CA1276752C

CA1276752C - Process for the preparation of cellular/noncellular polyurethane-polyurea molded articles having improved demolding properties

Info

Publication number: CA1276752C
Application number: CA000518426A
Authority: CA
Inventors: Peter Horn; Hans U. Schmidt; Matthias Marx
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 1985-10-05
Filing date: 1986-09-17
Publication date: 1990-11-27
Anticipated expiration: 2007-11-27
Also published as: EP0218175B1; DE3682159D1; DE3535711A1; ATE68802T1; EP0218175A3; EP0218175A2

Abstract

A PROCESS FOR THE PREPARATION OF CELLULAR/NONCELLULAR
POLYURETHANE-POLYUREA MOLDED
ARTICLES HAVING IMPROVED DEMOLDING PROPERTIES
Abstract of the Disclosure The discovery concerns a process for the prepara-tion of cellular or noncellular polyurethane-polyurea molded articles having improved demolding properties through the reaction of a) an organic polyisocyanate, b) a higher molecular weight compound having at least two and, optionally, reactive hydrogen atoms, c) an aromatic diamine, and, optionally d) a chain extender, and/or crosslinker and e) an internal mold release agent, in the presence of f) a catalyst, and, optionally, g) a blowing agent, h) auxiliaries and/or additives by reaction injection molding technique in a closed mold, wherein said internal mold release agent (e) comprises A) 0.1 to 10 percent by weight, preferably 1 to 8 percent by weight, based on the entire weight of the structural components (b), (c), (d), a mixture comprising i) 5 to 80 parts by weight, preferably 30 to 70 parts by weight, of at least one organic amine and/or cyclic lactam, ii) 20 to 95 parts by weight, preferably 40 to 70 parts by weight, of at least one metal salt of stearic acid and/or isostearic acid, and iii) 0 to 5 parts by weight, preferably 0.01 to 1 part by weight, of a metal salt of an organic mono-and/or dicarboxylic acid, and B) 0.01 to 2 percent by weight, preferably 0.1 to 1.5 percent by weight based on the total weight of the component (b), (c), (d) of at least one organic mono-and/or dicarboxylic acid, or their anhydride.

The internal mold release agents are used in the production of molded articles by polyisocyanate-addition polymerization in open or preferably closed, appropriate metal, heated molds using reaction injection techniques.

Description

Docket No. 38030 ~.Z7~752 A PROCESS FOR THE PREPARATION OF CELLULAR/NONCELLULAR
POLYURETHANE-POLYUREA MOLDED
ARTICLES HAVING IMPROVED DEMOLDING PROPERTIES
Backqround of the Invention 1. Field of Invention The present invention is directed to a RIM process using a molding composition which contains an internal mold release agent mixture comprising an organic amine, a metal salt of stearic acid, a metal salt of organic mono- and/or dicarboxylic acid, and an organic mono~ and/or dicarboxylic acid or their anhydrides.

2. Description of the Prior Art Preparation of cellular or noncellular molded articles, with a compact surface layer from polyurethane-polyurea elastomers using the reaction injection molding technique in closed molds, is the subject of numerous literature and patent publications. U.S. 4,218,543 (DE OS
26 22 951) describes polyurethane systems consisting of organic polyisocyanates, polyols, and reactive aromatic di-or polyamines with amino groups in the ortho position substituted by alkyl groups.
When the reaction time between the components of the polyurethane system is rapid and polished metal molding tools are utilized, it may not be necessary to employ demolding release agents. However, use of demolding release agents ba~ed on wax and silicone, as well as internal mold 12~7675Z

release agents are known in the art. See U.S. 3,726,952 tDE-AS 19 53 637) and GB 1,365,215 (DE-AS 21 21 670).
U.S. 3,726,952 (German Patent DE-AS 19 53 637) discloses release agents comprising salts having at least 25 aliphatic carbon atoms prepared from aliphatic mono- or polycarboxylic acids and primary mono-, di- or polyamines with two or more carbon atoms or amide or ester groups having amines which possess at least one primary, secondary or tertiary amino group. German Application DE AS 21 21 670 discloses a mixture of at least two compounds selected from the group consisting of amine carboxylic acid salts, as described in German Application DE AS 19 53 637, with saturated and unsaturated COOH and/or OH groups having esters of mono- and/or polycarboxylic acids, and polyvalent alcohols or naeural and/or synthetic oils, fats or waxes as release agents. It i9 also known in the art that use of mold release agent formulations containing only primary aromatic diamines exhibit insignificant improvement in the self-releasing properties. Additionally, release agents containing acid groups, especially carboxyl groups, may react with catalysts used in the polyurethane formulations producing molded articles without initial green strength.
To solve the above-described problems, polyethers comprising reactive groups of at least 50 percent primary and/or secondary amino groups are used to replace higher 1~7~75Z

molecular weight polyhydroxyl compounds in the relea~e agents. This is disclosed in EP OS 81 701 (AU 82/90150) However, the use of polyether-polyamines i9 costly, re-sulting in expensive molding articles. Additionally, due to changes in the mechanical properties of the molded article, there i9 limited commercial utility.
EP-A-153 639 discloses an improvement in self-releasing properties for the internal mold relea~e agents by using carboxylic e~ters and/or carboxylic amides, produced through esterification or amidization of mixtures of montanic acid, and at lea~t one aliphatic carboxylic acid having at least 10 carbon atoms, difunctional alkanolamines, polyols, and/or polyamines having molecular weightq from 60 to 400-U.S. Patent 4,519,965 (EP-A-173 888) disclo~es an internal mold release agent comprising a zinc carboxylate containing 8 to 24 carbon atoms per carboxylic group and a compatibilizer comprising a member selected from the group consisting of nitrogen-containing, isocyanate-reactive, acyclic compounds and nitrogen-containing, isocyanate-reactive polymers in an amount sufficient to stabilize the zinc carboxylate. However, thi~ system does not completely solve the problems associated with demolding.

~Z767~2 Summary of Invention The subject matter of this invention i3 a process for the preparation of celluar or noncellular polyurethane-polyurea molded article3 having improved demolding proper-tie~ through the reaction of a) an organic polyisocyanate, b1 a higher molecular compound having at lea~t two reactive hydrogen atoms, c) an aromatic diamine and, optionally, d) a chain extender or cro~slinker and e) an internal mold release agent, in the presence of f) a catalyst and, optionally, g) a blowing agent, and h) auxiliaries and/or additives by reaction injection molding technique in a closed mold, wherein ~aid internal mold release agent (e) comprises A) 0.1 to 10 percent by weight, preferably 1 to 8 percent by weight, based on the entire weight of the structural components (b), (c), (d), a mixture comprising:
i) 5 to 80 part~ by weight, preferably 30 to 70 parts by weight, of at least one organic amine and~or cyclic lactam, lZ76752 ii) 20 to 95 parts by weight, preferably 40 to 70 parts by weight, of at least one metal salt of stearic acid and/or isostearic acid, and iii) 0 to 5 parts by weight, preferably 0.01 to 1 part by weight, of a metal salt of an organic mono- and/or dicarboxylic acid, and B) 0.01 to 2 percent by weight, preferably 0.1 to 1.~
percent by weight based on the total weight of the component (b), tc), (d) of at least one organic mono- and/or dicarboxylic acid, or their anhy-drides.

The invention is also concerned with the inter-nal mold release agent (c) per se, which can be used in the production of molded articles by polyisocyanate-addition polymerization in open or preferably closed, heated metallic molds using reaction injection techniques.
Description of the Invention Since neither the known release agents or the formerly known compound combinations resulted in desired sufficient release effects, it could not be expected that the discovered internal mold release agent would demonstrate a preferable release ef~ect. Additionally, the paintability of molded articleq produced by the process of the invention is not affected. The following is a description of each of . .

~Z76752 the compounds of the formulation utilized in the process of the subject invention.
Organic Polyisocyanate A suitable organic polyisocyanate component (a) includes aliphatic, cycloaliphatic, araliphatic and prefer-ably aromatic multivalent isocyanates. In particular, the following may be named as examples: alkylene diisocyanates having from 4 to 12 carbon atoms in alkylene radicals, such as 1,12-dodecane-diisocyanate, 1,4-tetramethylene diisocya-nate and preferably 1,6-hexamethylene diisocyanate, cyclo-aliphatic diisocyanates, such as 1,3-cyclohexane and 1,4-diisocyanate, as well as, optional mixtures of the isomers, l-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl cyclohexane (isophorone diisocyanate), 2,4- and 2,6-hexahydrotoluene diisocyanate, as well as the corresponding isomeric mixture, 4,4'-, 2,2'- and 2,4'-dicyclohexylmethane diisocyanate, the corresponding isomeric mixtures, and preferably aromatics di- and polyisocyanate, such as 4,4'-, 2,4'- and 2,2'-diisocyanato diphenylmethane and the corresponding isomeric mixtures, 2,4- and 2,6-diisocyanato toluene and the corres-ponding isomeric mixtures, 1,5-diisocyanato naphthalene, polyphenyl-polymethylene polyisocyanate, 2,4,6-triisocyanato toluene, and preferably mixtures from diphenylmethane diisocyanate and polyphenyl polymethylene polyisocyanate.
The di- and polyi~ocyanate~ can be used either alone or in the form of mixtures.

lZ76752 Also, frequently used are the so-called modified multivalent isocyanates, that is, product~ obtained by the chemical reaction of di- and/or polyisocyanates as described above. Following are examples of modified organic di- and polyisocyanates: carbodiimide groups having polyisocyanates according to DE Patent 10 92 007, allophanate groups having polyisocyanates which are described, for example, in British Patent 994 890, 8elgium Patent 761 626, and NL-OS 71 02 524 i~ocyanurate groups having polyisocyanates as described in D~-Patent 10 22 789, DE-Patent 12 22 067, 10 27 394, DE-OS
19 29 034, and DE-OS 20 04 048; polyisocyanates with urethane groups as described in Belgium Patent 752 261, and in U.S. Patent 3,394,164; polyisocyanates containing acylated urea group as disclosed in DE-Patent 12 30 778;
polyisocyanates with biuret groups as disclosed in DE-Patent 11 01 394 and GB-Patent 889 050: polyisocyanate~ produced by teleomerization reactions as de~cribed in Belgium Patent 723 640, polyisocyanates with ester groups, for example, as described in GB-Patent 965 474, GB-Patent 1 072 956, U.S.
Patent 3,567,765 and in DE-Patent 12 31 688.
Preferred compounds include: polyisocyanate-containing urethane groups, for instance lower molecular linear or branched alkane diols, dialkylene glycols or polyoxyalkylene glycols having molecular weights up to 3000 based on ethylene oxide, 1,2-propylene oxide or mixtures of 127t;752 modified 4,4'- and/or 2,4'-diphenylmethane diisocyanate or 2,4- and/or 2,6-toluene diisocyanate, carbodiimide groups and/or polyi~ocyanates containing isocyanurate ring~, for example, 4,4'-, 2,4'-diphenylmethane diisocyanate, 2,4-and/or 2,6-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, mixtures of 2,4'- and 4,4'-diphenylmethane isocyanate, toluene diisocyanate, and polyphenyl-poly-methylene polyisocyanates and mixtures of toluene diisocya-nates and polyphenyl-polymethylene polyisocyanate.

Higher Molecular CompoundA Havinq at Least Two Reactive Hydroqen Atom~
Component (b) compounds are those compounds having a functionality from 2 to 8, preferably from 2 to 4, and a molecular weight from 1000 to 8000, preferably from 1200 to 6000. Polyether-polyamine and/or preferably polyols are ~elected from the groups of the polyether polyols, polyester diols, polythioether polyols, polyester amides, polyacetals containing hydroxyl groups and aliphatic polycarbonates containing hydroxyl groups or mixtures of at lea~t two of these polyols.
Polyester polyols and/or polyether polyols are preferred, particularly, polyester polyols which have a functionality from 2 to 3 and have a molecular weight from 1000 to 3000 and preferably 1800 to 2500. Suitable poly-ester polyols are prepared, for example, from organic dicarboxylic acids having from 2 to 12 carbon atoms, preferably aliphatic dicarboxylic acids containing 4 to 6 carbon atoms and multivalent alcohols, preferably diols having from 2 to 12 carbon atoms, preferably from 2 to 6 carbon atoms. Dicarboxylic acids include succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, maleic acid, and fumaric acid. The dicarboxylic acids can be used singly or as mixtures. Corresponding dicarboxylic acid derivatives can be used as substituees for uncombined dicarboxylic acids. For example, dicarboxylic acid esters of alcohols having from 1 to 4 carbon atoms, or dicarboxylic acid anhydrides. Preferably used are dicarboxylic mixtures of succinic, glutaric and adipic acids in quantity ratios of, for example, 20-35: 35-50: 20-32 parts by weight and preferably adipic acid. Examples of divalent and multi-valent alcohols, especially diols are: ethanediol, di-ethylene glycol, 1,2- or 1,3-propanediol, dipropylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, l,10-decanediol, glycerin and trimethylolpropane. Prefer-ably used are: ethanediol, diethylene glycol, 1,4-butane-diol, 1,5-pentanediol, 1,6-hexanediol or mixtures of at least two of the above-named diols, especially mixtures of 1,4-butanediol, 1,5-pentanediol and 1,6-hexanediol. In addition, polyester polyols from lactones can be u3ed, for _g_ 127~7S2 example, ~-caprolactone or hydroxycarboxylic acids, for example, ~-hydroxycapronic acid.
Suitable polyether polyols are produced by known processes, for instance, through anionic polymerization with alkali hydroxides, such as, sodium or potassium hydroxide, or alkali alkoxides, such as, sodium or potassium methylate or potas~ium isopropylate as catalysts, or through cationic polymerization with Lewis acids, such as, antimony penta-chloride, boron trifluoride etherate, or bleaching earth, as catalysts, from one or more alkylene oxides, having from 2 to 4 carbon atoms in the alkylene radical, and optionally, an initiator molecule which contains 2 to 8, preferably 2 to 4, reactive hydrogen atoms.
Suitable alkylene oxides are for example ethylene oxide, 1,3-propylene oxide, 1,2- or 2,3-butylene oxide, and preferably ethylene oxide and l,2-propylene oxide. Tetra-hydrofuran and styrene oxide may also be used. The alkylene oxides can be used singly, alternately one after another, or as mixtures. The following are examples of the initiator molecule: water, organic dicarboxylic acid, such as succinic acid, adipic acid, phthalic acid, and terephthalic acid, aliphatic and aromatic, optionally N-mono-, N,N- and N,N'-dialkyl ~ubstituted diamines having from 1 to 4 carbon atom~ in alkyl radicals, as possibly mono- and dialkyl subqtituted ethylene diamines, diethylenetriamine, tri 1'~76752 ethylenetetramine, 1,3-propylenediamine, 1,3- or 1,4-butylenediamine, 1,2-, 1,3-, 1,4-, 1,5- and 1,6-hexa-methylenediamine, phenylenediamines, 2,4- and 2,6-toluene-diamine and 4,4'- 2,4'- and 2,2'-diaminodiphenylmethane.
Additionally, other examples of the initiator molecules include the following: alkanolamines such as ethanolamine, diethanolamine, N-methyl- and N-ethyl-ethanol-amine, N-methyl- and N-ethyl-diethanolamine and triethanol-amine, ammonia, hydrazine and hydrazide. Preferably used are multivalent, especially bi- and/or trivalent alcohols such as ethanediol, 1,2- and 1,3-propanediol, diethylene glycol, dipropylene glycol, 1,4-butanediol, and 1,6-hexane-diol, glycerin, trimethylolpropane, pentaerythritol, sorbitol and saccharose.
The preferred polyether polyols have a function-ality from 2 to 4 and have a molecular weight from 1000 to 8000, preferably from 1200 to 6000, and especially 1800 to 4000. They can, just as the polyester polyol~, be used alone or in the form of mixtures. In addition, the poly-ester polyols may be used mixed with the polyester polyols,as well as, the hydroxyl group-containing polyesteramides, polyacetals, polycarbonates, and/or polyether polyamines.
Polyacetals containing a hydroxyl group include glycols, such as diethylene glycol, triethylene glycol, 4,4'-dihydroxyethoxy-diphenyldimethyl methane, hexanediol and formaldehyde produced compounds. Suitably polyacetals may also be produced through polymerization of cyclic acetals.
Polycarbonate containing hydroxyl groups are produced from diol reactions such as 1,3-propanediol, 1,4-butanediol, and/or 1,6-hexanediol, diethylene glycol, triethylene glycol or tetraethylene glycol with diaryl-carbonates, for example, diphenylcarbonate or phosgene.
Examples of polyesteramide~ are those from multivalent saturated and/or unsaturated carboxylic acids or their anhydrides and multivalent saturated and/or unsatu-rated amino alcohols or mixtures of multivalent alcohols and amino alcohols and/or polyamines derived chiefly from linear condensates.
Suitable polyether polyamines are produced by the above-identified polyether polyols according to conventional processes. For example, by cyanoalkylization of polyoxy-alkylene polyols and subsequently hydrogenation of the formed nitrile as described in U.S. 3,267,050, or the amination of polyoxyalkylene polyolq with amines or ammonia in the presence of hydrogen and catalysts a~ disclosed in DE
12 15 373.

127~752 Aromatic Diamine The aromatic diamines (c) of the subject process include primary amino groups which are ~terically hindered by at lea~t one ortho-positioned alkyl Qubstituent at each amino group when reacted with the polyisocyanate (a).
Preferred are mixtures of 50 to 99.9 percent by weight, preferably 65 to 78 percent by weight, of at least one of the primary aromatic diamine~ (c), and 0.1 to 50 percent by weight, preferably 22 to 35 percent by weight, of at least one unsubstituted or substituted primary aromatic diamine (ci) with amino groups which do not demon~trate decreased reactivity with the polyisocyanate through electron with-drawing substituents and/or stearic hindrance. The per-centage by weight is based on the entire weight of the mixture (c) and (ci).
EApecially suited as component (c) are primary aromatic diamines, which are liquid at room temperature and which are partially miscible with component (b). Preferably u~ed are akyl-sub~tituted meta-phenylenediamines having the structure 1~ NH 2 R~IIH 2 H2N- ~ R and/or ~ R

127~752 in which Rl is a hydrogen atom or linear or branched alkyl radical having from 1 to 12 carbon atoms, preferably from 1 to 6 carbon atoms, and where R and R3 are the same or different, linear or branched alkyl radicals having from 1 to 4 carbon atoms, for example, methyl, ethyl, propyl, isopropyl, butyl or sec.-butyl radicals.
Suited, especially, for alkyl radicals, R , are those with the branched position at the Cl carbon atom. In addition to hydrogen, the following are examples of alkyl radicals R : methyl, ethyl, n- and isopropyl, butyl, hexyl, octyl, decyl, l-methyloctyl, 2-ethyloctyl, l-methylhexyl, l,l-dimethylpentyl, 1,3,3-trimethylhexyl, l-ethylpentyl, 2-ethylpentyl and preferably cyclohexyl, l-methyl-n-propyl, tert.-butyl, l-ethyl-n-propyl, l-methyl-n-butyl and 1,1-dimethyl-n-propyl radicals.
Examples of alkyl substituted m-phenylenediamines are: 2,4-dimethyl-, 2,4-diethyl-, 2,4-diisopropyl-, 2,4-diethyl-6-methyl-, 2-methyl-4,6-diethyl-, 2,4,6-triethyl-, 2,4-dimethyl-6-cyclohexyl-, 2-cyclohexyl-4,6-diethyl-, 2-cyclohexyl-2,6-diisopropyl-, 2,4-dimethyl-6-(1-ethyl-n-propyl)-, 2,4-dimethyl-6-(1,1-dimethyl-n-propyl)- and 2-(1-methyl-n-butyl)-4,6-dimethyl-1,3-phenylenediamine.
In addition, alkyl substituted diamino diphenyl-methanes such as 3,3'-di- and 3,3',5,5'-tetra-n-alkyl-~ubstituted 4,4'-diaminodiphenylmethane, for example, 3,3'-1~7~75Z

diethyl-, 3,3',5,5'-tetraethyl- and 3,3',5,5'-tetra-n-propyl-4,4'-diaminodiphenylmethane are suitable.
An advantageous application results in using diaminodiphenylmethane with the following structure:

H2N~3_ CH2 ~ NH2 wherein R , R5, R and R are the same or different, either a methyl, ethyl, propyl, isopropyl, sec.-butyl or tert.-butyl radical, but at least one of the radicals mu~t be an isopropyl or sec.-butyl radical. The alkyl-substituted 4,4'-diaminodiphenylmethanes can also be used in mixtures with isomer~ having the ~tructures 2~--R 5 R 6 R4 - ~ CH2- ~ NH2 and/or R4- ~H - ~ - R 6 , wherein R4, R5, R6 and R7 have the above-identified meaning.
The followinq are examples: 3,3',5-trimethyl-S'-isopropyl-, 3,3',5-triethyl-5'-isopropyl-, 3,3',5-trimethyl-S'-sec.-butyl-, 3,3',5-triethyl-5'-sec.-butyl-4,4'-diamino-diphenylmethane, 3,3'-dimethyl-5,5'-diisopropyl-, 3,3'-diethyl-5,5'-di-sec.-butyl-, 3,3'-diethyl-5,5'-di-sec.-butyl-, 3,5-dimethyl-3',5'-diisopropyl-, 3,5'diethyl-3',5'-diisopropyl-, 3,5-dimethyl-3',5'-di-sec.-butyl-, 3,5-diethyl-3',5'-di-sec.-butyl-4,4'-diaminodiphenylmethane, 3-methyl-3',5,5'-triisopropyl-, 3-ethyl-3',5,5'-triisopropyl-, 3-methyl-3',5,5'-tri-sec.-butyl-. 3-ethyl-3',5,5'-tri-sec.-butyl-4,4'-diaminodiphenylmethane, 3,3'-diisopropyl-5,5'-di-sec.-butyl-, 3,5-diisopropyl-3',5'-di-sec.-butyl-, 3-ethyl-5-sec.-butyl-3',5'-diisopropyl-, 3-methyl-5-tert.-butyl-3',5'-diisopropyl-, 3-ethyl-5-sec.-butyl-3'-methyl-5'-tert.-butyl-, 3,3',5,5'-tetraisopropyl- and 3,3',5,5'-tetra-sec.-butyl-4,4'-diaminodiphenylmethane.
Preferably u~ed as the primary aromatic diamines are: 2,4-diethyl-, 2,4-dimethylphenylene diamine-1,3, 2,4-diethyl-6-methyl-, 2-methyl-4,6-diethyl-phenylene diamine-1,3, 2,4,6-triethylphenylene diamine-1,3, 2,4-dimethyl-6-tert. butyl-, 2,4-dimethyl-6-isooctyl- and 2,4-dimethyl-6-cyclohexylphenylene diamine-1,3, as well as 3,5-dimethyl-3', 5'-diisopropyl- and 3,3',5,5'-tetraisopropyl-4,4'-diaminodi-phenyl methane.

The primary aromatic diamines can be used alone or in the form of mixtures, for instance from alkyl-substituted 1,3-phenylenediamines, 3,3'-di- and/or 3,3',5,5'-tetraalkyl-substituted 4,4'-diaminodiphenyl methanes. In addition, the primary aromatic diamines can be mixed with a maximum of 50 percent by weight, primary alkyl-substituted aromatic tri-to pentamines, based on the total weight. For example, polyphenyl-polymethylene polyamines may be used wherein the amino group of the aromatic polyamineQ i8 substituted at an ortho position with an alkyl radical.
For diamine component (ci), unsubstituted primary aromatic diamines are preferably used. Also suited are substituted primary aromatic diamines, appropriately substituted monoalkyl ~ubstituted aromatic diamines, where the reactivity of the amino group by the substituent is not negatively influenced. Some examples are: 1,2-, 1,3- and 1,4-phenylenediamine, benzidine, 4,4'- and 2,4'-diaminodi-phenylmethane, 4,4'-diaminodiphenylether, 1,5-diamino-naphthalene, 1,8-diamino-naphthalene, 3,4-, 2,4- and 2,6-toluene diamine. The aromatic diamines (ci) can be used just as the aromatic diamines (c) singly or in the form of mixtures. Preferable application is 2,4- and/or 2,6-toluenediamine and especially 1,3-phenylene diamine.

~Z76752 For aromatic diamines, preferable mixtureq are for component (c) 50 to 80 percent by weight 2,4-dimethyl-6-tert.-butyl-phenylenediamine-1,3, 2,4-diethyl-6-methyl and/or 2-methyl-4,6-diethyl-phenylenediamine-1,3 and for component (ci) 20 to 50 percent by weight 1,3-phenylenedi-amine, wherein the percent by weight i~ based on the total weight of the mixture of the component~ (c) and (ci).
The aromatic diamine (c) or the mixture of the aromatic diamines (c) and (ci) are used in the process of the invention in quantities of from 5 to 50 parts by weight, preferably 10 to 40 part~ by weight and especially 15 to 30 parts by weight based on 100 parts by weight of the compo-nent (b).
Chain Extending Agents or Crosslinkers The chain extending agents or crosslinker~ (d) have molecular weights les~ than 500, preferably from 30 to 400 and exhibit preferably two active hydrogen atoms.
Crosslinkers (d) are, for example, aliphatic and/or arali-phatic diols having from 2 to 14, preferably 2 to 6 carbon atoms, such as propanediol-1,3, decanediol-l,10, diethylene glycol, dipropylene glycol, bi~-(2-hydroxyethyl)-hydro-quinone and, preferably, ethylene glycol, butanediol-1,4 and hexanediol-1,6 triols such as glycerin and trimethylolpro-pane, lower molecular polyoxyalkylkene polyol~ based on ethylene and/or l,2-propylene oxide and the previou~ly lZ76752 identified initiation molecules and sec. aromatic diamines, such as: N,N'dialkyl-substituted aromatic diamines, which optionally, on the aromatic ring can be sub~tituted by alkyl radicals, having from 1 to 20, preferably 1 to 4 carbon atoms in the N-alkyl radical, such as N,N'diethyl-, N,N'-di-sec-pentyl-, N,N'-di-~ec-hexyl-, N, N'-di-sec-decyl-, N, N'-dicyclohexyl-p- or m-phenylene diamine, N,N'-dimethyl-, N,N'-diethyl-, N,N'-diisopropyl-, N,N'-di sec-butyl-, N,N'-dicyclohexyl-4,4'-diamino-diphenylmethane and N, N ' -di-sec-butyl-benzidine.
The chain extending agent and/or crosslinker (d) can be used alone or in the form of mixtures. In mixtures of aromatic diamines (c) and chain extending agents and/or crosslinkers (d), the aromatic diamines (c) should contain per 100 parts by weight, 1 to 40, preferably 5 to 2 parts by weight of component (d).
Internal Mold Release Agents The internal mold release agent (e) of the sub~ect invention comprises:
A) a mixture of i) an organic amine and/or cyclic lactam, ii) a metal salt of stearic acid, or isostearic acid or a mixture of stearic and isostearic acid, 127~752 iii) a metal salt of an organic mono and/or dicarboxylic acid, and B) at least one organic mono- and/or dicarboxylic acid or their anhydride.

Examples of organic amines (Ai) include aliphatic and/or cycloaliphatic monoamines and/or polyamines having from 3 to 20 carbon atoms, preferably 4 to 13 carbon atoms, such as isopropyl-, n-butyl-, isobutyl-, ~ec.-butyl, n- and isoamyl-, l,2-dimethylpropyl-, n- and isohexyl-, 2-ethyl-hexyl-, octyl-, 6-methylheptyl-2-, 2-ethyloctyl-, decyl-, tridecyl-, dodecyl-, hexadecyl-, octadecyl-, stearyl- and cyclohexylamine. Examples of linear, branched, cyclic and/or heterocyclic alkanolamines having from 2 to 12 carbon atoms, preferably 2 to 10 carbon atoms, include ethanol-amine, propanolamine, butanolamine, 3-hydroxybutylamine, 2-hydroxybutylamine, pentanolamine, hexanolamine, 4-hydroxy-hexylamine, octanolamine, 1-(2-hydroxyethyl)-piperazine, N-methyl-, N-butyl-, N-neopentyl-, N-cyclohexylethanolamine, N-methylisopropanolamine, diethanolamine, dipropanolamine, and N-alkyl-dialkanolamine with from 1 to 6 carbon atoms in the alkyl radicals, such as N-methyl-, N-butyl-, N-cyclo-hexyl-diethanol-, diisopropanolamine, 1,4-di(2-hydroxy-ethyl)-piperazine, 1,4-diisopropanolpiperazine, triethanol-amine and triisopropanolamine. Suitable aliphatic or ~Z76752 cycloalipha~ic primary diamines having from 2 to 20 carbon atoms, preferably 2 to 12 carbon atoms, include ethylene-, 1,2- or 1,3-propylene, 1,4-butylene, 1,6-hexamethylene, neopentyl-, l,10-decylene, 1,12-dodecylene diamine and diaminocyclohexane. Example~ of aliphatic or cycloaliphatic primary mono- and/or polyamines having molecular weights from 103 to 2000, preferably from 117 to 800, which additionally contain secondary and/or tertiary amino groups and/or heterocyclic radicals and/or hydroxyl groups and/or ether groupg in bonded form, include diethylene triamine, dipropylene triamine, dihexamethylene triamine, l-diethyl-amino-4-pentyl-, 3-(2-ethylhexoxy)-propyl-, 3-~2-amino-ethyl)aminopropylamine, N,N'-bis(3-aminopropyl)ethylenedi-amine, condensation products from diethylenetriamine, N-2-aminoethyl-ethanolamine, 2-aminoethoxyethanol-2, 4,~-dioxadodecane-1,12-diamine, N,N'-bis-(3-aminopropyl)-ethylenediamine, 1-(2-aminoethyl-)piperazine, 1,4-Bis-(2-aminoethyl-)piperazine, 1,4-Bis-(3-aminopropyl-)piperazine, tris-(aminoethyl-)amine, tris-(3-aminopropyl-)amine and polyoxyalkylene polyamines having primary and/or secondary amino groups having functionality of from 1 to 6, preferably 2 to 4 and molecular weights of 400 to 5000, preferably from 400 to 2000, such as, polyoxypropylene diamine, polyoxy-ethylene diamine, polyoxypropylene-polyoxyethylene diamine, polyoxypropylene triamine, polyoxyethylene triamine, lZ76752 polyoxypropylene-polyoxyethylene triamine and polyoxypropy-lene-polyoxyethylene tetramine. Also suited are polyoxy-alkylene po1yamines which contain up to 50 percent, prefer-ably up to 15 percent terminal primary and/or secondary hydroxyl groups in bonded form. The organic amines (Ai) can be used alone or as mixtures of amines of the same groups or from amine~ of different groups.
In place of the organic amines (Ai) or in mixtures with these, cyclic lactams can al~o be used, whereby from 5 to 7 membered cyclic lactams, such as pyrrolidone and ~-caprolactam are used.
Preferred organic amine (Ai) examples are: n-butylamine, tridecylamine, 6-methylheptyl-2-amine, 1-(2-aminoethyl)-piperazine, 1-(2-hydroxyethyl)-piperazine, N-2-aminoethyl-ethanolamine, diethylenetriamine, and poly-alkylene-polyamine with a molecular weight from 117 to 800 such as polyethylene-polyamine, polyoxypropylene triamine and 3,3'-dimethyl-4-4'-diaminodicyclohexyl methane.
In the preparation of the metal salts (Aii), commercially available stearic acid and i~ostearic acid up to 10 percent by weight, preferably up to 5 percent by weight, are suitable without significantly influencing the releasing effect. Other suitable compounds are un~aturated carboxylic acid~ having from 8 to 24 carbon atoms, such as palmitic acids, oleic acids, ricinoleic acids, and others.

lZ76752 Metals suitable in the formation of metal salts (Aii) and (Aiii) are alkali metals, preferably sodium and potassium, earth alkali metals, preferably magnesium and calcium, and especially zinc. Preferentially used as metal salt~ are the stearic and/or isostearic acid, zinc stearates, zinc isostearate, calcium stearate and sodium ~tearate or mixtureY from at least two of these stearates.
Eapecially used is a mixture of zinc stearate and/or zinc isostearate, calcium and sodium stearate.
In addition to the metal salts (Aii) of the stearic and/or isostearic acid3, the internal mold release agent may contain metal salts or organic mono- and/or dicarboxylic acids (Aiii), wherein the carboxylic acid efficaciously exhibits pKa values of about 1.1 to 6.8, preferably from 2 to 6.8. The salts of the above-mentioned metals, preferably alkali metal Qalts, including sodium and potassium salts, as well a~ alkali earth metal salts such as calcium and magne~ium salt~ and especially zinc salts can be used.
The internal mold release agent contains as an essential structural component a mono- and/or dicarboxylic acid or their anhydrides (~). Examples include aliphatic monocarboxylic acids having from 1 to 20 carbon atoms, preferably 5 to 18 carbon atoms, aliphatic dicarboxylic acids having from 2 to 36 carbon atoms, preferably 2 to 12 carbon atoms aromatic mono- and/or dicarboxylic acids having from 7 to 12 carbon atoms, preferably 7 to 10 carbon atoms, which possibly can contain olefinic unsaturated unit~; and/or radicals reactive with isocyanate groups, such as, hydroxyl amino or alkyl amino groups. In place of the mono- and/or dicarboxylic acid or in mixtures with these, the corresponding carboxylic acid anyhdrides can also be used. Examples of aliphatic monocarboxylic acids are:
formic acid, acetic acid, propionic acid, isovaleric acid, caproic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, ricinoleic acid, arachidic acid, hydroxy stearic acid, isostearic acid, and oleic acid. Aliphatic dicarboxylic acids include oxalic acid, ~uccinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, undecanoic acid, dodecanoic acid, dimerized and trimerized fatty acids, maleic acid, fumaric acid, and aromatic mono- and/or dicarboxylic acidq, such as benzoic acid, toluic acids, hydroxy benzoic acids, aminobenzoic acids, phthalic acid, i30phthalic acid, and terephthalic acid. The following mono-, dicarboxylic acids, and carboxylic acid anhydrides are preferentially u~ed, oxalic acid, stearic acid, adipic acid, benzoic acid, and benzoic acid anhydride. The mono-, dicarboyxlic acids and their anhydrides can be used alone or in the form of mixtures.

lZ7~;75Z

In preparing the internal mold release agent the ~tructural components (Ai), (Aii), and (Aiii) and (~) can be mixed at the same time or one after another, efficaciously by stirring at temperatures from 20 to 130C, preferably from 40 to 100C. The resulting products are storage stable for up to two months. Another method, which has prefer-ential use, i~ blending the qtructural components at the ~ame time or one after another into the raw materials for production of polyurethane-polyurea molded articleA. For example, blending of component (A) at temperatures from 20 to 90C.
Catalvst CatalyAt component (f) which i8 especially useful to accelerate the reaction of the hydroxyl group-containing compound of component (b) and component (d) with polyisocya-nate (a), include organic metal compounds, preferably organic tin compounds, such as tin (II) salts of organic carboxylic acids, such as tin (II) acetate, tin (II) octoate, tin (II) ethylhexoate, and tin (II) laurate and the dialkyl tin (IV) ~alts of organic carboxylic acids, for example, dibutyl tin diacetate, dibutyl tin dilaurate, dibutyl tin maleate, and dioctyl tin diacetate. The organic metal compounds are used alone or preferably in combination with strong basic amines. Example~ are: 2,3-dimethyl-3,4,5,6-tetrahydropyrimidine, tertiary amines, ~uch as, triethylamine, tributylamine, dimethylbenzylamine, N-methyl-, N-ethyl-, N-cyclohexylmorpholine, N,N,N',N'-tetramethyl-ethylenediamine, N,N,N',N'-tetramethyl-butane-diamine, pentamethyl-diethylenetriamine, tetramethyl-diaminoethylether, bis-(dimethylaminopropyl)-urea, dimethyl-piperazine, 1,2-dimethylimidazol, 1-azo-bicyclo-(3,3,0)-octane and preferably 1,4-diazo-bicyclo-(2,2,2)-octane and alkanol compounds such as triethanolamine, triisopropanol-amine, N-methyl- and N-ethyl-diethanolamine and dimethyl-ethanolamine.
Addltional catalysts are: tris-(dialkyl-amino-alkyl)-s-hexahydrotriazine, especially tris-(N,N-dimethyl--aminopropyl)-s-hexahydrotriazine, tetraalkyl-ammonium hydroxide, such as tetramethyl-ammonium hydroxide, alkali hydroxide~, sodium hydroxide, and alkali alcoholate, such as sodium methylate and potassium propylate, as well a~, alkali salts of long chained fatty acid~ having from 10 to 20 carbon atoms and possibly side-chain OH groups. Preferably used are catalyst or catalyst combinations from 0.001 to 5 percent by weight, especially 0.05 to 2 percent by weight, depending on the weight of the component (b).
Blowinq Aqent~
Blowing agent (g) used in the process includes water, which react~ with the isocyanate groups forming carbon dioxide. The amount of water, which can be effica-ciou~ly used, i~ 0.5 to 2 percent by weight, based on theweight of component (b).
Other usable blowing agents are low boiling liquids which evaporate under the influence of the exo-thermic addition polymerization reaction. Suitable liquids are those which are inert to the organic polyisocyanates and have boiling points under 100C. Examples are halogenated hydrocarbonQ, such as, methylene chloride, trichlorofluoro-methane, dichlorodifluoromethane, dichloromonofluoromethane, dichlorotetrafluoroethane and 1,1,2-trichloro-2,2,2-tri-fluoroethane. Mixtures of these low boiling liquids can also be used together and/or with other substituted or un~ubstituted hydrocarbons.
The appropriate quantity of a low boiling liquid for the production of cellular polyurethane-polyurea molded articles depends on the desired density, as well as, the use of water in the reaction. Generally satisfactory results are obtained using quantities of from 0.5 to 15 parts by weight based on 100 parts by weight of component (b).
AuxiliarieQ and/or Additives The reaction mixture can also contain auxiliaries and/or additiveq (h). Examples are surface acting sub-stances, foam stabilizers, cell regulators, fillers, colorants, pigments, flame retardants, hydrolysis preventing agents, fungicide and bacteriological active substances.

Surface active substances include compounds which serve to support the homogenization of the raw materials and are also suited to regulate the cell structure. Examples are: emulsifiers, such as, sodium salts of castor oil sulfate or of fatty acids, such as, salts of fatty acids having amines, such as, a diethylamine salt of oleic acid, a diethanolamine salt of stearic acid, a diethanolamine salt of ricinoleic acid, salt of sulfonic acids, such as, alkali or ammonium salts of dodecylbenzyl- or dinaphthylmethane-disulfonic acid and ricinoleic acids. Examples of foam stabilizer~ include siloxane-oxyalkylene mixed polymers, organopolysiloxanes, oxyethylated-alkylphenols, oxyethylated fatty alcohols, paraffinic acid, castor oil or ricinic acid ester and Turkey red oil and cell regulators such as paraffins, fatty alcohols and dimethylpolysiloxanes. The surface active ~ubstances are normally used in quantities of 0.01 to 5 part~ by weight based on 100 parts by weight of component (b).
Fillers, especially strength effective fillers, include organic and inorganic fillers, strengthening agents, weighting material, substances improving the abraqion behavior in paint, and coating agents. In particular, the following are examples: inorganic fillers such as silicate minerals, stratified silicates such as antigorite, serpen-tine, hornblend, amphibole, crystallite, talcum, as well as, metal oxides such as kaolin, aluminum oxides, titanium oxides and iron oxides, metal salts, such as, chalk, baryte and inorganic pigments, such as, cadmium sulfide, zinc sulfide glass and powdered asbestos. Preferentially used are kaolin (China clay), aluminum silicate and co-precipi-tates from barium sulfate and aluminum silicate as well as natural and synthetic fiber formed minerals ~uch as asbestos, wollastonite and especially glass fibers of different lengths, which possibly can be smoothed. Examples of organic fillers include: carbon, melamine, rosin, cyclopentadieno resins and graft polymers based on styrene, and acrylnitrile, which are produced in ~itu by the polymer-ization of acrylnitrile-styrene mixtures in polyethers, as described in U.S. 3,304,273, 3,383,351, 3,523,093, (German Patents 11 11 394, 12 22 669), German Patent~ 11 52 536 (GB 1,040,452) and 11 52 537 tGB 987,618), and ~ubsequently which may be aminated. Also used as fillers are aqueous polymer dispersions, such as, polyoxyalkylene polyol or polyamine dispersions. Preferentially used are polyoxy-alkylene-polyol dispersions with a higher energy density and a particle size of less than 7 ~m.
The inorganic and organic fillers are used in the reaction mixture in quantities from 0.5 to 50 percent by weight, preferably 1 to 40 percent by weight based on the weight of components (a), (b), and (c). The inorganic and organic fillers may be used alone or as mixtures.

1276752`

To improve the flame resi~tance of the moldedarticle, flame retardant~ are added to the formulation.
Suitable flame retardants are: tricre~ylpho~phate, tris-2-chloroethylpho~phate, tris-chloropropylpho~phate and tri-q-2,3-dibromopropylphosphate. Inorganic flame retardant agents can be used, such as, aluminum oxyhydrate, antimony trioxide, arsenic oxide, ammonium polyphosphate and calcium sulfate. Generally, 5 to 50 parts by weight, preferably 5 to 25 parts by weight of a flame retardant agent for each 100 parts by weight of component (b) is ~ufficient.
The technical literature, for example, J.H.
Saunders and K.C. Frisch "High Polymer~" vol. XVI, Poly-urethanes, parts 1 and 2, Inter~cience Publi~her~ 1962 or 1964, can provide examples of other type~ of auxiliary and additive~.
Process of the Invention To produce cellular and preferably noncellular polyurethane-polyurea molded article~ the one-shot RIM
prOCe4~ i9 preferred. Thi~ method is described by Piechota and ~ohr in "Integralschaum~toff, n Carl-Hanser-Verlag, Munchen, Wien 1975: D. J. Prepelka and J. L. Wharton in the Journal of Cellular Plaqtics, March/April 1975, pages 87 to 98 and U. Knipp by in the Journal of Cellular Plasticq, March/April 1973, pages 76 to 84.

In the production of polyurethane-polyurea molded articles, the components (a), (b), (c), and optionally (d), are reacted in quantities 90 that the equivalent ratio of NCO groups of the polyisocyanate (a) to the sum of the reactive hydrogen atoms of components (b), (c), and option-ally (d), is 1:0.85 to 1:1.25, preferably 1:0.95 to 1:1.15.
If a mixing chamber containing several inlet nozzles is used, the raw material components can be injected singly and then mixed in the mixing chamber. Preferably used is a two-component process wherein the primary aromatic diamine (c) and chain extending agents and/or crosslinkers (d) are dissolved in the higher molecular weight compound having at least two reactive hydrogen components (b).
Optionally, component (A) comprising blowing agents, auxiliary and additive agents can be blended with component (B) comprising an organic polyisocyanate, a modified polyisocyanate, and/or an NCO prepolymer. In this process, components (A) and (B) can be stored and tran~ported separately. This is advantageous in saving time and space, as well a~, in the process itself.
Density specifications for the noncellular molded article and the cellular molded article are from 1.0 to 1.4 g~cm , preferably from 1.0 to 1.2 g/cm and from 0.2 to 1.2 g/cm , preferably from 0.8 to 1.0 g/cm , respec-tively. The rate of compre~sion to obtain molded articles with the above-specified dengity is 1.1 to 8, preferably 2 to 8. The raw material components have a temperature of 15 to 80C, preferably 40 to 55C as they enter the mixing chamber. The temperature of the mold itself is 20 to 100C, preferably 30 to 80C.
The polyurethane, polyurea molded articles obtained according to the process are usable in the automo-tive indu~try, especially as bumper covers, crash protection articles, and vehicle body parts such a~ window frames, fenders, spoilers, and window box expanders, as well as, technical case parts, rollers, and shoe soles. Cellular molded articles are usable as armrests, headre~ts, seats for motorcycles and bicycles and as skin in overlay foam materials.
Examples The following examples illustrate the subject invention. The portions of the components in the examples are ba~ed on parts by weight unless stated otherwise.
Starting components (c), (d), (b) and optionally blowing agent (a) auxiliaries and additives (h) are combined in component (A). Starting materials (a), and modified polyisocyanate and/or NC0 prepolymers are combined in component (B).

1276i752 Example 1 Component A: Mixtures of 73.3 parts by weight of a triol composed of 80 percent parts by weight polyoxypropylene, 20 percent parts by weight polyoxyethylene, with a hydroxyl number of 26, produced by the addition polymerization of 1,2-propylene oxide and trimethylolpropane followed by polyaddition of ethylene oxide, 21.0 parts by weight 1-methyl-3,5-diethyl-2,4-diamino-benzene, 0.33 parts by weight dibutyltin dilaurate, 5.0 parts by weight of a fatty acid ester, produced by eqterification of 15.4 moleq of montanic acid, 292.5 molex talloleic acid and 102.6 moles triisopropanol amine, 3.144 parts by weight of a solution comprising 1.5 parts by weight n-butylamine, 1.5 part~ by weight zinc stearate, 0.072 parts by weight calcium stearate, 0.072 parts by weight sodium Qtearate, 0.036 parts by weight zinc oxalate, 0.21 parts by weight benzoic acid anhydride.

~276752 Component B:
partq by weight of a mixture of 4,4'-diphenylmethane diisocyanate with polyoxypropylene qlycol, containing carbodiimide groups, with an NC0 content of 26.5 percent by weight.
Component~ (A) and (B) are heated to 50C and then injected by a high pressure proportioning machine, for example, Elastogran'~ model Puromat~ 30 into an aluminum mold of the desired shape with an inner dimension from about 2 x 1000 x lO mm, and heated to 60 to 70C.
Before beginning of production, each mold was treated with an external release wax, for example, Fluoricon 36/134/2 from Acmos. The shot time was about 1 second and the mold time was 45 seconds.
Up to 40 molded articles were removed from the mold without an adhesion/sticking problem or distortion of the article.
The molded articles exhibited the following mechanical properties:
Density per DIN 53 420 (g/cm ) 1.1 Shore D Hardness per DIN 53 505 53 Tensile Strength per DIN 53 504 (N/mm ) 25 Elongation per DIN 53 504 (~) 330 lZ76752 Tear Strength per DIN 53 507 (N/mm) 29.5 Example 2 Component A:
73.3 parts by weight of a triol composed of 80 percent partR by weight polyoxypropylene, 20 percent parts by weight polyoxyethylene with a hydroxyl number of 26.0 produced by the addition polymerization of 1,2-propylene oxide with trimethylpropane followed by polyaddition of ethylene oxide, 21.0 part~ by weight 1,3-dimethyl-5-tert-butyl-2,4-diaminobenzene, 0.33 part~ by weight 1,4-diazabicyclo-2,2,2-octane, 0.3 parts by weight dibutyltin dilaurate, 5.0 part~ by weight of a fatty acid ester, produced by esterification of 15.4 moles montanic acid, 292.5 moles talloleic acid and 102.6 moles triisopropanol amine, 3.114 parts by weight of a solution comprising:
1.5 parts by weight of an amine mixture comprising:
57 parts by weight N-2-aminoethyethanolamine and 43 parts by weight N-butylamine, 1.5 part-~ by weight zinc ~tearate, 0.072 parts by weight calcium stearate, 0.072 parts by weight sodium stearate, ~Z7675Z

0.036 parts by weight zinc oxalate 0.11 parts by weight benzoic acid.
Component B:
45 parts by weight of a mixture of 4,4'-diphenylmethane diisocyanate with polyoxypropylene glycol, containing carbodiimide groups, with an NC0 content of 26.5 percent by weight.
Components (A) and (B) are heated to 50C and then injected by a high pressure proportioning machine, for example, Elastogran's model Puromat~ 30 into an aluminum mold of the desired Rhape with an inner dimension from about 2 x 1000 x 10 mm, and heated to 60 to 70C.
Before beginning of production, each mold was treated with an external release agent, for example, Fluoricon 36/134/2 from Acmos. The shot time was about 1 second and the mold time is 45 seconds.
The process was terminated after 40 molded articles were removed from the mold without any distortions or adhesion problems.
The molded articles exhibited the following mechanical properties:
Density per to DIN 53 420 (g/cm ) 1.1 Shore D Hardness per to DIN 53 505 52 Tensile Strength per to DIN 53 504 (N/mm ) 25.5 ~276752 Elongation per DIN 53 504 (%) 340 Tear Strength per DIN 53 507 (N/mm) 28.7 Example 3 Component A:
73.3 parts by weight of a triol composed of 80 percent parts by weight polyoxypropylene, 20 percent parts by weight polyoxyethylene with a hydroxyl number of 26.0 produced by addition polymerization of l,2-propylene oxide with trimethylol propane followed by polyaddition of ethylene oxide, 21.0 parts by weight 1,3-dimethyl-5-tert-butyl-2,4-diaminobenzene, 0.33 part~ by weight 1,4-diazabicyclo-2,2,2-octane, 0.3 parts by weight dibutyltin dilaurate, 5.0 parts by weight of a fatty acid ester, produced by esterification of 15.4 moles montanic acid, 292.5 moles talloleic acid and 102.6 moles triisopropanol amine, 3.114 parts by weight of a solution comprising:
1.5 parts by weight of an amine mixture comprising, 28.2 percent by weight 1-(2-aminoethyl-)piper-azine 127f~752 12.3 percent by weight 1-(2-hydroxyethyl)-piperazine, 54.8 percent by weight N-2-aminoethylethanol-amine, 3.6 percent by weight diethylenetriamine and 1.1 percent by weight N,N'-bis(3-aminopropyl)-ethylenediamine 1.5 parts by weight zinc stearate, 0.072 parts by weight calcium stearate, 0.072 parts by weight sodium stearate, 0.036 parts by weight zinc oxalate, 0.11 parts by weight benzoic acid.

Component B:
parts by weight of a mixture of 4,4'-diphenylmethane diisocyanate with polyoxypropylene glycol, containing carbodiimide groups, with an NC0 content of 26.5 percent by weight.
Components (A) and (B) are heated to 50C and then injected by a high pressure proportioning machine, for example, Elastogran's model Puromat~ 30 into an aluminum mold of the desired shape with an inner dimension from about 2 x 1000 x 10 mm and heated to 60 to 70C.
Before beginning of production, each mold was treated with an external release agent, for example, lZ76752 Fluoricon 36/134/2 from Acmos. The shot time was about 1 second and the mold time was 45 seconds.
The process was terminated after 40 molded articles were removed from the mold without distortion or adhesion problems.
The following mechanical properties were measured on the molded article produced:
Density per DIN 53 420 (g/cm ) 1.1 Shore D Hardness per DIN 53 505 53 Tensile Strength per DIN 53 504 (N/mm ) 26 Elongation per DIN 53 504 (~) 330 Tear Strength per DIN 53 507 (N/mm) 29 Comparison Example 1 This example was carried out in exactly the same manner as Example 1. However, in the formulation component A lacked benzoic anhydride, as in Example 1, and lacked benzoic acid, as in Example 2. The formulation utilized was as follows:
Component A:
73.3 parts by weight of a triol compo~ed of 80 percent parts by weight polyoxypropylene, 20 percent part~ by weight polyoxyethylene with a hydroxyl number of 26.0, produced by polymerization of 1,2-propylene oxide with trimethylolpropane followed by poly-addition of ethylene oxide, 21.0 part~ by weight 1-methyl-3,5-diethyl-2,4-diamino-benzene, 0.33 partq by weight 1,4-diazabicyclo-(2.2.2)-octane 0.3 parts by weight dibutyltin dilaurate and 5.0 partq by weight of a fatty acid ester, produced by esterification of 15.4 moles montanic acid, 292.5 moleq talloleic acid, and 102.6 moleR triisopropanol amine.
Component B:
45 parts by we$ght of a mixture of 4,4'-diphenylmethane diisocyanate with polyoxypropylene glycol, containing carbodiimide groupq, with an NC0 content of 26.5 percent by weight.
Components (A) and (B) are heated to 50C and then injected by a high pre~sure proportioning machine, for example, Elantogran'~ model Puromat~ 30 into an aluminum mold of the desired ~hape with an inner dimenRion from about 2 x 1000 x 10 mm, and heated to 60 to 70C.
Before beginning of production, each mold waq treated with an external releaqe agent, for example, Fluoricon 36/134/2 from Acmoq. The ~hot time wa~ about 1 second and the mold time wa~ 45 ~econd~.

lZ7~;752 After 10 demoldings, the molded article could not be removed from the mold without distortion. The produced molded article possessed the following mechanical proper-ties:
Density per DIN 53 420 (g/cm3) 1.1 Shore D Hardness per DIN 53 505 53 Tensile Strength per DIN 53 504 (N/mm ) 25 Elongation per DIN 53 504 (%) 330 Tear Strength per DIN 53 507 (N/mm) 29.5 As is illustrated in Examples 1, 2, and 3 andComparison Example 1, the addition of benzoic acid or benzoic anhydride greatly affected the efficiency of the internal mold release agent. Without the carboxylic acid and/or its anhydride, demolding problems were evident after only ten moldings. With the dicarboxylic acid and/or its anhydride, no demolding problems were apparent until greater than 40 moldings occurred.
Example 4 Components A:
73.3 parts by weight of a triol composed of 80 percent parts by weight polyoxypropylene, 20 percent parts by weight polyoxyethylene with a hydroxyl number of ~27~i752 26.0, produced by polymerization of 1,2-propylene oxide with trimethylolpropane followed by poly-addition of ethylene oxide, 21.0 parts by weight 1-methyl-3,5-diethyl-2,4-diamino-benzene, 0.33 part~ by weight 1,4-diazabicyclo-(2.2.2)-octane 0.3 parts by weight dibutyltin dilaurate and 5.0 parts by weight of a fatty acid ester, produced by esterification of 15.4 moles montanic acid, 292.5 moles talloleic acid, and 102.6 mole~ triisopropanol amine.
3.12 part~ by weight of a solution comprising 50 parts by weight of a polyoxypropylene triamine (JeffamineO
T 403 from the Texaco Company) and 50 parts by weight zinc stearate which is warmed to 80 to 100C, 0.43 parts by weight benzoic acid.

Component B:
45 part~ by weight of a mixture of 4,4'-diphenylmethane diisocyanate with polyoxypropylene glycol, containing carbodiimide groups, with an NC0 content of 26.5 percent by weight.
Components (A) and (B) are heated to 50C and then injected by a high pressure proportioning machine, for example, Elastogran's model Puromat~ 30 into an aluminum mold of the 1~7~;752 desired shape with an inner dimension from about 2 x 1000 x 10 mm, and heated to 60 to 70C.
Before beginning of production, each mold was treated with an external release agent, for example, Fluoricon 36/134/2 from Acmos. The shot time was about 1 second and the mold time was 45 ~econdc.
After 18 demoldings, a slight distortion in the molded articles occurred.
The molded article~ exhibited the following mechanical propertie~:
Den~ity per DIN 53 420 (g/cm ) 1.07 Shore D Hardness per DIN 53 505 53 Ten~ile Strength per DIN 53 504 (N/mm ) 25.8 Elongation per DIN 53 504 (%) 285 Tear Strength per DIN 53 507 (N/mm) 27 Comparison Example 2 The formulation used in this example was exactly the same a~ that used in Example 4 except without the use of benzoic acid. The processes are otherwise identical.
After 12 demolding~ the molded article could not be removed without distortion. The molded articles ex-hibited the following mechanical properties:
Density per DIN 53 420 (g/cm ) 1.08 Shore D Hardne~s per DIN 53 505 52 Tensile Strength per to DIN 53 504 (N/mm ) 26.5 Elongation per DIN 53 504 (%) 315 Tear Strength per DIN 53 507 (N/mm) 27 This example illustrates the effect that the addition of benzoic acid in the internal mold release formulation has on demolding properties. Without benzoic acid in the formulation, demolding problem~ are evident, offer a relatively short amount of moldings (12). With the addition of benzoic acid, over three times as many de-moldings occur before any distortion in the molded article.
Example 5 Component A:
73.3 part~ by weight of a triol having 80 percent by weight polyoxypropylene, 20 percent by weight polyoxyethylene having a hydroxyl number of 26.0, produced by the addition polymerization of 1.2-propylene oxide with trimethylolpropane followed by polyaddition of ethylene oxide, 21.0 parts by weight 1-methyl-3,5-diethyl-2,4-diamino-benzene, 0.33 part~ by weight diazabicyclo-(2.2.2)-octane 1;~7~752 0.3 part~ by weight dibutyltin dilaurate 5.0 parts by weight of a fatty acid ester, produced by e~terification of 15.4 moles montanic acid, 292.5 moles talloleic acid, and 102.6 moles triisopropanol amine, 3.12 part~ by weight of a solution compri~ing 50 parts by weight of a polyoxypropylene triamine (JeffamineO T
403 from the Texaco Company) and 50 part~ by weight zinc stearate warmed to 80 to 100C, 0.072 partY by weight sodium stearate, 0.072 parts by weight calcium stearate, and 0.43 parts by weight benzoic acid.

Component B:
parts by weight of a mixture of 4,4'-diphenylmethane diisocyanate with polyoxypropylene glycol, containing carbodiimide groups, with an NC0 content of 26.5 percent by weight.
Components (A) and (B) are heated to 50C and then injected by a high pressure proportioning machine, for example, Elastogran's model Puromat 30 into an aluminum mold of the desired shape with an inner dimension from about 2 x 1000 x 10 mm, and heated to 60 to 70C.
Before beginning of production, each mold was treated with an external release agent, for example, ~276752 Fluoricon 36/134/2 from Acmo~. The shot time was about 1 second and the mold time was 45 seconds.
The process was terminated after 40 molded articles were removed from the mold without any distortions or adhesion problems.
The molded articles exhibited the following mechanical properties:

Density per DIN 53 420 (g/cm ) 1.1 Shore D Hardne~s per DIN 53 505 54 Tensile Strength per DIN 53 504 (N/mm ) 26.2 Elongation per DIN 53 504 (%) 310 Tear Strength per DIN 53 507 (N/mm) 28 Example 6 Components A:
73.3 parts by weight of a triol composed of 80 percent parts by weight polyoxypropylene, 20 percent part~ by weight polyoxyethylene having a hydroxyl number of 26.0, produced through the addition polymerization of 1,2-propylene oxide on trimethylolpropane and subse-quently addition polymerization of ethylene oxide on the resulting trimethylolpropane polyoxypropylene adduct, ~.Z7~i752 21.0 parts by weight 1-methyl-3,5-diethyl-2,4-diamino-benzene, 0.33 parts by weight diazabicyclo-~2.2.2)-octane 0.3 parts by weight dibutyltin dilaurate and S.0 part~ by weight of a fatty acid ester, produced through esterification of 15.4 moles montanic acid, 292.5 moles talloleic acid, and 102.6 moles triisopropanol amine, 3.12 parts by weight of a solution produced through the warming of the component~ to 80-100C, con~isting of 50 part~ by weight of a polyoxypropylene triamine (Jeffamine~ T 403 from the Texaco Company) and 50 parts by weight zinc stearate, 0.072 parts by weight sodium ~tearate, 0.072 parts by weight calcium stearate, 0.036 part~ by weight zinc oxalate, and 0.96 parts by weight ~tearic acid.

Components B:
45 part~ by weight of a mixture of 4,4'-diphenylmethane diisocyanate with polyoxypropylene glycol, containing carbodiimide groups, with an NC0 content of 26.5 percent by weight~
Component~ (A) and (B) are heated to 50C and then injected by a high pressure proportioning machine, for example, 127~i752 Elastogran's model Puromat~ 30 into an aluminum mold of the desired shape with an inner dimension from about 2 x 1000 x 10 mm and heated to 60 to 70C.
~ efore beginning of production, each mold was treated with an external release agent, for example, Fluoricon 36/134/2 from Acmos. The shot time was about 1 second and the mold time was 45 seconds.
The process was terminated after 40 molded articles were removed from the mold without any distortions or adhesion problems.
The molded articles exhibited the following mechanical properties:
Density according to DIN 53 420(g/cm ) 1.12 Shore D Hardne~s per DIN 53 505 53 Tensile Strength per DIN 53 504 (N/mm ) 25 Elongation per DIN 53 504 (%) 320 Tear Strength per DIN 53 507 (N/mm) 25 Example 7 Component A:
73.3 parts by weight of a triol composed of 80 percent parts by weight polyoxyproylene, 20 percent parts by weight polyoxyethylene with a hydroxyl number of 26.0 produced by addition polymerization of l,2-propylene ~Z76752 oxide with trimethylolpropane followed by poly-addition of ethylene oxide, 21.0 parts by weight 1-methyl-3,5-diethyl-2,4-diamino-benzene, 0.33 parts by weight diazabicyclo-(2.2.2)-octane 0.3 parts by weight dibutyltin dilaurate and 5.0 part~ by weight of a fatty acid ester, produced through esterification of 15.4 moles montanic acid, 292.5 moles talloleic acid, and 102.6 mole~
triisopropanol amine, 3.12 partq by weight of a solution produced through the warming of the component~ to 80-100C, con~isting of 50 part~ by weight of a polyoxypropylene triamine (JeffamineO T 403 from the Texaco Company) and 50 parts by weight zinc stearate, 0.072 parts by weight sodium stearate, 0.072 parts by weight calcium stearate, 0.036 parts by weight zinc oxalate, and 0.309 parts by weight benzoic anhydride.
Component B:
parts by weight of a mixture of 4,4'-diphenylmethane diisocyanate with polyoxypropylene glycol, containing carbodiimide groups, with an NC0 content of 26.5 percent by weight.

lZ7675Z

Components (A) and (B) are heated to 50C and then injected by a high pressure proportioning machine, for example, Elastogran's model Puromat0 30 into an aluminum mold of the desired shape with an inner dimension from about 2 x 1000 x 10 mm and heated to 60 to 70C.
Before beginning of production, each mold was treated with an external releaqe agent, for example, Fluoricon 36/134/2 from Acmos. The shot time was about 1 second and the mold time was 45 seconds.
The process was terminated after 40 molded articles were removed from the mold without any di~tortions or adhesion problem~.
The molded articles exhibited the following mechanical properties:
Density according to DIN 53 420 (g/cm ) 1.13 Shore D Hardness according to DIN 53 505 55 TenQile Strength according to DIN 53 504 (N/mm ) 27.3 Elongation according to DIN 53 504 (%) 318 ~ear Strength according to DIN 53 507 (N/mm) 31.0 ~276752 In Example~ 8, 9, and 10 specific internal mold relea~e agent formulations are utilized. The following discloses the preparation of the~e internal mold release agents.
Internal Mold Release Aaent I
Preparation of this internal mold release agent i9 as follows:
421.35 parts by weight tridecylamine, 421.35 parts by weight zinc stearate, 28.09 parts by weight sodium ~tearate, 28.09 parts by weight calcium stearate, and 56.18 parts by weight benzoic acid anhydride.
The constituents are dissolved in a 2-liter, three-neck flask by stirring at 60C for 1.5 hours.
Following cooling to 30C, a yellow brown storage stable suspension resulted.

Internal Mold Release Agent II
Preparation of this internal mold release agent is as follows:
421.35 parts by weight of an amine mixture consisting of 28.2 percent by weight 1-(2-aminoethyl)-piperazine, 12.3 percent by weight 1-(2-hydroxyethyl)-piper-azine, 54.8 percent by weight N-2-aminoethylethanolamine, lZ7675~

3.6 percent by weight diethylenetriamine and 1.1 percent by weight N,N'-bis-(3-aminoropyl)-ethylenediamine 421.35 partq by weight zinc ~tearate, 28.09 parts by weight sodium stearate, 28.09 part~ by weight calcium ~tearate, 44.94 parts by weight zinc oxalate, and 56.18 part~ by weight benzoic acid anhydride.

The con~tituents are di~olved in a 2-liter three-neck fla~k by ~tirring at 60C for 1.5 hour~. Following cooling to 30C, a yellow-brown ~torage stable ~u~pen~ion resulted.
Internal Mold ReleaQe Agent III
Preparation of thi~ internal mold relea~e agent i~
aq follow~:
459.41 parts by weight of an amine mixture con~i~ting of 48.89 percent by weight N-2-aminoethyl-ethanolamine 11.13 percent by weight 1-(2-hydroxyethyl)-piper-azine, 20.04 percent by weight 1-(2-aminoethyl)-piperazine, 5.01 percent by weight dipropylenetriamine and 14.93 percent by weight n-butylamine, The constituents were added to a 2-liter three-neck flask, which was fitted with a stirrer and reflux condenser at room temperature. 278.78 partq by weight oleic acid was charged into the flask. Sub~equently, the mixture was stirred for one hour at 100C. The mixture was then cooled to room temperature and blended with the following:
723.97 parts by weight zinc stearate, 26.03 partq by weight sodium stearate, and 26.03 parts by weight calcium stearate.
The mixture wa~ stirred until the formation of a clear solution at 100C, about 1.5 hours.

Internal Mold Release Agent IV
Preparation of this internal mold release agent is as follows:
459.19 part~ by weight 1-(2-hydroxyethyl)-piperazine 264.78 parts by weight oleic acid.

The constituents were added to a 2 liter three-neck flask while stirring at room temperature. The mixture was qtirred subsequently one hour at 100C. The mixture was allowed to cool to 60C and the following were added proportionately while stirring:
723.97 parts by weight zinc stearate 26.03 parts by weight calcium stearate.

Following the last addition, the mixture was stirred for about 2 hours until a completely clear solution resulted.
Example 8 Component A:
74.78 parts by weight of a triol composed of 80 percent parts by weight polyoxypropylene, 20 percent parts by weight polyoxyethylene havinq a hydroxyl number of 26.0, produced through the addition polymeriza-tion of 1,2-propylene oxide, trimethylolpropane, and subsequently addition polymerization of ethylene oxide on the resulting trimethylolpropane-polyoxy-propylene adduct, 20.0 parts by weight 1-methyl-3,5-diethyl-2,4-diamino-benzene, 1.0 part by weight 1,4-diazabicyclo-(2,2,2)-octane, (33 percent by weight solution in dipropylene glycol) 0.22 part by weight dibutyltin dilaurate, and 4.0 parts by weight of Internal Mold Relea3e Agent III.

20 Component B:
parts by weight of a mixture of modified 4,4'-diphenylmethane diisocyanate and polyoxypropylene glycol having an NC0 content of 23 percent by weight.

lZ7f~752 The process was terminated after 100 molded articles were removed from the mold without any distortion or adhesion problems.
The molded articles exhibited the following mechanical propertie~:
Density per DIN 53 420 (g/cm3) 1.1 Shore D Hardness per DIN 53 505 52 Tensile Strength per DIN 53 504 (N/mm ) 25.5 Elongation according to DIN 53 504 (%) 330 Tear Strength according to DIN 53 507 (N~mm) 29.0 Example 9 Component A:
74.78 part~ by weight of a triol composed of 80 percent part~ by weight polyoxypropylene, 20 percent parts by weight polyoxyethylene havins a hydroxyl number of 26.0, produced through the addition polymeriza-tion of l,2-propylene oxide, trimethylolpropane, and subsequently addition polymerization of ethylene oxide on the resulting trimethylolpropane-polyoxy-propylene adduct, ~Z7f~752 20.0 parts by weight 1-methyl-3,5-diethyl-2,4-diamino-benzene, 1.0 part by weight 1,4-diazabicyclo-(2,2,2)-octane, (33 percent by weight solution in dipropylene glycol) 0.22 part by weight dibutyltin dilaurate, and 4.0 parts by weight of Internal Mold Release Agent IV.

Component B:
parts by weight of a mixture of modified 4,4-diphenylmethane diisocyanate and polyoxypropylene glycol having an NC0 content of 23 percent by weight.

The process terminated after 40 molded articles were removed from the mold without any distortion or adhesion problems. The molded articles exhibit the fol-lowing mechanical properties:

Density per DIN 53 420 (g/cm ) 1.1 Shore D Hardness per DIN 53 505 52 Tensile Strength per DIN 53 504 (N/mm ) 26 Elongation per DIN 53 504 (~) 320 Tear Strength per DIN 53 507 (N/mm) 29.0

Claims

1. A process for the preparation of cellular or noncellular polyurethane-polyurea molded articles having improved demolding properties comprising reacting a) an organic polyisocyanate, b) a higher molecular weight compound having at least two reactive hydrogen atoms, c) an aromatic diamine, d) optionally, a chain extender and/or crosslinker, and e) an internal mold release agent, in the presence of f) a catalyst, and, optionally, g) a blowing agent, h) auxiliaries and/or additives by reaction injection molding technique in a closed mold, wherein the internal mold release agent (e) comprises A) 0.1 to 10 percent by weight based on the entire weight of the structural components (b), (c), (d), of a mixture comprising i) 5 to 80 parts by weight of at least one organic amine and/or cyclic lactam, ii) 20 to 95 parts by weight of at least one metal salt of stearic and/or isostearic acid, and iii) 0 to 5 parts by weight of at least one metal salt of an organic mono- and/or dicarboxylic acid, and B) 0.01 to 2 percent by weight based on the total weight of the components (b), (c), (d), of one organic mono-and/or dicarboxylic acid or their anhydride.

2. An internal mold release agent for the preparation of molded articles according to the poly-isocyanate addition polymerization process comprising:
A) a mixture comprising:
i) 5 to 80 parts by weight of one organic amine and/or cyclic lactam, ii) 20 to 95 parts by weight of one metal salt of stearic and/or isostearic acid, and iii) 0 to 5 parts by weight of a metal salt of an organic mono- and/or dicarboxylic acid, and B) 0.1 to 20 percent by weight, based on the total weight of mixture (A) of one organic mono- and/or dicarboxylic acid or their anhydride.

3. The internal release agent of claim 2 wherein said organic amine (Ai) is selected from the group com-prising primary aliphatic and/or cycloaliphatic monoamines having from 3 to 20 carbon atoms a linear, branched, cyclic and/or heterocyclic alkanolamine having from 2 to 12 carbon atoms, an aliphatic or cycloaliphatic primary diamine having from 2 to 20 carbon atoms an aliphatic or cycloaliphatic primary mono- and/or polyamine, which contains secondary and/or tertiary amino groups and/or heterocyclic radicals and/or hydroxyl groups and/or ether groups, and a polyoxy-alkylene polyamine having molecular weights from 204 to 5000.

4. The internal mold release agent of claim 2 wherein said metal salts (Aii), (Aiii) are selected from the group comprising zinc, earth alkali salts and alkali metal salts.

5. The internal mold release agent of claim 2 wherein said metal salts (Aii), (Aiii) are selected from the group comprising zinc, calcium, magnesium, potassium, and sodium salts.

6. The internal mold release agent of claim 2 wherein said metal salt (Aii), (Aiii) are selected from the group comprising zinc stearate, zinc isostearate, calcium stearate, or sodium stearate and mixtures of at least two of said stearates.

7. The internal mold release agent of claim 2 wherein the metal salts are a mixture of zinc, calcium and sodium stearate.

8. The internal mold release agent of claim 2 wherein said metal salts (Aii) are prepared from organic mono and/or dicarboxylic acids with pKa values of from 1.1 to 6.8.

9. The internal mold release agent of claim 2 wherein said mono- and/or dicarboxylic acids or their anhydrides (B) are selected from the group comprising aliphatic monocarboxylic acids having from 1 to 20 carbon atoms, aliphatic dicarboxylic acids having from 2 to 36 carbon atoms, aromatic mono and dicarboxylic acids having from 7 to 12 carbon atoms and their anhydrides.

10. A cellular or noncellular polyurethane polyurea molded article obtained by the process of claim 1.