CA1218190A - Process for the preparation of polyurethane-polyurea molded parts and alkyl-substituted phenylenediamines used therefor - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE:

The subject invention relates to a process for preparing polyurethane-polyurea parts and alkyl-substituted phenylenediamines used therefor. The non-cellular molded parts are particularly suited for use in the automobile industry, for example, as bumper coating, body parts such as fenders, spoilers, and wheel well expansions. They may also be used for preparing shoe soles and rollers. The cellular foams may be used as arm supports, seats, and cover layers in composite foams. The alkyl substituted phenylenediamine have a structural formula selected from the group consisting of -IMAGE- -IMAGE- -IMAGE-(I) (II) (III) and mixtures thereof in which R1 and R2 are the same or different and represent an alkyl radical with 1 to 4 carbon atoms, which are arranged linearly or branched, and in which R3 denotes an alkyl radical having 4 to 12 carbon atoms or a 5 or 6 member cycloalkyl radical.

Description

- ` 131 PROCESS FOR THE PREPARATION OF
POLY~RETHANE~POLYUREA MOLDED PARTS
AND ALKYL-SUBSTITUTED PHENYLENEDIAMINES USED THEREFORE
Background of the Invention 1 Field of the Invention The subject invention relates to a process for preparing polyurethane-polyurea parts and alkyl-substituted phenylene dominoes used therefore

2 Description of the Prior Art __ The preparation of cross linked plastics according to the isocyanate-polyaddition method is known. According to German Application if 96 864 USE. 3,099,516), hydroxyl group-containing compounds and polyisocyanates are foamed in molds for this purpose in the presence of blowing agents and - catalysts.
With the suitable selection of the hydroxyl group-containing compounds such as polyesters, polyethers and polyester Amadeus and organic polyisocyanates, as well as by additional usage of chain extenders such as glycols or 20 dominoes, elastic as well as rigid polyurethane elastomers was well as all intermediate modifications) can be produced according to this method.
For the preparation ox polyurethane elastomers, isocyanato group-containing propellers are initially produced prom the hydroxyl group-containing cc~pounds and polyisocyanates according to German Patent 831 604 (US. 2,778,810). In a second step the prepolymers are then reacted with chain extenders to result in high molecular weight elastomers.
Dominoes as chain extenders could generally not be processed according to the one-shot method. According to German Application 11 49 523 So 3,105,062), crystalline aromatic diprimary dominoes, in an amount which is not sufficient for saturating the isocyanate groups, are incur-prorated in the liquid isocyanato group-containing pro-polymers at a temperature below the melting point of the Damon and the Ionizes are subsequently cured by applying heat. According to German Patent 12 40 654 USE.

3,42~,610), the isocyanato group-containing prepolymers are reacted at room temperature or moderately increased tempera-lures with liquid or dissolved aromatic dominoes which have at least one linear alkyd substituent in the ortho position to the first amino group and two linear alkyd substituents with 1 to 3 carbon atoms in the ortho position to the second amino grout.
A process for the preparation of elastic molded parts with a closed surface layer of polyurethane-polyurea elastolners by reaction injection oiling is described in German Application 26 22 951 (US. 4,218~543~. The systems mentioned consist primarily of organic polyisocyanates, polyols, active aromatic do-, and/or polyamides, which are substituted by alkyd groups in the ortho position to the amino group, and a strong catalyst or the reaction between hydroxyl and isocyanato groups. It is important that the aromatic dip and polyamides are miscible with polyols having molecular weights of 1200 to 1800 in any ratio, that the alkyd substituents have 1 to 3 carbon atoms with at least two of the alkyd substituents having 2 to 3 carbon atoms, and that every one of the ortho positions to the amino groups is substituted. Such systems have cream times of less than one second. The transition of the liquid to solid phase takes place nearly instantaneously which results in the liquid reaction mixture solidifying in the mold along the walls of the mold.
It is further known that the reactivity of aromatically bonded amino groups with respect to isocyanates can he greatly reduced by electron attracting subset-tents. According to German Patent 12 16 538 (British Patent 981 935), examples of such aromatic dominoes are 3,3'-dichloro-4,4'-diaminodiphenylmethane, donator-

4,4'-diamino~iphenylmethane and 3,3'-dichloro-4,4'-diamino-diphenyl~ Louvre, processing with these amine requires expensive installations which decrease the productivity because of possible health hazards.
According to German Patent Application P 29 40 738.9, 3,3',5,5'-te~ra-alkyl-substituted 4,4'-diaminodiphenylmethanes, the alkyd radicals of which are the same or different and denote a methyl-, ethyl-, isopropyl-, secondary bottle or tertiary bottle radical, with at least one ox the radicals having to be an isopropyl or secondary bottle radical, as well as the corresponding diaminodiphenylmethane isomers, also have a reduced reactivity. The described tetra-alkyl-substituted diaminodiphenylmethanes are very well miscible with the polyols in the required quantities at room temperature and show only a snowily or no tendency toward crystallization so that the formulations can be handled well under conditions which are normal for conventional reaction injection molding (RIM) systems However, it was also found that the reactivity ox the described tetra-alk~l-substituted 4,4'diaminodiphenylmethanes can be too low for specific applications.
The purpose of this invention was to develop polyurethane systems which can be processed particularly according to the method of reaction injection molding (RIP). Compared with the systems disclosed in German Patent Application P 29 40 738.9, these systems should be somewhat more reactive. It was, on the other hand, not required thaw the downiness be miscible with the polyols at any ratio as long as they are sufficiently soluble under processing conditions. Furthermore, the systems should have sufficient liability with a relatively high Damon content. The 8~0 resultant molded part should have high thermal dimensional stability and should not display a progressive deterioration of the shear modulus curves between 100C and 200C.
Summary of the Invention _ _ The subject invention relates to a process for preparing molded polyurethane-polyurea parts comprising reacting the following ingredients:
1. an organic polyisocyanate, 2. a polyol, and 3. an alkyl-substituted phenylenediamine having a structural formula selected from the group consisting of (I) (II) (III) HEN- -R H and R

in which Al and R2 are the same or different and represent an alkyd radical with 1 to 4 carbon atoms, which are arranged linearly or branched, and in which R3 represents an alkyd radical with 4 to 12 carbon atoms or a 5 or 6 member cycloalkyl radical.

--S

' I

The process may be carried out in the presence of a blowing agent and catalyst. Other chain extenders may be used in addition to the alkylated phenylenediamines.
The invention also relates to alkylated phenylene-dominoes having a structural formula corresponding to 1, II, or III as previously defined.
At room temperature the phenylenediamines to be used in accordance with this invention are sufficiently soluble in the polyols, particularly the polyether polyols and polyester polyols. They display a reduced reactivity with respect to 2,4- and/or 2,6-toluenediamine and increased reactivity with respect to tetra-alkyl-substituted Damon-diphenylmethanes and, therefore, result in systems with considerable flyability even with high contents of alkyd-substituted phenylenediamines. Injection times of up to three seconds are possible on high pressure machinery Another advantage is that only a relatively low amount of polyisocyanate is needed for molded parts in order to achieve a certain shore hardness for the polyurethane formulation. Accordingly, molded parts with good mechanical properties can be produced in an advantageous fashion from mixtures of diphenylmethane diisocyanates and polyphenyl-polyethylene polyisocyanates (crude MID) and crude MID
prepolymers. The higher functionality of crude MID is only slightly noticeable, an advantage which has a very positive effect upon the profitability of the process according to this invention.
he molded parts produced in accordance with the process of this invention using ROY technology have a high thermal dimensional stability (or materials with a shore D-hardness of 6~:130, up to 140C according to ISSUER, Method B) and do not display a progressive deterioration of the shear modulus curve between 100C and 20~C.
Description of the Preferred Embodiment The following should be stated concerning the starting components to be used or the process ox this invention.
Possible isocyanates are aliphatic, cycloali-phatic, araliphatic and preferably aromatic multi functional diisocyanates. retailed examples include tune following:
alkaline diisocyanates with 4 to 12 carbon atoms in the alkaline radical, such as 1,12-dodecane diisocyanate, 1,4-tetramethylene diisocyanate, and preferably 1,6 hex-ethylene diisocyanate; cycloaliphatic diisocyanates such as cyclohexane-1,3' and 1,4-diisocyanate, as well as any desired mixture of tune isomers, l-isocyanato try-~ethyl-5-isocyanatomethyl-cyclohexane ( isophoro~e~di-isocyanate), 2,4- and 2,~-hexahydrotoluene diisocyanate as well as the corresponding isomer mixtures, 4,4'-, 2~2'- and 2,4'-dicyclohexylmethane diisocyanate, as well as the I I

corresponding isomer mixtures; and preferably aromatic dip and polyisocyanates such as 4,4'-, 2,4'~ and dyes-cyanato-diphenylmethane and the corresponding isomer mixtures, 2,4-and 2,6-diisoeyanato-toluene and the core-spondin~ isomer mixtures, 1,5-diisocyanato-naphthalene, polyphenyl-polymethylene-polyisocyanates, Tracy-cyanato-toluene and preferably mixtures of dip and polyp phenyl-polymethylene-polyisoeyanates (crude DOW). The dip and polyisocyanates mentioned above may be used individually or in forms ox mixtures.
So called modified multiEunctional isocyanates, that is products which were~obtaine~ by chemical reaction ox the aboYe-~entioned dip and/or polyisoeyanates are also frequently used. Suitable modified organic dip and polyp isoeyanates include, for instance: carbodii.~ide group-containing pol~isocyanates according to German Patent lo 92 007; allophonate ~roup-containing polyisocyanates as described or instance in British Patent 994 890, Belgian Patent 761 626, and Dutch Application 71 02 524; issues-curate group-eontaining ~olyisocyanates as are described for instance in German Patents 10 22 789, 12 22 067 and lo 27 394, as well as Published German Applications lo 29 034 an 20 04 048; urethane group-containing pulse-sonnets as are described for instance in Belgian Patent 752 261 or US. Patent 3,394,164; acrylated urea group-~Z~8~90 containing polyisocyanates, for instance, in accordance with German Patent 12 30 778; Burt group-containing pulses-notes, for instance, in accordance with German Patent 11 01 394 and British Patent 889 050; polyisocyanates produced by trimerization reaction, for instance, in accordance with Belgian Patent 723 640; and ester group-containing polyisocyanates such as are described in British Patents 965 474, German Patent 10 72 956, US. Patent 3,567,765, and German Patent 12 31 638.
lo Preferably used, however, are urethane group-containing polyisocyanates, for instance, dill, trio, or polypropylene glycol modified 4,4'-diphenylmethane dyes-Senate or Tulane diisocyanate; carbodiimide group and/or isocyanurate ring containing polyisocyanates, for instance, based on diphenylmethane diisocyanate, and/or Tulane diisocyanate; and particularly Tulane diisocyanate, diphenylmethane-diisocyanate, mixtures of diphenylmethane-diisocyanate and polyphenyl-polymethylene polyisocyanates (crude DOW), and mixtures of Tulane ~iisocyanates and crude Employed as polyols in the process according to this invention are preferably commonly used linear and/or branched, that is dip to tetra-~unctional, preferably dip and trifunctional polyester polyols, and particularly polyether polyols with molecular weights of 1000 to 8000, ~z~9~

and preferably 2000 to 7000. However, other hydroxyl group-containing polymers with the mentioned molecular weights are also suitable Examples for these include polyester asides, polyacetals, such as polyoxymethylene and butanediol/formals and polycarbonates, particularly those produced from diphenyl carbonate and 1,6-hexanediol by transesterifi-cation.
Suitable polyester polyols may be produced, or instance, from dicarl~oxylic acids, preferably aliphatic dicarboxyllc assess with 2 to 12, preferably 4 to 8 carbon atoms in the alkaline radical, and multi functional alcohols, preferably dills. examples include aliphatic dicarboxylic acids, such as succinic acid, glutaric acid, pime1ic acid undecanedioic acid, dodecanedioc acid, and preferably adipic acid, and aromatic dicacboxylic acids such as phthalic acid and terephthalic acid. Examples of bit and multi~unctional, particularly bifunctional alcohols are propylene 31ycol, 1,3-propanediol, trim ethylene glycol, dipro~ylene glycol, 1,5-pentamethylene glycol, 1,6-hexamethylene luckily, 1,10-decamethylene glycol, glycerine, trilnethylolpropane, and preferably ethylene glycol, diethylene glycol and 1,4- -butanediol. In audition to this, alkanolamines such as triethanolamine and triisopropanolamine may be used as multi functional alcohols. If polyfunctional, particularly trifunctional compounds, are also used for the manufacture --10~

of the polyester polyols, their content must be chosen in such a manner that the functionality of the resultant polyester polyols is 3.5, preferably 2 to 3.0 maximum.
Polyester polyols produced by polycondensation of a dicarboxylic acid mixture which contains 20 to 35 percent by eta, preferably 28 to 33 percent by weight of succinic acid, 35 to 50 percent by weight, preferably 40 to 45 percent by weight of glutaric acid, and 20 to 32 percent by weight, preferably 24 to 28 percent by weight of adipic acid, and alcohol mixtures of ethylene glycol/1,4-butane-dill, ethylene glycol/diethylene glycol, ethylene glycol/-trimethylolpropane, diethylene glycol/tri~nethylolpropane, ethylene glycol/triisopropanolamine, and diethylene glycol/triisopropanolamine, based on the overall weight of the mentioned dicarboxylic acids, have also proven to work well. The polyester polyols have molecular weights of 1000 to 3000 and preferably 18û0 to 2500.
However, preferably used as polyols are polyether polyols which are produced according to known methods prom one or more epoxies, preferably alkaline oxides with 2 to 4 carbon atoms in the alkaline radical, and an initiator molecule containing 2 to 8, preferably 2 to 4 active hydrogen atoms.
Suitable epoxies include, for instance, twitter-hydrofuran, 1,3-propylene oxide, 1,2- and/or battalion oxide, styrenes oxide, eipchlorohydrin, and preferably ethylene oxide and propylene oxide. The epoxies may be used individually, alternatingly in sequence, or as mix-lures. Suitable initiator molecules include: water, organic dicarboxylic acids such as succinic acid, adipic acid, phthalic acid, and terephthalic acid, aliphatic and aromatic, optionally N-mono, NUN- and N,N'-dialkyl-substituted dominoes with 1 to 4 carbon atoms in the alkyd radical, such moo- and dialkyl-substituted ethylenediamine, diethylenetriamine, triethylenetetramine, 1,3-propylene-Damon, 1,3- and/or 1,4-butylenediamine, 1,2- 1,3- I
1,5- and 1,6-hexamethylenediamine, phenylenediamine, 2,4-and 2,6-toluenediamine, and I Andy diamond-phenylmethane. Of particular interest of the compounds of the mentioned group are N,rl,N',N'tetrakis(2-hydroxyethyl)-ethylenediamine, NUN ' ON ' tetrakis~2-hydroxypropyl)ethylene-Damon, N,N,N',~'',N"pentakis(2-hydroxypropyl)diethylene-thiamine, phenyl-diisopropanolamine and higher alkaline oxide adduces of aniline.
other suitable initiator molecules include alkanolamines such as ethanol amine, diethanolamine, N-methyl- and rl-ethyl-ethanolamine, N-methyl- and r1-ethyl-diethanolamine and triethanolamine, ammonium, hydrazine and hydrazides. Priorly used are multiunctional, paretic-ularly bit and/or trifunctional alcohols such as ethylene I

glycol, 1,2- propylene glycol, and trim ethylene glycol, diethylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexamethylene glycol, glycerine, trimethylolpropane and pentaerythrlte.
Other applicable polyols are the non-reducing sugars, the non-reducing sugar derivatives and preferably their alkaline oxide adduces, wherein the alkaline oxides have 2 to 4 carbon atoms. Applicable non-reducing sugars and sugar derivatives include, or instance sucrose, alkylglycosides, such as methylglycoside an ethylene glucoside, and also glycolglycosides such as ethylene glycol glucoside, propylene glycol glucoside, glycerine glucosi.de and 1,2,6-hexane trio glucoside.
Also taken into consideration are polyols based on polyphenols and preferably their alkaline oxide adduces in which the alkaline oxides have 2 to 4 carbon atoms.
Applicable polyphenols include, or instance, bisphenol A, bisphenol F, condensation products of phenol an formal-Dodd, particularly the novolacs, condensation products ox various phenol compounds and acrylene, with the simplest substances ox this group being the 1,1,3-trislhydroxy-phenol)propanes, condensation products of various phenol compounds with glyoxal, glutaraldehyde, and other dialed-hypes, with the simplest substances ox this group being the 1,1,2,2-tetrakis(hydroxy-phenol~ethanes.

I

Another applicable group of polyols are the alkaline oxide preferably the ethylene oxide, 1,2-epoxypro-pane, epoxy butane, and mixtures thereof) adduces of condemn-station products of an aromatic amine, phenol, and alluded. The condensation products are obtained by condensing an aromatic amine, for instance, aniline or Teledyne, a phenol such as phenol or crossly, and an alluded, preferably formaldehyde, at increased temperatures, for instance, in the range of 60C to 180C. The condense-~10 lion product is then isolated and is reacted with an alkaline oxide resulting in the formation of the polyols.
Particularly worth mentioning are the propylene oxide and propylene oxide/ethylene oxide adduces of aniline/phenol/for-muddied condensation products.
The alkaline oxide adduces of phosphoric and polyphosphoric acids are another applicable group of polyols. Preferred alkaline oxides are ethylene oxide, 1,2 epoxy propane, the epoxy butane, and 3-chloro-1,2-epoxy-propane. Advantageous phosphoric acids are phosphoric acids, phosphorus acid, the polyphosphoric acids, such as tripolyphosphoric acid, and the polymetaphosphoric acids.
The polyether polyols have molecular weights from 2000 to 8000, and preferably 2500 to 7000. They may be used individually or in form of mixtures. In addition to this, they can often be mixed with the polyester polyols and L8~9~

hydroxyl group-containing polyester asides, polyacetols and polycarbonates.
As already mentioned, the alkyl-substituted phenylenediamines to be used in accordance with this invention are selected from the group consisting of come pounds with the following structural formulae:

(I) R NH

H 2N--~R

Al (II) ¢ Jo R3 I .
R NH2 , and (III) Al Ho 31 Z~8~

In these formulae Al and R2 are the same or different and represent an alkyd radical having 1 to 4 carbon atoms, preferably a methyl-, ethyl-, propel-, isopropyl-, bottle-, isobutyl-, secondarybutyl or tertiarybutyl radical, and R3 represents an alkyd radical with 4 to 12, preferably 4 to 8 carbon atoms. Preferred as R3 are branched alkyd radicals with 4 to carbon atoms.
Examples for the radicals R3 include n-butyl, 1-methylpropyl, 2-methylpropyl, tertiaryhutyl, n-pentyl, 1-it methylbu~yl, l-ethylpropyl, l,l-dimethylpropyl, n-hexyl, 1-methylpentyl, l-ethylbutyl, l,l-dimethylbutyl, l-methyl-l-ethylpropyl, Natalie, l-methyl-hexyl, l-ethylpentyl, 1,1-dimethylpentyl, l,l-diethylpropyl, n-octyl, l-methylheptyl, l-ethylhexyl, 2-ethylhexyl, l-propylpentyl, l,l-dimethyl-Huxley, l-methyl-l-ethyl-pentyl, l,l-diethylbutyl, 1,1,3,3-tetramethylbutyl ! n-nonyl, l-methyloctyl, l,l-dimethyl-hotly, l-methyl-l-propylpentyl, n-decyl, l-methylnonyl, l,l-diethylhexyl, l,S-dimethyl-l-ethylhexyl, n-undecyl, 1-methyldecyl, l-ethylnonyl, l-butylheptyl, l-pentylhexyl, n-dodecyl, l-methylundecyl, cyclopentyl, cyclohexyl, and methylcyclohexyl radicals.
Examples ox alkyl-substituted phenylenediamines include: 2,4-dimethyl-6-n-butyl-phenylenediamine-1,3; I
dimethyl-6-tl-methylpropyl)phenylenediamine-1,3; I
dimethyl-6-t2-methylpro~y1)phenylenediamine-1,3; 2,4-dimethyl-6-tertiarybutyl-phenylenediamine-1,3; 2-methyl-4-ethyl-6-n-butyl-phenylenediamine-1,3; 2-methyl-4-ethyl-6-(1-methylpropyl)phenylenediamine-1,3; 2-methyl-4-ethyl-6-(2-,nethylpropyl)phenylenediamine-1,3; 2-methyl-4-ethyl-Ç-tertiarybutyl-phenylenediamine-1,3; 2-methyl-4-isopropyl-6-n-butyl-phenylenediamine-1,3; 2-methyl-4-isopropyl-6-(1-methylpropyl)phenylenediamine-1,3; 2-methyl-4-isopropyl-6-~2-methylpropyl)phenylenediamine-1,3; 2-methyl-4-isopropyl-6-tertiarybutyl-phenylenediamine-1,3; 2-methyl-4,6-di-n-butyl-phenylenediamine-1,3i 2-methyl-4,6-bis(l-lnethyl-propyl)phenylenediamine-1,3; 2-methyl-4,6-bis(2-methyl-propyl)phenylenediamine-1,3; 2-methyl-4,6-ditertiarybutyl-phenylenediamine-1,3; 2-ethyl-4,6-di-n-butyl-phenylene-Damon; 2-ethyl-4,6-bis(l-methylpropyl)phenylene-Damon; 2-ethyl-4,6-bis(2-methylpropyl)phenylene-Damon; 2-ethyl-4,6-di-tertiarybutyl-phenylenedia.nirle-1,3; 2-isopropyl-4,6-di-n-butyl-phenylenediamine-1,3; 2-isopropyl-4,6-bi~ methylpropyl)phenylenediamine-.l,3; 2-isopropyl-4,6-bis(2-methylpropyl)phenylenediamine--1,3; 2-isopropyl-4,6-di-tertiarybutyl-phenylenediamine-1,,3; 2,4-diisopropyl-4-n-butyl, 2,4-diisopropyl-4-(1-methylpropyl)-phenylenediamine-1,3; 2,4-diisopropyl-4-(2-methylpropyl)-phenylene~iamine-1,3; 2,4-diisopropyl-4-tertiarybutyl-phenylenediamine-1,3; 2,4,6-tri-n-butyl-phenylenediamine-1,3; 2,4,6-tris(l-methylpropyl)phenylenediamine-1,3; 2,4,6,-I

tri-tertiarybutyl-phenylene~iamine-1,3; 2,4-dimethyl-6-n-pentyl-phenylenediamine-1,3; 2,4-dimethyl-6-(1-methylbutyl)-phenylenediamine-1,3; 2,4-dimethyl-6-(1-ethylpropyl)-phenylenediamine-1,3; 2,4-dimethyl-6-(1,1-dimethyl-propyl)-phenylenediamine-1,3; 2-methyl-4,6-di-n-pentyl-phenylenedi-amine-1,3; 2-methyl-4,6-bis(l-methylbutyl)phenylene~iamine-1,3;2-methyl-4,6-bis(l-ethylpropyl)phenylenediamine-1,,3; 2-,nethyl-4,6-bis(l,l-dimethylpropyl)phenylenediaminNoah; 2-ethyl-~,6-~i-n-pentyl-phenylenediamille-1,3; 2-ethyl-4,6--bis(l-ethylhutyl)phenylenediamine-1,3; 2-ethyl-4,6-bi~(l-ethylpropyl)phenylenediamine-1,3; 2-ethyl-4,6-bis(l,l-dimethylpropyl)phenylenediamine-1,3; 2-propyl~4,6-bis(l-methylbutyl)phenylenecliamine-1,3; 2-isopropyl-~,6-di-n-pentyl-phenylenediamine-1,3; 2-i~opropyl-~,6-bi-,(1-methyl-butyl)phenylenediamine-1,3; 2-isopropyl-4,6~bis(2-methyl-propyl)phenylenediamine 1,3; 2-isopropyl-4,6-bis(l,l-dimethylpropyl)phenylenediamine-1,3; 2-n-b~ltyl-4,6-bis(l-methylbutyllphenylenediamine-1,3; 2,4-dimethyl-6-n-hexyl-phenylenediamine-1~3; 2,~-dimethyl-~-(1-methylpent~ll-phenylenediamine-1,3; 2,4-dimethyl-6-(1,1 dimethylbutyl)-phenylenediamine-1,3; 2-methyl-4-isopropyl-6-n-hexyl-phenylenediamine-1,3; 2-methyl-~-isopropyl-6-(1-methyl-pentyl)phenylenediamine-1,3; 2-methyl-4,6-di-n-hexyl-pllenylenediamine-1,3; 2-ethyl ~,6-di-n-hexyl-phenylenedi-amine-1,3; 2-ethyl-4,6-bis(l~metllylpentyl)phenylenediamine-I o 1,3; 2-isopropyl-4,6-di-n-hexyl-phenylenediamine-1,3; 2-.isopropyl-4,6-bis(l-methylpentyl)phenylenediaminee-1,3; 2-n-butyl-4,6-bis(l-methylpentyl)phenylenediamine-1,3;; 2,4-dimethyl-6-n-heptyl-phenylenediamine-1,3; 2,4-dimethyl-6-(1-methylhexyl)phenylenediamine-1,3; 2,4-dimethyl-6-(1,1-~imethylpentyl)phenylenediamine-1,3; 2-methyl-4-isopropyl-6-n-heptyl-phenylenediamine-1,3; 2-methyl-4-i~opropyl-6-~1-methylhexyl)phenylenediamine-1,3; 2-methyl-4,6-di-n-heptyl-ohenylenediamine-1,3; 2-ethyl-4,6~di n-heptyl-phenylene-(immune; 2-ethyl-4,6-bis(l-methylhexyl)phenylenediamine-1,3; 2-isopropyl-~,~-di-n-heptyl-phenylenediamine-1,3; 2-isopropyl-4,6-bis(l-methylhexyl)phenylenediamine-11,3; 2-n-butyl-4,6-bis(l-methylhexyl)phenylenediamine-1,3; 2,4-dimethyl-6-n-octyl-phenylenediamine-1,3; 2,4-dimethyl-6-(1-methylheptyl)phenylenediamine-1,3; 2,4-dimethyl-6-(1-ethylhexyl)phenylenediamine-1,3; 2,4-dimethyl-6-(2-ethyl-hexyl)phenylenediamine-1,3; 2,4-dimethyl-6~(1,1-dimethyl-hexyl)phenylenediamine-1,3; 2,4-dimethyl-6-(1-methyl.-1-ethylpentyl)phenylene~iamine-1,3; 2,4-dimethyl-6-(1,1,3,3-tetramethylbutyl)phenylene~iamine-1,3t 2,4-~imethyl-6-(1-propylpentyl)phenylenediamine-1,3; 2 methyl-4-isopropyl-6-n-octyl-phenylene~iamine-1,3; 2-methyl-4-isopropyl-6-(1-methylheptyl)phenylenediamine-1,3; 2-methyl-4-isop~opyl-6-(2-ethylhexyl)phenylenediamine-1,3; 2-methyl-4-isopropyl-6-(l-me~hyl-l~ethylpentyl)phenylenediamine-1,3, 2-methyl-4-isopropyl-6-(1,1,3,3-tetramethylbutyl)phenylenediaamine-1,3;
2-methyl-4-isopropyl-6-(1-propylpentyl)phenylenediimmune, 2-methyl-4,6,di-n-octyl-phenylenediamine-1,3; 2-methyl-4,6-bis(l-methylheptyl)phenylenediamine-1,3; 2-methyl-4,6-bist2-ethylhexyl)phenylenediamine-1,3; 2-methyl-~,6-bis(1,1,3,3-tetramethylbutyl)phenylenediamine-1,3; 2-methyl-4,6-his(l-methyl-l-ethylpentyl)phenylenediamine-1,3; 2-methyl-4,6-bis-(l-propylpentyl)phenylenediamine-1,3; 2-ethyl-4,6-di-n-octyl-phenylenediamine-1,3; 2-ethyl-4,6-bis(l-methylheptyl)-phenylenediamine~l,3; 2-ethyl-4,6 bis(2-ethylhexyl)phenylene-Damon; 2-ethyl-4,6-bis(l-methyl-1-ethylpentyl)phenyl-enediamine-1,3; 2-ethyl-4,6-bis(1,1,3,3-tetramethylbutyl)-phenylenediamine-1,3; 2-ethyl-4,6-bis(l-propylpentyl)phenyl-enediamine-1,3; 2-isopropyl-4,6-di-n-octyl-phenylene~iamine-1,3;2-isopropyl-4,6-bis(l-methylheptyl)phenylenediaminno-1,3;2-isopropyl-4,6-bis-(2-ethylhexyl)phenylenediaminee-1,3;
2-isopropyl-4,6-bis(l-methyl-1-ethylpentyl)phenyleenediamine-1,3;2-isopropyl-4,6-bis(1,1,3,3-tetramethylbutyl)phenyylene-diamine~l,3; 2-isopropyl-4,6-bis(l-propylpentyl)phenylene~
amine-1,3; 2-n-butyl-4,6-di-n-octyl-phenylenediamine-1,3; 2-n-butyl-4,6-bis(l-methylheptyl)phenylenediamine-1,,3; on butyl-4,6-bis(2-ethylhexyl)pnenylene~iamine-1,3; 2-n-butyl-4,6-bis(l-methyl-1-ethylpentyl)phenylenediamine-1,,3; 2-n-butyl-4,6-bis(1,1,3,3-tetramethylbutyl)phenylenec~immune;
2-tertiarybutyl-4,6-bis(l-propylpentyl)phenylenediimmune;

o 2,4-dimethyl-6-n-nonyl-phenylenediamine-1,3; 2,4-dimethyl-6-( l-methyl-octyl )phenylene~1iamine-1, 3; 2, 4-climethyl-6-( 1,1-dimethylheptyl)phenylenediamine-l,3; 2-methyl-4-isopropyl-6-n-nonyl-phenylenediamine-l, 3; 2-methyl-4-isopropyl-6-( 1-methyloctyl )phenylenediamine-l, 3; 2-methyl-4-isopropyl-6-t 1, l-dimethylheptyl )phenylenediamine-l, 3; 2-methyl-4, Dunn-nonyl-phenylenediamine 1,3; 2-methyl-4,6-bis(l-methyloctyl)-phenylened lamine-l, 3; 2-methyl -4, 6-his ( 1, 1 -d imethylheptyl ) -phenylened iamb no- 1, 3; 2-e thy- 4, 6 -d i-n-nonyl-phenylened i-amine-1,3; 2-ethyl-4,6-his(l-methyloctyl)phenylenediamine-1,3;2-ethyl-4,6-bis(l,l-dimethylheptyl)phenylenediaminno-1,3; 2-isopropyl-4,6-di-n-nonyl-phenylenediamine-1,3; 2-isopropyl-4,6-bis(l-methyloctyl)phenylenediamine-11,3; 2-osopropyl-4,6-~is( 1,1-dime~hylhepty1)pllenylenediamine-1,3;
2-tertiarybutyl-4,6-di-n-nonyl-phenylenediamine-1,,3; 2-tertiarybutyl-4, byway ( l-methyloctyl )phenylenediamine-l, 3; 2-tertiaryl~utyl-4,6-bis(l,l-dimethylheptyl)phenylennediainine-1, 3; 2, 4 d imethyl-6-n-decyl-phenylene(liamine 1, 3; 2, 4-dimethyl-6-(1-methylnonyl)phenylenediamine-1,3; Dow-Inethyl-6-(l,l-~liethylhexyl)phenylenediamine-1,3;; 2,4-Dimethyl-6-(1,5-dimethyl-1-ethylhexyl)phenylenediaamine-1,3;
2-methyl-4-isopropyl-6-n-decyl-phenylenecl iamine-l, 3; 2-methyl-4-isopropyl-6-(1 methylnonyl)phenylenedia,nine-1,3; 2-methyl-4-isopropyl-6-( 1, l-die~hylhexyl )phenylenediamine-l, 3;
2-methyl-~-isopropyl-6-( 1, 5-dimethyl-1-ethylhexyl )phenylene-I

Damon; 2-methyl-4,6-di-n-decyl-phenylenediamine-1,3;
2-methyl-4,6-bis(l-methylnonyl)phenylenediamine-1,,3; 2-methyl-4,6-bis(l-diethylhexyl)phenylenediamine-1,33; 2-methyl-4,6-bis(1,5-dimethyl-1-ethylhexyl)phenyleneediamine-1,3; 2-ethyl-4,6-di-n-decyl-phenylene~3iamine-1,3; 2-ethyl-4,6-bis(l-methylnonyl)phenylenediamine-1,3; 2-ethyl-4,6-bis(l,l-diethylhexyl)phenylenediamine-1,3; 2-ethyl-4,6-bis(l,5-dimethyl-1-ethylhexyl)phenylenediamine-1,33; 2-isopropyl-4,6-di-n-decyl-phenylenediamine-1,3; 2-isopropyl-4,6-bis(l-methylnonyl)-phenylenediamine-1,3; 2-isopropyl-4,6-bis(l,l-diethylhexyl)phenylenediamine-1,3; 2-isopropyl-4,6-bis(1,5-dimethyl-l,ethylhexyl)-phenylenediaminNoah; 2-tertiarybutyl-4,6-di-n-decyl-phenylenediamine-1,3;; 2-tertiarybutyl-4,6-bis(l-methylnonyl)phenylenediamiinn; 2-tertiarybutyl-4,6-bis(l,l-diethylhexyl)phenylenediimmune;
2-tertiarybutyl-4,6-bis(1,5-dimethyl-1-ethylhexyl))phenylene-Damon; 2,4-dimethyl-n-undecyl-phenylenedi~mine-1,3;
2,4-dimethyl-6-(1-methyldecyl)phenyl~nediamine-1,33; 2-methyl-4-isopropyl-6-n-undecyl-phenylenediamine-1,,3; 2-methyl-4-isopropyl-6-ll-methyldecyl)phenylenediamiinn; 2-methyl-4,6-di-n-undecyl-phenylenediamine-1,3; 2-methyl-4,6-bis(l-methyldecyl)phenylenediamine-1,3; 2-ethyl-4,6-di-n-undecyl-phenylenediamine-1,3; 2-ethyl-4,6-bis(l-methyl-decyl)phenylellediamine-1,3; 2-isopropyl-4,6-n undecyl-phenylenediamine-1,3; 2-isopropyl-4,6-bis(l-methyldecyl)-~'21~

phenylenediamine-1, 3; 2-tertiarybutyl-4, 6-di-n-undecyl-phenylenediamine-l, 3; 2-tertiarybutyl-4 Boyce l-methyl-decal )phenylenediamine-l, 3; 2, 4-dimethyl-6-n-doclecyl-phenylenediamine-1,3; 2,4-dimethyl-6-( l-methylundecyl)-phenylenediamine-l, 3; 2-methyl-4-isopropyl-6-n-dodecyl-phenylened iamine-l, 3; 2-methyl-~-isopropyl-6-( l-methylun-decal )phenylenediamine-1, 3; 2-methyl-4-tertiarybutyl-n-dodecyl-phenylenecliamine-1, 3; 2-methyl~4-tertiarybutyl-6-( 1-methylundecyl)phenylenediamine-1,3; 2-methyl-4,6-di-n-dodecyl-phenylenediamine-1,3; 2-methyl-4,6-bis(l-methyl-decal )phenylenediamine-l, 3; 2-ethyl-4, 6-d i-n-undecyl-phenylenediamine-l, 3; 2-ethyl-4, Boyce ( l-methylclecyl ) -phenylenediamine-l 3; 2-isopropyl-4, 6-n-undecyl phenylene-Damon; 2-isopropyl-4,6-bi~( l-lnethyldecyl )phenylene-diamine-l, 3; 2-tertiarybutyl-4, find i-n-undecyl-phenylene-Damon; 2-tertiarybutyl-4,6-bis(l-methyldecyl)phenyl-enediamine-1,3; 2,4-dimethyl-6-n-dodecyl-?henylenediamine-1l3;2,4-dimethyl-6-(1-methylunclecyl)phenylenediamine--1,3;
2-methyl-4-isopropyl-6-n-dodecyl-phenylenediamine--1,3; 2-methyl-4-isopropyl-6-( l-methyl~ndecyl )phenylenediamine-l, 3;
2-methyl-4-tertiarybutyl-n-dodecylphenylenediamineeye; 2-,nethyl-4-tertiarybutyl-6-( l-methyl~lnclecyl )phenylenediamine-1,3; 2-methyl-4,6-di-n-dodecyl-phenylenecliamine-1,3; 2-methyl-4,6-bis( 1-methylundecyl)phenylenediamine-l,3; 2-ethyl-4,6-di-n-dodecyl-phenylenediatnine-1,3; 2-ethyl-4,6-bus ( l-methylundecyl ) -phenylenediamine-l, 3; 2-isopropyl-4, 6-di-n-dodecyl-phenylene~iamine-1,3; 2-isopropyl-4,6-bis(l-methylundecyl ) -phenylenediamine-l, 3; 2-tertiarybutyl-4, Dow-n-dodecyl-phenylened iamb Nell, 3; turret iarybutyl-4, Boyce ( 1-methylundecyl)phenylenediamine-1,3; 2-methyl-4-n-butyl-6-( 1, l-dimethylpropyl )phenylenediamine-l, 3, methyl 1-nethylpropyl ) -6-n-pentyl-phenylenediamine-1, 3; 2-methyl-4-tertiarybutyl-6-n-hexyl-phenylenediamine-1, 3; 2-methyl-4-n-Huxley 2-ethylhexyl )phenylenediamine-l, 3; 2-ethyl-4-lug tertiarybutyl-5-n-octyl-phenylenediamine-1, 3; ethyl 1-methylpropyl ) I l-methylheptyl )phenylenediamine-l, 3; 2-isopropyl-4-(1,1-dimethylpropyl)-6-n-octyl-phenyleenediamine-1, 3; I l-methylpropyl )-4-n-hexyl-6-n-decyl-phenylene-Damon;, 2,4-dimethyl-6-cyclopentyl-phenylenediamine-1, 3; 2, 4-diethyl-6-cyclopentyl-2henylenediamine-1, 3; 2-methyl-4-isopropyl-6-cyclopentyl-phenylenediamine-lo 2-methyl-4-tertiarybutyl-6-cyclopentyl-phenylenediammine-1, 3;
2, 4-dimethyl-6-cyclohexyl-phenylenediamine-1, 3; 2, deathly-6-cyclohexyl-phenylenediamine-1, 3; 2-methyl-4-isopropyl-6-cyclohexyl-phenylenediamine-1,3; 2 methyl-4-tertiary bottle-6-cyclohexyl-phenylened immune, 3; 2, 4-d imethyl-6- ( 4-methylcyclohexyl )phenylenediamine-l, 3.
Preferably used are 2, 4-dimethyl-4-n-butyl phenylenediamine-l, 3; 2, 4-dimethyl-4-( l-methylpropyl ) -phenylenediamine-1,3; 2,~-dimethyl-4-tertiarybutylphenyl--24~

enediamine-1,3; 2,4-dimethyl-6-n-pentyl-phenylenediamine-1,3;2,4-dimethyl-6-(1,1-dimethylpropyl)-phenylenediamiire-1,3; 2,4-dimethyl-6-n-hexyl-phenylenediamine-1,3; 2,4-dimethyl-6-n-octyl-phenylenediamine-1,3; 2,4-dimethyl-6-(1-methylheptyl)phenylenediamine-1,3; 2,4-dimethyl-6-(2-ethylhexyl)phenylenediamine-1,3; 2,4-dimethyl-6-(1,1,3,3-tetramethylbutyl)phenylenediamine-1,3; 2-methyl-4,6-di-n-butyl-phenylenediamine-1,3; 2-methyl-4,6-bis(l-methyl-propyl)phenylenediamine 1,3; 2-methyl-4,6-di-tertiarybutyl-phenylenediamine-1,3; 2-methyl-4-n-butyl-6-(1-methylpropyl)-phenylenediamine-1,3; 2-;nethyl-4-(1-methylpropyl)-6-ter-tiarybutyl-phenylenediamine-1,3; 2-methyl-4,6-~i-4-pentyl-phenylenediamine-1,3; 2-methyl-4,6-bis(l,l-dimetilylpropyl)-phenylenediamine-1,3' 2-methyl-4,6-di-n-hexyl-phenylene-Damon; 2-methyl-4,6-di-n-octyl-phenylenediamine-1,3;
2-methyl-4,6-bi~(l-methylheptyl)phenylenediamine-11,3; 2-methyl-4,6-bis(2-ethylhexyl)phenylenediamine-1,3; 2-ethyl-4,6-di-n-butyl-phenylenediamine-1,3; 2-ethyl-4,6-bis(l-methylQropyl)phenylenediamine-1,3; 2-methyl-~,6~di-~ertiary-butyl-phenylenediamine-1,3; 2-methyl-4-n-butyl-6-(1-methyl-propyl)phenylenediamine-1,3; 2-ethyl-4-(1-methylpropyl)-6~
tertiarybutyl-phenylenediamine-1,3; 2-ethyl-4,6-di-n-pentyl-phenylenediamine-1,3; 2-ethyl-4,6-bis(l,l-dimethylpropyl)-phenylenediamine-1,3; 2-ethyl-4,6-di-n-hexyl-ph~nylenedia mine 1,3; 2-ethyl-4,6-di-n~octyl phenylenediamin2-1,3; 2--I o ethyl-4,6-bis(l-methylheptyl)phenylenediamine-1,3;; 2-ethyl-~,6-bis~2-ethylhexyl)phenylenediamine-1,3; 2,4-dimethyl-6-cyclohexyl-phenylenediamine-1,3. The above listing also includes the isometric 1,3-phenylenediamines in accordance with formula I.
sable in accordance with this invention are individual compounds corresponding with formulas (I), (II) or (III) as well as mixtures of compounds of formulas (I), (II) or (IIIj as well as mixtures of alkyl-substituted phenyienediamines having formulas (I), (II) or (III) with chain extenders, secondary dominoes (I), (II), or (III), with chain extenders, secondary aromatic Clemens and/or 3,3',5,5'tetra-alkyl-substituted ~,4'-diaminodiphenyl-methanes.
The preparation of the aromatic Damon mixtures to be used in accordance with this invention takes place in a well known fashion by nitrating the corresponding trialkyl benzenes and subsequently hydrogenating or reducing the resultant donator compounds. The trialkyl benzenes used as starting materials can be prepared from easily accessible one- or 1,3-dialkyl benzenes in accordance with the methods described, or instance, in "Rhodes Chemistry of Carbon Compounds," Vol. III/A, page 102 et sex (lust Edition) and/or page 156 et sex (end Edition); J. Matthew and J. Will-annul, "Formation ox C-C-Bonds," Volume II, page 280 et sex; or "Methodicum Chimicum", Vol. 4, page 171 et sex.
Along the methods cited in the above literature, the alkylation of a moo- or 1,3-dialkyl Bunsen with an open chained or cyclic alkyd halide alkene or alcohol is gent orally preferred for economic reasons. Instead of the pure 1,3,5-trialkyl benzenes, mixtures of such compounds as are produced by these alkylation reactions may be used for the further reaction.
The alkyd benzenes are nitrated to a mixture of isometric donator compounds according to basically known methods. Suitable methods include, for example, Houben-Well, "methods ox Organic Chemistry," Vol. X/l, page 32 et seq. The reduction ox the vitro groups to the corresponding aromatically bonded amino groups may he implemented by catalytic hydrogenation, for instance, ho using Raney-Nickel or palladium as catalyst. It may of course be implemented also according to other basically known reduction methods using, for instance, iron, zinc, tin or also hydrazine as reduction agents. The amine mixture, obtained for instance after removing the catalyst, and the solvent used for the reduction, may be reacted with polyisocyanates which may optionally be modified without further purification, or if special value is placed upon purified products, aster crystallization or distillation.

~2~9~3 The alkyl-substituted phenylenediamines of formula (I), (II) or (III), or their mixtures, are used for the process according to this invention in quantities of 5 to 150 parts by weight, preferably 8 to 100 parts by weight, and particular 10 to I parts by weight based on 100 parts by weight of polyol.
Used as catalysts are particularly those compounds which greatly accelerate the reaction of the polyols and optional hydroxyl group-containin~ chain extenders with the polyisocyanate. Suitable examples are organic metal compounds, preferably organic tin compounds such as tin-(Isolates of organic carboxylic acids, for example tin-(II)-acetate, tin-(II)-octoate, tin-(II)-ethylhexoate, and tin-(II)-laurate; and the dialkyl tin (IV)-salts of organic carboxylic acids, for example, dibutyl tin diacetate, dibutyl tin dilaurate, dibutyl tin Malta, and ~ioctyl tin diacetate. The organic metal compounds are used alone or preferably in combination with strongly basic amine.
Examples include amidine~ such as 2,3-dimethyl-3,~,5,6-tetrahydropyrimidine; tertiary amine such as triethylamine, tributylamine, dimethylbutylamine, N-methyl m~rpholine, N-ethyl morpholine, N-cyclohexyl morphine NUN .-tetramethylethylenediamine, N,NrN',N'-tetramethyl-butanediamine, pentylmethyl-diethylenetriamine, tetramethyl-diaminoethyl ether, bis(dimethylaminopropyl~ure~r dim ethyl-I

piperazine, 1,2-dimethylimidazol, 1-azo-bicyclo-(3,3,0)-octane, and preferably 1,4-cliazobicyclo-(2,2,2)-octane; and alkanol compounds such as triethanolamine, triisopropanol-amine, methyl diethanolamine, and Methyl diethanolamine, and dimethylethanolamine.
then suitable catalysts include: tris(dialkyl-aminoalkyl)-s-hexahydrotriazine, particularly treason (dimethylaminopropyl)-s-hexahydrotriazine; tetra-alkyl-ammonium hydroxides, such as tetramethyl-ammonium hydroxide;
alkali hydroxides, such as sodium hydroxide; and alkali alcoholates, such as sodium methyl ate and potassium is propylate; as well as alkali salts of long chained fatty acids with 10 to 20 carbon atoms, and possibly hydroxyl groups in side positions. Preferably used are 0.001 to 5 percent by weight, particularly 0.05 to 2 percent by weight of catalysts, or catalysts combinations based on the polyol weight.
Under certain circumstances, particularly for the manufacture of cellular polyurethane puller molded parts, it may also be advantageous to partially replace the above-mentioned alkyl-substituted phenylenediamines by chain extenders, secondary aromatic dominoes, and/or 3,3'-5,5'-tetra--alkyl-substituted 4,4'-diaminodiphenylmethanes. The chain extenders advantageously have molecular weights of less than 500, preferably 30 to 400, and preferably have two ~2~8~9~3 active hydrogen atoms. Suitable examples include, for example, aliphatic and/or araliphatic dills with 2 to 14, preferably 2 to 6 carbon atoms, such as ethylene glycol, 1,3-propanediol, l,10-decanediol, diethylene glycol, dipropylene glycol, his(2-hydroxyl-ethyl)hydroquinone, and preferably ethylene glycol 1,4-butanediol, and 1,6-hexane-dill; trios such as glycerine and trimethylolpropane; and Lot molecular hydroxyl group-containing polyalkylene oxides based on ethylene and/or propylene oxide, and the above-mentioned initiator molecules.
Examples of secondary aromatic dominoes include:
~,N'-dialkyl-substituted aromatic dominoes which may option-ally be substituted by alkyd radicals at the aromatic nucleus, with 1 to 20, preferably 1 to 4 carbon atoms, in the Noel radical, such as N,N'-diethyl-p and/or -m-phenylenediamine, N~N'-di-secondary-pentyl-p and/or m-phenylenediamine, N,il'-di-secondary-hexyl-p and/or m-phenylenediamine, NUN' di-secondary-decyl-p and/or m-phenylenediamine, N,N'-dicyclohexyl-p and/or m-phenylene-Damon, N,N'-dimethyl-diaminodiphenylmethane, N~N~-diethyl-diaminodiphenylmethane, N,N-diisopropyl-diaminodiphenyl-methane, ~,N'-di-secondary-butyl-diaminodiphenylmethane, ~,~l'-dicyclohexyl-4,4~diaminodiphenylmethane~ and N,N'-di-secondary-butyl-benzidine.

~30-I

Examples of suitable 3,3',5,5'-tetra-alkyl-substituted 4,~'-diaminodiphenylmethanes include 3,3',5,5'-tetramethyl-diaminodiphenylmethane, 3,3',5,5'-tetraethyl-diaminodiphenylmethane, 3,3'5,5'-tetra-n-propyl-4,~'-diaminodiphenylmethane, 3,3'-diisopropyl-5,5'-diethyl-diaminodiphenyl~ethane, 3,5-diisopropyl-3',5'-dimethyl-diaminodiphenylmethane, 3,3',5 triisopropyl-5'-methyl-diaminodiphenylmethane, and preferably twitter-isopropyl-4,4' diaminodiphenylmethane. Mixtures of the alkyl-substituted phenylenediamines and the above-mentioned chain extenders, secondary aromatic dominoes, and/or 3,3',5,5'-tetra-alkyl-substituted 4,~'~diaminodiphenyl-methanes applicable according to this invention have also proven to work well.
the slowing agents which may be used optimally in the method according to this invention include water which reacts with isocyanate groups by forming carbon dioxide.
The amount of water which is advantageously used is Owl to 2 percent ho weigh based on the polyol weight.
other applicable blowing agents are low boiling liquids which evaporate under the influence of the ego-thermal polyaddition reaction. Seattle for this purpose are liquids which are inert with respect to the organic polyisocyanate and have boiling points below 100~.
Employs or such preferably used liquids are halo~enated hydrocarbons such as ethylene chloride, trichlorofluoro-methane, dichlorodi~luoromethane, dichloromonofluoromethane, dichlorotetrafluoroethane and 1,1,2-trichloro-1,2,2-tri-fluoroethane. Mixtures of these low boiling inert liquids and/or with other substituted or unsubstituted hydrocarbons may also be used.
The most advantageous amount of low boiling liquid for the preparation of cellular polyurethane-polyurea molded parts is a function of the density to be achieved as well as optionally upon the use of water. enroll amounts of 1 to lo parts by weight based on 100 parts by weight of polyol provide satisfactory results Auxiliaries and additives may also be incorporated in the reaction mixture. Examples include surface-active substances, foam stabilizers, cell regulators, fillers, dyes, pigments, flame retardants, hydrolysis protection agents, fungi stats, and bacteria stats.
Possible surface active substances include those substances which support the homogenization of the starting materials and optionally are also suited for regulating the cell structure. Examples include emulsifiers, such as sodium salts of castor oil sulfites or of fatty acids, as well as salts of fatty acids with amine, for example, owlet diethylamine, or Stewart diethanolamine; salts of sulfonic acids, for example, alkali or ammonium salts of zig dodecylbenzene, disulphonic acid or dinaphthylmethane-disulphonic acid and ricinoleic acid; foam stabilizers such as siloxane-oxalkylene mixed polymers, and other organ-polysiloxanes, ethoxylated alkyd phenols, ethoxylated fatty alcohols, paraffin oils, esters of castor oil and/or ricinoleic acid and Turkish red oil, and cell regulators such as paraffins, fatty alcohols and dim ethyl pulse-laxness. The surface active substances are generally used in quantities of 0.01 to 5 parts by weight hosed on 100 parts by weight of polyol.
Fillers, particularly reinforcing fillers, are understood to he the well known, commonly used, organic and inorganic fillers, reinforcing agents, wetting agents, agents for improving the abrasion behavior in coatings, paints, etc.
Detailed examples include: inorganic fillers such as silica tic minerals, for example silicates such as antiart serpentine amphibolites, amphiboles, Crusoe-tile, and talcum; metal oxides such as kaolin, aluminum oxides, titanium oxides and iron oxides metal salts such as chalk, and heavy spar; and lnor~anic pigments such as cadmium sulfide, zinc sulfide as well as glass, asbestos meal and others. Preferably used are kaolin (china clay), aluminum silicate, and co-precipitates of barium sulfite and aluminum silicate, as jell as natural and synthetic v fibrous minerals, such as asbestos, wollastonite, and particularly glass fibers of various lengths which may optionally be sized. examples of organic fillers include:
carbon, mailmen, kollophonium, cyclopentadienyl resins, and preferably graft polymers based on styrene-acrylonitrile which are produced by in situ polymerization of acrylo-nitrile-styrene mixtures in polyether polyols as described in German Patents 11 11 394, 12 22 669 USE. Patents 3,304,273, 3,383,351, 3,523,Q93), 11 52 53G (British Patent 1,040,452), and 11 52 537 (British Patent 987,618), as well as filler polyols where aqueous polymer dispersions are transformed into polyol dispersions.
The inorganic and organic fillers may be used individually or as mixtures. Preferably used are stable filler-polyol dispersions where the fillers in the presence of polyols are crushed to a particle size of less than 7 microns on situ and with high local energy densities and are simultaneously dispersed. Filler-polyol dispersions of this type are described, for example, in German Published Application 28 50 609, 28 50 610 and 29 32 304.
The inorganic and organic fillers are preferably added to the reaction mixture in quantities of 0~5 to 50 percent ho weight, preferably 1 to 40 percent by weight based on the weight of the polyisocyanate-polyol mixture.

Suitable flame retardants include tricresol phosphate, tris-2-chloroethyl phosphate, tris-chloropropyl phosphate and tris-2,3-dibromopropyl phosphate.
In addition to the already mentioned halogen-substituted phosphates, inorganic lame retardants such as aluminum oxide hydrate, antimony trioxides arsenic oxide, ammQnium polyohoshate and calcium sulfate, as well as the esteri~ication products of lo molecular polyols, and halogenated phthalic acid derivatives may be used for rendering the polyurethane roams flame resistant. It has generally proven advantageous to use 5 Jo 50 parts by weight, preferably 5 to 25 parts by weight, of the mentioned flame retardant per 100 parts by weight of polyol.
Gore detailed data on the above-mentioned other commonly use auxiliaries and additives are contained in the appropriate literature, for instance, in the monograph by J. H. Saunders and I. C. Fresh, "High Polymers," Vol. XVI, Polyurethane, Parts 1 and 2, Intrusions Publishers, 1962 and 1964.
For the preparation of the optionally cellular polyurethane-polyurea molded parts, the organic pulse sonnets, polyols, alkyl-substituted phenylenediamines, and optionally the chain extenders, secondary aromatic dominoes and/or 3,3'5,5'-tetra-alkyl-substituted diamond-phenylmethanes are reacted in such quantities that the ratio of isocyanate groups to Zerewitinoff active hydrogen atoms bonded to hy~roxyl, amine, and alkyklamine groups is 1:0.90 to 1.25, preferably 1:0.95 to 1.15.
The preparation of the cellular and preferably noncellular polyurethane-polyurea molded parts is preferably implemented by the one-shot method according to the well known reaction injection molding technique. This mode of operation is described, for instance, by Pocket and Pyre in "Integral Foams," Carl-Hanser Publishers, Munich Vienna 1~75; D. J. Prepelka and J. L. Wharton in the Journal of Cellular Plastics, March/April 1975, pages 87 through 98 and by U. Knapp in the Journal of Cellular plastics, arch April 1973, pages 76 through 84. However, the formulations may also be processed by conventional methods into molded elastomers and integral foams.
The alkyl-substituted phenylenediamines to be used in accordance with this invention are dissolved in the polyols while being stirred, optionally at increased temperatures for instance, in a range of 30C to 120C.
According to an advantageous version, the molten alkyd-substituted phenylenediamines are incorporated in the heated polyols while being stirred.
Using a mixing chamber with several feed nozzles, the liquid starting components or solutions of solid in liquid starting components may be introduced individually and may be mixed intensively in the mixing chamber. It has proven to be particularly advantageous to work according to the two-component method and to combine the solution of alkyl-substituted phenylenediamines and polyols with the catalysts and possibly the chain extenders, secondary aromatic dominoes, tetra-alkyl-suhstituted diaminodiphenyl-methanes, blowing agents, auxiliaries and additives to form component A and to use the organic polyisocyanate as component B. An advantage of this method is, or example, that the A and B components can be stored separately and can be transported in a space saving manner and only require mixing of the appropriate amount prior to processing.
The amount of reaction mixture introduced into the mold is measured in such a manner that the resultant non-cellular molded parts have a density of I to 1.4 grams per cubic centimeter, preferably of 0.9 to 1.35 grams per cubic centimeter, and that the cellular molded parts have a density of 0.1 to 0.8 grams per cubic centimeter, preferably 0.15 to 0.6 grams per cubic centimeter. The starting components are introduced in the mold at a temperature of 15C to 70C, preferably 20C to 55C. The temperature of the mold advantageously is 20C to 90C, preferably 40C to 85C. and it may be advantageous Jo use commonly applied release agents, for example, those based on wax or silicone, in order to improve the unfolding process. The degrees of compression normally are located between 1 and 8, preferably between 1.5 and 6.
The non-cellular polyurethane-polyurea molded parts obtainable according to the process of this invention are particularly well suited for use in the automobile industry, for example, as bumper coatings and body parts such as fenders, spoilers and wheel well expansions. They may also be used in preparing parts for houses and for preparing shoe soles and rollers. The cellular foams are used, for example, as arm supports, heat supports, safety features inside the automobile, as well as bicycle and motorcycle seats and seat cushions, and cover layers in composite foams.
The Examples which follow will illustrate in more detail the practice of the subject invention The parts referred to in the examples are parts by weight.

I I

Examples 1-6 illustrate the preparation of several al)cyl-substituted phenylenediamines.
Example 1 A At 0C to 10C, a mixture of 89 grams of 98 percent nitric acid and 120 grams of 90 percent sulfuric acid was added drops into 97.2 grams of 1,3-dimethyl-5-tertiarybutyl-Bunsen which had been produced in accordance with the procedure set forth in the Journal of the American Chemical_Soclety, 61, 101 (1939). Subsequently the mixture was stirred at 0C to 10C for 3 hours and at room temperature for 12 hours. Following hydroly-skis with ice water the mixture was extracted with Tulane, the combined organic phases were washed with dilute sodium hydroxide solution and water, and the solvent was removed under reduced pressure. Remaining as a residue were 145 grams of a slowly crystallizing oil.
8. Carrying out the nitration in aliphatic hydrocarbons (for example, hectane) in accordance with German Application 11 05 800 resulted in 22 grams of crude donator mixture from 16.2 grams ox 1,3-dimethyl-5-tertiary ~utylhenzene.

3LZ~ 0 C. In a mixing vessel, 50.4 grams of the crude donator compound were dissolved in 200 milliliters of ethanol, and mixed with 50 grams of hydrazine hydrate. The mixture was heated to 50C and Rangy nickel suspended in ethanol was added by batches until the gas development was completed. The mixture was heated to boiling for 1 hour, the hot catalyst was removed by filtration, and the filtrate was concentrated under reduced pressure. The remaining residue crystallized upon cooling.
Obtained were 35 grams of a dimethyl-tertiary-butyl-phenylenediamine mixture having a melting point of 73C to 75C.
D. In a reaction vessel, 600 grams of donator-dimethyl-tertiarybutylbenzene in two liters of ethanol were hydrogenated with 60 grams of Haney nickel as catalyst at 100C and 100 bars of hydrogen pressure. The catalyst was removed by filtration and the filtrate was distilled under reduced pressure. Obtained were 367 grams of a diaminodimethyl-tertiary-butylbenzene mixture having a boiling point ox 127C to 131C (0.4 mulberry which slowly solidifies upon cooling.

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Example 2 The preparation of 2-methyl-4,6-di-tertiarybutyl-phenylenediamine-1,3 is described in Rec. Tray. Chum., Pays Bass Vol. 75, 301 (1956).
Example 3 A. The tertiary butylation ox l-methyl-3-iso-propylbenzene and the subsequent nitration were implemented according to German Reich Patent 542 252 (Example I
B. Hydrogenation of the mixture of isometric dinitromethyl-isopropyl-tertiarybutylbenzene obtained according to (A) in accordance with the above-described process resulted in the corresponding methyl-isopropyl-tertiarybutyl-phenylenediamine-1,3-mixture having a bailing point of 115C to ll9~C (0.5 mulberry).
Example 4 A. At room temperature, 96.5 grams of n-octyl~

bromide were added drops into a mixture of 106 grams of m-xylene and 26 grams aluminum chloride. After slowing of the hydrogen chlorite development, the mixture was heated to SKYE to 60~C for 1 hour and was poured onto ice hydrochloric acid aster cooling The organic phase issue separated, was washed until neutral with soda solution, and, after drying over sodium sulfite, was distilled under reduced pressure. Obtained were 80 grams of dimethyl-octylbenzene having a boiling point of 114C to 120C (1.33 mulberries).
B. While being well cooled (0C to 10C), a mixture of 44.5 grams of 98 percent nitric acid and 90 percent sulfuric acid was added drops into 65.4 trams of dimethyl-octyl-Hanson. Subsecluently the mixture was stirred at 0C to 10C for 3 hours and at room temperature for 12 hours. The reaction mixture was then poured into ice water and the organic phase was abstracted with Tulane.
The Tulane extract was washed with water, dried over calcium chloride, and concern-treated. Ike residue containing the crude dinitro-dimethyl-octylbenzene mixture was dissolved in 450 milliliters of ethanol and mixed with Rangy nickel. At 50C, 75 Millie liters of hydrazine hydrate was added drop-wise, the mixture was heated to boiling for L
hour, and the catalyst was removed from the warm reaction solution by Eiltr~tion. The filtrate was distilled under reduced pros-~'2~8~

sure. Obtained were 42.2 grams of a Damon mixture boiling at 190C to 200C ~0.66 to 0.8 mulberries).
Example 5 A. In accordance with US, Patent 2,955,929, 1,3-3imethyl-5~cyclohexylbenzene was prepared.
B. In a reaction vessel, 18.8 grams of the product obtained in accordance with (A) were slowly mixed with 14 grams of 98 percent nitric acid] and 34 grams of 95 percent sulfuric acid at room temperature. Subset quaintly the mixture was stirred at room temperature for 20 minutes and at 50C for 15 minutes. After cooling the product was poured onto ice, and the organic phase was absorbed with ethylene chloride. The ethylene chloride extract was washed until neutral and Armed. The residue remaining after ~istilla-lion of the solvent was treated with hydrazine hydrate/Raney nickel, analogous to Example 1. After the usual processing the dimethylcyclohexyl phenylene~iamine-1,3 was obtained in the form of an oil which was use for the preparation ox prepolymers without additional purification.

I

I

Example 6 A. In this Example, 1,3-dimethyl-5-tertiary-amylbenzene was produced in accordance with the process described in the Journal of the American Chemical Society, 61, 1413 (1939) from m-xylene and 2-methylbutanol-2. The fraction boiling at 105C to lQ8C (18 Torn) was used for the additional reaction.
B. At 0C to 10C a mixture consisting of 44.5 parts of 98 percent nitric acid and 60 parts of 90 percent sulfuric acid were added drops to 53.1 parts of the hydrocarbon produced in accordance with (A). The mixture was stirred at 0C to 10C for three hours and at room temperature for 12 hours. Subset quaintly, the mixture was poured onto ice, was absorbed with zillion, and the organic phase was separated and washed with a dilute sodium hydroxide solution and water. After concern-treating under reduced pressure, 76 parts of crude dinitro-1,3-dimethyl-5-tertiaryamyl-Hanson were obtained C. The donator compound obtainer according to (B) was dissolved in 450 parts of ethanol and mixed with 5 parts of Rangy nickel. Beginning I

at 50C, 75 parts of hydra~ine hydrate were added drops, the mixture was heated for 1 hour to boiling, was filtered while hot, and the filtrate was concentrated. Distillation of the residue under reduced pressure (approx-irately 0.4 mulberries) resulted in 28.4 parts of a diamino-1,3-dimethyl-5-tertiaryamylben-zone mixture of which boiled at 152C to 162C.
The following Examples will illustrate the use of the various alkyl-substituted phenylenediamines as chain extenders in preparing polyurethane-polyurea parts by reaction injection molding (RIM). Unless otherwise noted, the system formulations described were processed with high pressure metering devices in which mixing takes place according to a type of counter-current injection. The equipment used was the Puromat*and Puromat*SV Series manufactured by Elastogran, machine Construction, Stress-tech, Germany.
For the mechanical tests, panels were produced with various dimensions (300 x 300 to 1000 x 4 millimeters and/or 600 x 400 x 4 millimeters) in heatable-closed panel molds of steel or aluminum. In addition to this, molded parts were produced such as automobile fenders, spoilers, motorcycle fenders, fender expansion strips, shock absorber * (Trademark) , .. Jo , .

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covers and other parts. Steel-aluminum and epoxide molds were used. The molds were filled via direct gate or fan gate, or accumulator heads, optionally with integrated post-mixing elements. The injection weights varied from 350 to approximately 5000 grams.
For larger molded parts the metering devices had to have a high output capacity approximately 2 kilograms per second with a molded part having a weight of approxi-mutely 5 kilograms). In spite of the high reactivity at the liquid system components, however, it was also possible to achieve injection times of 0.4 to 3.5 seconds.
Smaller panels and molded parts (100 gram weight) could also be produced with low pressuring metering devices (for instance, EM F 6 and F 20 STY of the above-mentioned company). In this case, it was found that the use of small mixing chambers with Teflon coated surfaces and Teflon coated mixing devices is preferred.
Example 7 Mixed as the polyol component were 75.~ parts of a hock copolyether polyol based on trimethylolpropane-propylene oxide-ethylene oxide with a hydroxyl number of 25;
23.0 parts 2,4-dimethyl-6-tertiarybutyl-phenylenediamine-1,3; 1.0 part of a 33 percent solution of diazahicyclo-octane in dipropylene glycol; and 0.2 parts of dibutyl yin dilaurate.

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The polyol component was heated to 50~C. The polyol component and 54.5 parts corresponding with an index of 1.05) of a reaction product of dipropylene glycol and 4,4'-diphenylmethane diisocyanate having an isocyanate content of 23 percent were processed by reaction injection molding techniques using Permute 80 as the high pressure metering device.
The temperature of the system components was 50C, and the panel mold (500 x 300 x 4 millimeters) was also heated to 50C. The mold time was 20 seconds. At this point the panels did not form any cracks when bent by 180.
The density of the panels was 1.05 to 1.08 grams per cubic centimeter. After tempering at 120C for 1 hour, the following properties were determined by testing the panels:

Density (grams/cubic centimeter 1.10 Tear Strength (M/mm2) 33.4 Breaking elongation (percent) 260 Graves Tear Strength (~/mm)120.5 Shore D-~lardness 64 wending E-Modulus (N/mm2) at 23C ~60 Thermal Dimensional Stability (C) According to ISO-75/B 136.

~Z~190 Example 8 Mixed as the polyol component were 72. a parts of a block copolyether polyol based on trimethylol-propane-propylene oxide-ethylene oxide having a hydroxyl number of 25; 26.0 parts of 2,4-dimethyl-6-cyclohexyl-phenylene-Damon; 1.0 parts of a 33 percent solution of disobey-cycle octane in dipropylene glycol; and 0.20 parts of dibutyl tin dilaurate. The polyol component was heated to 50C. The polyol component and 54.5 parts (corresponding with an index of 1.05) of the isocyanate prepolymer used in Example 1 were processed according to the conditions described in Example 1 an made into test panels. The properties of these panels were as follows:

Density (grams/cubic centimeter) 1.08 Tear Strength (tl/mm2) 29.4 Breaking Elongation (percent) 310 Graves Tear Strength (N/mm)103.5 Shore D-~lardness 60 Bending Fiddles at 23C (~/mm2) 390 Thermal Dimensional Stability According to ISO-75/B (C~ 121.
Example 9 iced as the polyol component were ~9.1 parts of a block copolyether polyol based on trimethylolpropane-I

propylene oxide-ethylene oxide having a hydroxyl number of 25î 29.7 parts 2,4-dimethyl-6-n-octyl-phenylenediamine-1,3; 1.0 parts of 33 percent solution of diazobicyclo-octane in dipropylene glycol; and 0.20 parts of doughtily tin dilaurate.
The polyol component was heated to 50C. The polyol component and 43.2 parts (corresponding with an index of 1.05) of a reaction product of diphenylmethane-diisocy-ante and polyphenylpolymethylene polyisocyanates (crude lo DOW) with propylene glycol and o1igopropylene glycols (NO
continuity percent) were processed according to the conditions of Example 1 and made into test panels. The properties of these panels were as follows:

Density grams per cubic centimeter) 1~05 Tear Strength (N/mm2) OWE
Breaking Elongation (percent) 205 Graves Tear Strength (N/mm~ 75.4 Shore D-~3ardness 61.

Claims (23)

The embodiments of the invention in which an exclusive privilege or property is claimed are defined as follows:

1. A process for the preparation of polyurethane-polyurea molded parts comprising reacting the following ingredients:

(1) an organic polyisocyanate, (2) a polyol, and (3) an alkyl-substituted phenylenediamine having a structural formula selected from the group consisting of (I) (II) (III) and mixtures thereof in which R1 and R2 are the same or different and represent an alkyl radical with 1 to 4 carbon atoms, which are arranged linearly or branched, and in which R3 denotes an alkyl radical having 4 to 12 carbon atoms or a 5 or 6 member cycloalkyl radical.

2. The process of claim 1 wherein the ratio of isocyanato groups of the isocyanate to active hydrogen atoms of the polyol component is from 1:0.90 to 1:1.25.

3. The process of claim 2 wherein a catalyst is used.

4. The process of claim 3 wherein a blowing agent is used.

5. The process of claim 1, 2 or 3, wherein the reactants are processed according to reaction injection molding techniques.

6. The process of claim 4 wherein the alkyl radical R3 is a branched alkyl radical.

7. The process of claim 1, 2 or 3, wherein the reactants are processed according to reaction injection molding techniques and wherein the alkyl radical R3 is a tertiarybutyl radical.

8. The process of claim 1, 2 or 3, wherein the reactants are processed according to reaction injection molding techniques and wherein the alkyl radical R3 is a linear or branched octyl radical.

9. The process of claim 1, 2 or 3, wherein the reactants are processed according to reaction injection molding techniques and wherein the alkyl radical R3 is a cyclohexyl radical.

10. The process of claim 1, 2 or 3, wherein the reactants are processed according to reaction injection molding technique and wherein the alkyl radicals R1 and R2 are methylbutyl groups and R3 is a tertiarylbutyl group.

11. The process of claim 1, 2 or 3, wherein the reactants are processed according to reaction injection molding techniques and wherein R1 and R2 are a methyl- and R3 is a linear or branched octyl group.

12. The process of claim 1, 2 or 3, wherein the reactants are processed according to reaction injection molding techniques and wherein R1 and R2 are a methyl- and R3 a cyclohexyl group.

13. The process of claim 1, 2 or 3, wherein the reactants are processed according to reaction injection molding techniques and wherein the alkyl- substituted phenylenediamines are used as mixtures with chain extenders, secondary aromatic diamines and/or 3,3',5,5'-tetra-alkyl-substituted 4,4'-diaminodiphenylrnethanes.

14. A molded polyurethane part prepared in accordance with the process of claim 1, 2 or 3, wherein the reactants are processed according to reaction injection molding techniques.

15. The process of claim 4, wherein the reactants are processed according to reaction injection molding techniques.

16. The process of claim 4, wherein the reactants are processed according to reaction injection molding tech-niques and wherein the alkyl radical R3 is tertiarybutyl radical.

17. The process of claim 4, wherein the reactants are processed according to reaction injection molding tech-niques and wherein the alkyl radical R3 is a linear or branched octyl radical.

18. The process of claim 4, wherein the reactants are processed according to reaction injection molding tech-niques and wherein the alkyl radical R3 is a cyclohexyl radical.

19. The process of claim 4, wherein the reactants are processed according to reaction injection molding technique and wherein the alkyl radicals R1 and R2 are methylbutyl groups and R3 is a tertiarybutyl group.

20. The process of claim 4, wherein the reactants are processed according to reaction injection molding tech-niques and wherein R1 and R2 are a methyl- and R3 is a linear or branched octyl group.

21. The process of claim 4, wherein the reactants are processed according to reaction injection molding tech-niques and wherein R1 and R2 are a methyl- and R3 a cyclohexyl group.

22. The process of claim 4, wherein the reactants are processed according to reaction injection molding tech-niques and wherein the alkyl- substituted phenylenediamines are used as mixtures with chain extenders, secondary aromatic diamines and/or 3,3',5,5'-tetra-alkyl-substituted 4,4'- diamino-diphenylmethanes.

23. A molded polyurethane part prepared in accordance with the process of claim 4, wherein the reactants are processed according to reaction injection molding tech-niques.