under vacuum at 150 ° C.

The ester formed has an OH number of 53.1, an acid number of 5.6 and an average molecular weight of 1320.

Fatty acid ester D

300 parts of castoric acid are heated to 140 ° C in water jet vacuum and stirred at this temperature for 35 hours. Thereby a clear polyester of average molecular weight 1800 is obtained, with an OH number of 30.3 and an acid number of 34.6.

1 Al 851 16

Fatty acid ester E

This ester is prepared in the same way as fatty acid ester D, however, keeping the mixture at 140 ° C in water jet vacuum for 15 hours. The ester formed has an average molecular weight of 1070.

Fatty acid ester F

An ester is prepared from 4 moles of tranyl fatty acid (average molecular weight about 285) and 1 mole of sorbitol with an acid number of approx. 3 and an OH number of approx. 130th

Fatty acid ester G

Natural wool grease, OH number approx. 53, acid number ca. 0.7. The molecular weight of such a natural product cannot be precisely stated.

Mix the fatty acid esters A-G with one of the isocyanates mentioned in the examples below, so that the mixture contains approx. 5-10% by weight of fatty acid ester, after a few hours to a few days, a division of such mixture prepared at room temperature into two phases will occur. This effect is undesirable, but according to the invention, as shown in the following examples which serve to illustrate the process of the invention, it can be avoided by a temperature treatment at which the reaction products used in the process of the invention are formed.

Accordingly, the isocyanate reaction product mixtures used in the examples below do not exhibit any phase separation effect.

Example 1 A) Preparation of the reaction product used in the invention according to the invention in the polyisocyanate.

95 parts by weight (0.38 mol) of a polyisocyanate produced by phosgenation of aniline-formaldehyde condensates having a viscosity at 25 ° C of 320 cP and an NCO content of 31.5 wt% are used. 5 parts by weight (0.004 mol) of fatty acid ester A.

The components are reacted at 70 ° C. The reaction mixture is kept under stirring at 70 ° C for 4 hours. When the reaction is complete, the NCO content of the polyisocyanate contained in the reaction product is 29% by weight.

B) The method of the invention

As starting components, 100 parts by weight of a polyol blend having OH number 550 and a viscosity at 25 ° C of 1650 cP consisting of 1) 60 parts by weight of a polyether having OH number 830 made by addition of propylene oxide to trimethylol propane are used and 2 40 parts by weight of a polyether with OH number 42 made by addition of propylene oxide and ethylene oxide (in admixture) to a mixture of trimethylol propane and propylene glycol (molar ratio 3: 1), 1 part by weight of a polysiloxane-polyalkylene oxide block copolymer as foam stabilizer, 0.7 parts by weight of tetramethylguanidine as catalyst, 12 parts by weight of monofluorotrichloromethane and 156 parts by weight of the polyisocyanate of 1A).

Polyol blend and propellant are premixed and fed to a 2-component dosing mixer where it is intimately mixed with the polyisocyanate to produce the foamed reaction mixture which is immediately introduced into a 60 ° C hot metal tool. The die of the tool consists of galvanic non-nickel, while the cartridge is made of roll aluminum. The molding part, a right-angled box with a wall thickness of 15 mm, has the following dimensions: base surface = 360 x 250 mm, side height: 40 mm. The tool is clamped on a hydraulic pressure unit, which enables accurate measurement of the tearing forces. Via a power generator, the driving force is converted into an electrical signal which is amplified in a carrier frequency measuring amplifier and recorded with a compensation line printer. From the recorded data, the specific exhaust forces required to open the tool are first calculated and then the forces required to remove the fumel from the die with the ejectors are calculated. The take-out, ie. removal of the fume part from the fome takes place 7 minutes after the reaction mixture is introduced into the tool. The foam is a hard polyurethane foam with dense outer skin.

The tool can be opened with a specific tear force <0.02 kp / cm. The ejector requires a specific tear force of 2 0.11 kp / cm to eject the barrel. Analogous results are obtained when the fatty acid esters B or C. are used instead of the fatty acid ester A.

Example 2 (Comparative Example)

As starting materials, 100 parts by weight of polyol blend according to IB), 12 parts by weight of monofluorotrichloromethane and 147 parts by weight of a polyisocyanate prepared by phosgenation of aniline-formaldehyde condensates having a viscosity at 25 ° C of 320 cP and an NCO content of 31.5%.

The foaming is carried out as described in Example 1B).

2

With the maximum hydraulic output of 0.8 kp / cm the tool cannot be opened. If one tries to remove the mold part from the mold by means of the ejectors, the mold part is punched. The foam is of the same type as in Example 1.

Example 3 A) Preparation of the reaction product used in the process of the invention in the polyisocyanate 95 parts by weight (0.32 mol) of a polyisocyanate prepared by phosgenation of aniline-formaldehyde condensates with subsequent reaction with a diol (a polypropylene glycol) with OH number 580 and having a viscosity at 25 ° C of 430 cP and an NCO content of 28% by weight are reacted with 5 parts by weight (0.004 mol) of fatty acid ester A at 70 ° C. The reaction mixture is kept at 70 ° C with stirring for 4 hours. When the reaction is complete, the NCO content of the turnover-containing polyisocyanate is 26% by weight.

B) The method according to the invention

As starting components, 100 parts by weight of a polyol blend with OH number 510 and a viscosity at 25 ° C of 1230 cP is used, consisting of 1) 20 parts by weight of a polyether with OH number 540 made by the addition of ethylene oxide to trimethylol propane and 2) 20 parts by weight of a polyester with OH number 380 prepared by reaction of 1 mole of adipic acid, 2.6 moles of phthalic anhydride, 1.3 moles of oleic acid and 6.9 moles of trimethylolpropane, 1 part by weight of a polysiloxane-polyalkylene oxide block copolymer as foam stabilizer, 0.7 parts by weight of tetramethylguanidine as catalyst, 5 parts by weight of monofluorotrichloromethane and 160 parts by weight of polyisocyanate according to 3A).

The raw material mixture is foamed to a font portion as described in IB). A hard polyurethane mold foam with closed outer skin is available.

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After a standing time of 7 minutes in the mold, the force required for 2 opening of the tool is 0.03 kp / cm. The ejector expresses the mold part from the tool at a specific force of 2 0.01 kp / cm. Analogous results are also obtained when using fatty acid esters B and C.

Example 4 (Comparative Example).

Proceed as described in Example 3B), but in the foaming mixture, the polyisocyanate described in Example 3B) does not contain the reaction product with the acid ester, but only the polyisocyanate described in Example 3A. A mold part is prepared as described in Example 1B). After a standing time of 7 minutes in the mold, the tool cannot be opened using the built-in hydraulics, which means that the opening forces are greater than 0.8 kp / cm. The mechanical ejector destroys the mold part when pressed out of the tool. The foam is of the same type as in the previous examples.

Example 5 A) Preparation of the reaction product used in the process of the invention in the polyisocyanate 95 (0.38 mol) parts by weight of a polyisocyanate prepared by aniline-formaldehyde condensation with subsequent phosgenation is reacted with 5 parts by weight (0.003 mol) fatty acid ester D, which has a viscosity of 1075 cP at 25 ° C and has a molecular weight of 1600. The reaction takes place at 70 ° C. The reaction mixture is kept at 70 ° C with stirring for 4 hours. When the reaction is complete, the NCO content of the turnover-containing polyisocyanate is 29% by weight.

B) The process according to the invention 100 parts by weight of polyol blend according to IB), 1 parts by weight of a polysiloxane-polyalkylene oxide block copolymer as foam stabilizer, 12 parts by weight of monofluorotrichloromethane, 0.7 parts by weight of tetramethylguanidine as catalyst and 156 parts by weight as modified in Example 5A) IB) for a polyurethane mold part. A hard polyurethane foam fabric with closed outer skin is available. After 7 minutes, the mold part is removed from the 60 ° C hot metal mold. To open the tool a specific force of 0.16 kp / cm is required. The mechanical ejector ejects the mold member with a specific compressive force of 0.38 kp / cm2.

Analogous results are obtained when using the fatty acid ester E.

Example 6 A) Preparation of a polyisocyanate containing the reaction product used in the process of the invention 90 parts by weight (0.52 mol) of an isomer mixture consisting of 80% by weight toluylene-2,4-diisocyanate and 20% by weight toluylene - 2.6 diisocyanate (viscosity at 25 ° C 3 cP, NCO content: 48.3% by weight) is reacted with 10 parts by weight (0.008 mol) of fatty acid ester A at 70 ° C. The reaction mixture is kept at 70 ° C for 4 hours with stirring. When the reaction is complete, the NCO content of the turnover-containing polyisocyanate is 43% by weight.

B) The process according to the invention 100 parts by weight polyol mixture according to IB), 1 parts by weight foam stabilizer according to IB), 12 parts by weight monofluorotrichloromethane, 0.7 parts by weight tetramethylguanidine, 3 parts by weight amidamine oleic acid salt, prepared from 1 mole of 3-dimethylamino-propylamine-1 and 2 moles oleic acid (known release agent) and 95 parts by weight of polyisocyanate according to 6A) are placed in a stirrer container and the components are intensively mixed for 10 seconds by a rapid stirrer (3000 rpm) and immediately introduced into a 60 ° C mixture. hot metal tool. The metal tool consists of a water-heatable aluminum block. The tool hole in which the polyurethane mold body is made has dimensions of 300 x 200 x 10 mm. The tool is arranged so that it can be opened and closed by hand. The foaming mixture results in a foam "mold portion which can be easily removed manually from the metal mold described above. The foam is a hard polyurethane foam with closed outer skin.

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Example 7 (Comparative Example).

100 parts by weight of polyol mixture according to IB), 1 parts by weight of foam stabilizer according to IB), 12 parts by weight of monofluorotrichloromethane, 0.7 parts by weight of tetramethylguanidine and 85 parts by weight of an isomer mixture of 80% by weight toluylene - 2,4-diisocyanate and 20% by weight toluylene-2,6-diisocyanate is used to make a mold part in the manner described in Example 6. The same foam type is available as above. After a shelf-life of 7 minutes, one tries to remove the mold part from the tool, but thereby breaks the mold part into pieces in the mold. The individual fragments adhere to the walls. -

Example 8 A) Preparation of a Polyisocyanate Containing the Processing Method According to the Invention According to the Invention 99 parts by weight (0.4 mole) of a polyisocyanate produced by phosgenation of aniline-formaldehyde condensate and having a viscosity at 25 ° C of 320 cP and an NCO content of 31.5 wt%, are reacted at 100 ° C with 1 wt of fatty acid ester G (mole weight cannot be stated for natur this natural product).

The reaction mixture is kept at 100 ° C with stirring for 8 hours. When the reaction is complete, the NCO content of the turnover-containing polyisocyanate is 31% by weight.

B) The process according to the invention 100 parts by weight polyol mixture according to IB), 1 parts by weight foam stabilizer according to IB), 12 parts by weight monofluorotrichloromethane, 0.7 parts by weight tetramethylguanidine, 3 parts by weight amidamine oleic acid salt (similar to that used in example, 6B) and 132 parts by weight polyisocyanate according to 8A) is reacted as described in Example 6B) to a mold part. When the reaction is complete and the material has remained in the mold for 7 minutes, the mold part can be easily removed manually from the metal mold. The same type of foam is available as in the previous examples.

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Example 9 A) Preparation of a polyisocyanate containing the reaction product used in the process of the invention. 95 (0.38 mol) parts by weight of a polyisocyanate used according to Example 1A are reacted at 170 ° C with 5 parts by weight (0.006 mol). fatty acid ester F.

The reaction mixture is kept under stirring at 70 ° C for 4 hours. When the reaction ep is complete, the NCO content of the reaction product-containing polyisocyanate is 29% by weight.

E) The process of the invention 100 parts by weight of polyol mixture according to IB), 1 parts by weight of foam stabilizer according to IB), 12 parts by weight of monofluorotrichloromethane, Q, 7 parts by weight of tetramethylguanidine as catalyst, 3 parts by weight of amidamine oleic acid salt (similar to that used in Example 6B and 156 parts by weight of polyisocyanate according to Example 9A) is converted into a mold part as further described in Example 6B). The mold part can easily be removed manually from the metal tool. The foam has the same structure as the previous examples.

Example 10 (Comparative Example).

The components described in Example 9B) are used, however, using as a polyisocyanate 132 parts by weight of a polyisocyanate made by phosgenation of aniline-formaldehyde condensate and having a viscosity at 25 ° C of 320 cP and an NCO content of 31.5% by weight.

The reaction mixture is reacted as described in Example 6B) and a mold part having the same structure spm above is prepared. The mold part can only be easily removed from the metal tool, but no fracture is obtained.

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Example 11 A) Preparation of the reaction product used in the process of the invention 70 parts by weight (0.26 mol) of a polyisocyanate prepared by phosgenation of aniline-formaldehyde condensate and having a viscosity of 320 cP at 25 ° C. NCO content of 31.5% by weight is reacted with 30 parts by weight (0.022 mol) of fatty acid ester A.

The polyisocyanate is heated to 70 ° C and the fatty acid ester is slowly added with good stirring. The reaction mixture is kept at 70 ° C for 6 hours and then the NCO content of the reaction product is 20.5% by weight, while the viscosity is 460 cP.

B1 The process according to the invention 100 parts by weight of a polyol mixture of Example 1B), 12 parts by weight of monofluorotrichloromethane, 3 parts by weight of amidamine oleic acid salt (prepared from 1 mole of 3-dimethylamino-propylamine-1 and 2 moles of oleic acid), 110 parts by weight of unmodified polyisocyanate, which is prepared by phosgenation of aniline-formaldehyde condensate and having an NCO content of 31.5 percent, as well as 33 parts by weight of the modified polyisocyanate described in Example 11A) are used as starting components. Polyol blend and propellant are fed to a 2-component dosing mixer and foamed as described in Example 1A). The foam is of the same type as in the other examples. The tool can be opened with a specific force 2 2 <0.02 kp / cm. The ejector requires a specific force of 0.08 kp / cm to eject the mold member.

Example 12 A) Preparation of the reaction product used in the process of the invention 96 parts by weight of a monoisocyanate prepared by reaction of 1 mole of 4,4'-diisocyanate diphenylmethane with 1 mole of a polyether with OH number 74 (n -butanediol + 48% ethylene oxide and 52% propylene oxide), having a NCO content of 4%, are mixed with 100 parts by weight of fatty acid ester B.

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The components are reacted at 60 ° C. The reaction mixture is kept at 60 ° C with stirring for 4 hours. When the reaction is complete, the NCO content of the polyisocyanate is 0%.

B) The process of the invention 100 parts by weight of a polyol blend with OH number 517 and a viscosity at 25 ° C of 1650 cP consisting, first of all, 60 parts by weight of a polyether with OH number 830 made by addition of propylene oxide to trimethylol propane and, second, 40 parts by weight of a polyether with OH number 42 made by addition of propylene oxide and ethylene oxide (in admixture) to a mixture of trimethylolpropane and propylene glycol (molar ratio: 3: 1), 1 part by weight of a polysiloxane polyalkylene oxide -block copolymerisate as foam stabilizer, 0.7 parts by weight of tetramethylguanidine as catalyst, 12 parts by weight of monofluorotrichloromethane, 135 parts by weight of a polyisocyanate produced by phosgenation of aniline - formaldehyde condensate and having a viscosity at 25 ° C 110 cP and an NCO content of 31.5% by weight, as well as 6 parts by weight of an additive according to the invention 12A) are used as starting components. Polyol blend and propellant are fed to a two-component dosing mixer where the blend is intimately blended with the polyisocyanate to produce the foamed reaction mixture which is immediately introduced into 60 ° C hot metal tool. The die of the tool consists of galvano-nickel, while the die is made of roll aluminum. The molding section, a rectangular box with a wall thickness of 15 mm, has the following dimensions: base surface: 360 x 250 mm, side height: 40 mm. The tool is clamped on a hydraulic pressing unit which allows accurate measurement of the tearing forces. Via a power generator, the tearing power is converted into an electrical signal that is amplified in a carrier frequency measuring amplifier and recorded with a compensation line printer. From the recorded data, the specific forces required to open the tool are first calculated, and then the forces required to eject the die from the die by means of the ejectors. The take-out, ie. removal of the mold part from the mold takes place 7 minutes after the reaction mixture is introduced into the tool. The foam is of the same type as in the other examples.

2 The tool can be opened with a specific force of 0.06 kp / cm.

o 2

The ejectors require a specific force of 0.20 kp / cm 'to remove the mold part from the tool. Analogous results are obtained when using the fatty acid ester B instead of the fatty acid ester A.

Example 13 A) Preparation of the reaction product used in the process of the invention - 174 parts by weight (1 mol) of an isomer mixture consisting of 80% by weight of toluylene-2,4-diisocyanate and 20% by weight of toluylene-2,6-diisocyanate (viscosity at 25 ° C = 3 cP, NCO content = 48.3% by weight) is reacted with 14 g (1 mole) of tetradecanol to a monoisocyanate (NCO content = 10.8%).

36 parts by weight of this monoisocyanate are reacted Bread 100 parts by weight of fatty acid ester B at 60 ° C with stirring for 8 hours. The NCO content of the additive used in the process according to the invention is 0%.

B) The process according to the invention 100 parts by weight polyol blend according to 12B), 1 parts by weight foam stabilizer according to 12B), 12 parts by weight monofluorotrichloromethane, 0.7 parts by weight tetramethylguanidine, 3 parts by weight amidamine oleic acid salt (prepared from 1 mole of 3-dimethylamino-propylamine-1 and 2 moles oleic acid), 132 parts by weight of polyisocyanate according to 12b) and 6 parts by weight of the additive according to the invention described in 13A) are foamed as described in example 12B). for a mold part of the same type as in the other examples. After a delay time of 7 minutes, the power required to open the tool is less than 0.05 kp / cm. The expressors express the mold part of the tool at a specific force of 0.10 kp / cm. Analogous results are obtained using fatty acids A.

Example 14 A) Preparation of the reaction product used in the process of the invention - 174 parts by weight (1 mole) of an isomer mixture consisting of 80% by weight of toluylene-2,4-diisocyanate and 20% by weight of toluylene-2,6-diisocyanate (viscosity at 25 ° C = 3 cP, NCO content = 48.3% by weight) is reacted with 256 g (1 mole) of fatty alcohol mixture (C-14 to C-20 fraction) to a monoisocyanate. The NCO content is 9.7%.

39 parts by weight of this monoisocyanate are reacted with 100 parts by weight of fatty acid ester B at 70 ° C for 4 hours with stirring. At the end of the reaction, the NCO content is 0%.

B) The process according to the invention 100 parts by weight of polyol mixture according to 12B), 1 parts by weight of foam stabilizer according to 12b), 12 parts by weight of monofluorotrichloromethane, 0.7 parts by weight of tetramethylguanidine, 135 parts by weight of polyisocyanate according to 12b) and 6 parts by weight of the additive of the invention according to 14A) is converted into a polyurethane. mold part of the same type as in the other examples in the manner described in Example 12. After 7 minutes, the mold part is removed from the tool.

2

A specific force of 0.02 kp / cm is required to open the tool.

The mechanical expressor removes the mold part at a specific force 2 of 0.20 kp / cm.

Example 15 A) Preparation of the reaction product used in the process of the invention. 107 parts by weight of phenyl isocyanate are reacted with 100 parts by weight of fatty acid ester B at 80 ° C for 3 hours. The NCO content of the isocyanate thus modified is 0%. 5 kg of this additive useful in the process of the invention is mixed in cold condition with 95 parts by weight of a polyisocyanate prepared by phosgenation of aniline-formaldehyde condensate with subsequent reaction with a diol with OH number 580 and having a viscosity at 25 ° C of 430 cP and an NCO content of 28% by weight. The viscosity of this modified polyisocyanate at 148 ° C is 148 cP. The NCO content is 27.4%.

B) The process according to the invention 100 parts by weight of a polyol mixture with OH number 510 and a viscosity at 25 ° C of 1230 cP consisting of a) 20 parts by weight of a polyether with OH number 540 made by the addition of ethylene oxide to trimethylol propane, and b) 20 parts by weight of a polyester with OH number 380 prepared by reaction of 1 mole of adipic acid, 2.6 moles of phthalic anhydride, 1.3 moles of oleic acid and 6.9 moles of trimethylolpropane, 1 part by weight of a polysiloxane-polyalkylene. lenoxide block copolymer as foam stabilizer, 0.7 parts by weight tetramethylguanidine as catalyst, 5 parts by weight of monofluorotrichloromethane and 154 parts by weight of the polyisocyanate of Example 15A) are used as starting components. The raw material mixture is foamed into a mold part of the same type as in the other examples described in Example 12b). After a shelf-life of 7 minutes 2, the force required to open the tool is 0.1 kp / cra. The expressors express the mold part of the tool at a specific force of 0.3 kp / cm. Analogous results are obtained when using fatty acid ester A.

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