United States Patent (19) (11) 3,835,191 Wagner Et Al

United States Patent (19) (11) 3,835,191 Wagner et al. (45) Sept. 10, 1974

54 ALDIMNES AND KETIMINES 2,394,530 2/1946 Bruson et al...... 260/566 R CONTAINING HYDROXYMETHYL GROUPS 3,420,800 1/1969 Haggis...... 260/566 R AND PREPARATION THEREOF 3,529,023 9/1970 Leshin...... 260/566 R 75 Inventors: Kuno Wagner; Manfred Hajek, both of Leverkusen, Germany OTHER PUBLICATIONS 73) Assignee: Bayer Aktiengesellschaft Layer, Chemical Reviews, Vol. 63, pg. 492 (1963) 22 Filed: Nov. 26, 1969 Primary Examiner-Leon Zitver (21) Appl. No.: 880,420 Assistant Examiner-Gerald A. Schwartz Attorney, Agent, or Firm-Connolly and Hutz (30 Foreign Application Priority Data Dec. 14, 1968 Germany...... 1814832 57 ABSTRACT 52 U.S. Cl...... 260/566 R, 260/77.5 AT, 260/464, Novel aldimines and ketimines which contain hydroxy 260/465 E, 260/465.5 R, 260/468 H, methyl groups are provided. These new compounds 260/468 J, 260/471 A, 260/482 R are prepared by reacting Schiff's bases which have ac (5ll Int. Cl...... C07 c 119/00 tive hydrogen atoms in a-position to the C=N-group 58 Field of Search...... 260/566 R, 468 H, 468 J, with formaldehyde or formaldehyde yielding com 260/471 A, 464, 465 E, 465.5 R, 482 R pounds. The new compounds can, e.g., be used as 56 References Cited plasticizing chain lengthening agents for the prepara UNITED STATES PATENTS tion of polyurethane plastics. 2,000,041 5/1935 Semon et al...... 260/566 R 11 Claims, No Drawings 3,835,191 1. 2 ALDIMINES AND KETIMINES CONTAINING in which HYDROXYMETHYL GROUPS AND PREPARATION R is an n-valent C-Cls saturated aliphatic radical, THEREOF an n-valent Ca-Co saturated alicyclic hydrocarbon, Mono- and polyketimines and aldimines have re cently attracted interest in the diisocyanate polyaddi tion process because they react as masked amines and polyamines with polyisocyanates or with masked poly isocyanates, the reaction resulting in chain lengthening or cross-linking. These ketimines, for example, react O with the polyisocyanates either via cyclo-addition reac tions of the azomethine group or in the presence of HC CHs moisture, with the formation of o-hydroxyamino com pounds. In addition, depending on the carbonyl compo CH nent in the ketimine, NH groups which are formed dur 15 ing the formation of enamines may react with the poly X.CH ( )-CH- { X- and isocyanates, so that when polyketimines react with HC CE polyisocyanates several reactions eventually take place -CH-CH-N-CH-CH-; simultaneously and these contribute to the chain lengthening or chain branching of the macromolecule. In practical terms, it is particularly the bisketimines, which are easily commercially available from many carbonyl compounds, and aliphatic, cycloaliphatic and araliphatic diamines, which exhibit serious disadvan tages in their reaction with polyisocyanates. Thus, very 25 wherein R and R2 are each selected from the group many ketimines have an unpleasant, amine-like odour consisting of (a) hydrogen, (b) C-C alkyl, which does not always completely disappear even after C-Cio cycloalkyl, substituted derivatives thereof the reaction with the polyisocyanates have been com wherein the substituent is cyanoethyl, -CH-CH pleted. Furthermore, ketimines obtained from aliphatic 2-CO-ORs, and cycloaliphatic polyamines are usually much too 30 highly reactive with aromatic polyisocyanates, so that -CH2-CH-CO-OR difficulties arise in working up. One particular disad &H, vantage, however, resides in the fact that in the pres ence of moisture, ketimines are not sufficiently stable O in storage for practical purposes, and that when keti 35 mines are deliberately used in the presence of moisture R5 O-C O-H-CH-co-o R5 the ketone component of the ketimine is partly re leased by way of the a-hydroxylamine which forms. wherein Rs is C-Cls alkyl or C4-Cio cyclalkyl and This not only results in unwanted softening effects in (c) hydroxymethyl; Ra and R are each selected from the resulting diisocyanate polyaddition products, but 40 the group consisting of hydrogen, C1-C18 alkyl, also results in the finished moulded articles having an unpleasant odour due to the ketone component liber C-Co cycloalkyl and hydroxymethyl; R2 and R3 when ated. taken together form a trimethylene bridge between the The invention relates to new ketimines and/or aldi carbon atoms to which they are attached; X is hydro mines which contain hydroxymethyl groups, the ketone 45 gen cyanoethyl, -CH,-CH,-CO-ORs, component of which containing hydroxyl groups, which are reactive with isocyanates, and which do not -CH-CH-CO-ORs, -CH-CH-CO-OR5 have the above mentioned disadvantages. H3 The present invention thus relates to hydroxyl containing aldimines or ketimines of the following gen 50 Ot eral formula

55 wherein Rs is as aforesaid; Y is hydrogen or hydroxy methyl and n is an integer from 1 to 2. N The following are examples of the compounds ac Y R cording to the invention l------GHot CEOH { H -(CH2)6-N-K H IO OE 2------{)--(D-on-O-ski)CHOH CHOH

3,835,191 5 6 2------O HC CH CH-CH-C-O CH x)-- X C H HOCH, CHOH YN HC-O-C-CH-CH,O CHO H CHO N/ (1210 c. in ca. 50% solution: 6,424 cp.). 18------O HC CH3 HOCH CH-CH- t–o CH

{-K)pH, HOCH CHO N C.H.O-(-CH-CHO CHOH H CH, OH

(n210 c. in 51% solution 8,450 cp.). 14------O HC CH HOCH CH-CH-8-0 CE N4- Y4 Krth. > HocácionX. X O N CH-O-(-CH.H.C CHO HOCH, H CHOH N/ (210 c. in ca. 53% solution: 10,500 cp.). 15.------CH3O-CO-CH-CH-CO-OCHal-K) CHOI

3H O N CH-C-O-CH BOCH &H (-oCH,

O 55 CH-OH,--O-cal, Compounds 1 to 9 are particularly valuable. HC Neg H > Hydroxymethyl-containing aldimines and ketimines HC sc - which are particularly valuable according to the inven- HOCH tion are those bases on hexamethylene diamine, iso- 60 CHOH pore diamine- and m-xylylene diamine,iamine, e.g. ththe fol - CH, CH-N H >

H-CH-C-O-CH 65 (7219 c. in ca. 48% solution 2,950 cp.).

... -- - T 3,835,191 7 O 3C CII CH-CH,--0 CH

3CX--> CH HOCH2CH2OH ch, N too--shotro /\ (nzio c. in ca. 49% solution 5,544 cp.). O CH 3 CH-CH2- -O Cho

{ pH,H > HocácioK.) H N O CHOH CHO - -CH-CH H CHOH

(nzio c. in 50% solution 6,424 cp.).

EO CH2 CH2OH HOH2C Cl2OH CH

&H,- HC CBOH HO-CH C3 Ca / N N CH HC CeN-R-N=C Ca NC-CH-CH-CH Hé-CH-CH-ON Ho &B, & HoH CHCH H3C CH2OH. HOCH2 CH CE

HOCH2CH2OH. HOCH2CH2OH. Y

H H-CH2CNst H-C-CN The insertion of hydroxymethyl groups into keti I mines and aldimines has not hitherto been known. Syn theses, e.g. by the condensation of various methylol ke Ho CH, H CHOH tones or permethylated ketones such as tetramethylol 55 -- HN-(CH2)6-NH. cyclohexanone, are unsuccessful since, according to HOCH2 CHOEI Mannich, Ber. 56, 833 (1923), the keto group cannot be made to react in the required manner with the usual carbonyl reagents such as phenyl hydrazine, hydroxyl Y. amine and semicarbazide. It has also been shown that 60 HO CB CIO HOCH CEO even pure tetramethylolcyclohexanone which is com pletely free from formaldehyde and which has a melt H a-N-CH2)6-N- E. -- 2 H2O ing point of 139C will not react in accordance with HOCH CHOI HOCH, CHOH equation I indicated below, for example with hexa methylene diamine, but reacts exclusively according to 65 equation II, an amorphous, white, insoluble reaction HO CH H CHOH product being formed from hexamethylene diamine and formaldehyde, namely the well known three HO CH CHOH dimensionally crosslinked polymer of N,N'-bis O methylene hexamethylenediamine. 3,835, 191 9 10 - CH-CH-CO-Rs or Rs Q-CO-C-C-C - Rs. () CHs Y O 5 wherein Rs is as Surprisingly, it has now been found that many differ aforesaid, and n is an integer from 1 to 2, at -10 to ent organic condensation products of aldehydes or ke 150°C with a compound selected from the group con tones and amines, provided that they contain at least sisting of formaldehyde, semiacetals of formaldehyde one ketimine and/or aldimine group in their molecule and substances which give off formaldehyde which (Schiff's bases) react very easily and in almost quanti 10 compound has a maximum water content of 3 percent tative yields with formaldehyde, retaining their azome by weight. thine group and forming new ketimines and aldimines The quality of and the absence of water in the mono which are partially or quantitatively hydroxyme meric formaldehyde is often of great importance for thylated in the o-position to the azomethine group. carrying out the process of the invention. The maxi New ketimines with hydroxyl group content can be pre 5 mum water content of the gaseous formaldehyde, pared in this way particularly in the polyketiminese semiacetals of formaldehyde and/or compounds which ries. These new ketimines represent important reac split off formaldehyde should be 3 percent by weight. tants for the diisocyanate polyaddition process. Preferably these compounds have a maximum water The invention thus also relates to a process for the content of 0,5 percent by weight. Most preferably.an preparation of hydroxymethyl-containing aldimines 20 hydrous gaseous formaldehyde is used. The water con and ketimines, which consists in that Schiff's bases of tent is of greatimportance especially in the case of keti the general formula mines which are particularly sensitive to hydrolysis. The reaction according to the invention can be carried out with gaseous formaldehyde, paraformaldehyde, 25 oligomers or polymers of formaldehyde or with semia cetals which may be monovalent or polyvalent semia cetals, e.g. semiacetals of monomeric formaldehyde and methanol, ethanol, propanol, butanol, ethylene glycol, diethylene glycol, triethylene glycol, glycerol, 30 and hexanetrio, (see examples). In general, formaldehyde, semiacetals of formalde hyde and/or compounds which give off formaldehyde wherein R is an n-valent C-Cls saturated aliphatic may be used for the reaction with Schiff's bases accord radical, an n-valent C-Co saturated alicyclic hydro ing to the given formula. Monomeric, anhydrous, gase carbon, 35 ous formaldehyde, semiacetals of formaldehyde ob tained from formaldehyde and mono- or polyalcohols, p-formaldehyde and/or oligomeric and high molecular weight polyoxymethylenes which have not been stabi lized with regard to the end groups are preferred. 40 The process according to the invention may be car ried out in the absence or presence of inert solvents C CH3 such as benzene, toluene, xylene, butylacetate or car bon tetrachloride, at as a rule temperatures of -10° to 150°C and preferably attemperatures of 30°C to 70°C. CH 45 It is surprising that even when extremely pure formal dehyde is used, the very marked tendency of formalde (X,C <)-CH- ()- and hyde to undergo polymerisation is completely sup HC CE pressed, so that no formation of high molecular weight -CH-CH-N-CH-CH2-; polyoxymethylenes occurs in the process according to H 50 the invention; instead, readily soluble, hydroxyl bH, containing polyketimines and/or aldimines are ob tained which have excellent solubility in many organic solvents. R" and R', are each selected from the group consisting The ketimines and/or aldimines which may be used of (a) hydrogen, (b) C-C alkyl, Ca-Cio cycloalkyl, 55 as starting material for the process according to the in substituted derivatives thereof wherein the substituent vention, which have the following formula is cyanoethyl, -CH-CH-CO-ORs, X R. -CH-CH-CO-OR4 or RO-C o-bH-CH-C O-ORs 60 ^ CH R. NeC / Y', - wherein R is C-Cls alkyl or C-Cio cycloalkyl and R', R" and R', are each selected from the group consisting oé of hydrogen, C-Cls alkyl, Ca-Cio cycloalkyl, R" and 65 R' in R' when taken together form a trimethylene bridge be in which R, R', R', Ra', R', X" and n have the mean tween the carbon atoms to which they are attached; X ing already indicated above, can be prepared in known is hydrogen, cyanoethyl, -CH-CH-CO-ORs, manner by condensation or mixed condensation of ke

3,835,191 11 12 tones and/or aldehydes (with the exception of formal the addition products of acrylonitrile with monohydric dehyde) with primary mono- and/or polyamines. and polyhydric alcohols such as methanol, ethanol, bu These primary mono- and/or polyamines have the tanol, ethylene glycol, butanediol, hexanediol, bishy general formula droxyalkylated diols, neopentyl glycol, diethylene gly col, triethylene glycol, hydroquionone, and 4,4'- RNH) in which R and n have the meaning already dihydroxy-diphenyldimethylmethane and hydrogena mentioned above. tion products of cyanoethylated mono and polyamines The following are mentioned as examples of suitable in general. monoamines: Methylamine, ethylamine, propylamine, Among the polynuclear aromatic polyamines or poly isopropylamine, butylamine, isobutylamine, tertiary 10 amines which contain aromatic polyether radicals, it is butylamine, amylamine, allylamine, isoamylamine, particularly advantageous to use those which can be dodecylamine, tetradecylamine, 3-methoxy prepared e.g. by acid catalysed condensation of aniline propylamine, 3-sthoxy-propylamine, 3-butyloxy with formaldehyde and those which can be prepared propylamine, myristylamine, hexadecylamine, stearyl from bis-epoxides, e.g. from 4,4-dihydroxy-dimethyldi amine, cyclohexylamine, benzylamine, aniline, o-, m 15 phenylmethane and epichlorohydring by reacting them and p-toluidine, o-, m- and p-chloroaniline, o-, m- and with a large excess of e.g. ethylene diamine, tetrameth p-nitroanline, o-, m- and p-nitroaniline, and p ylene diamine, hexamethylene diamine, m- and p-xyl anisidine. yene diamine or isophorone diamine, i.e., polyamines The following are mentioned as examples of poly which have primary amino groups, additional hydroxyl amines: 20 Ethylene diamine, propylene diamine, 1,4- groups and secondary NH groups which are formed by diaminobutane, hexamethylenediamine, trimethylhex addition to the oxirane ring. amethylenediamine, diaminomethylcyclobutane (pre For the reaction with primary amines, aldehydes and pared by hydrogenation of dimerized acrylonitrile) di /or ketones of the general formula may be used ethylenetriamine, triethylenetetramine, tetrae 25 X R. thylenepentamine, pentaethylenehexamine, 1,2- ^ diaminopropane, dipropylene triamine, t - ^ Ye', propylenetetramine, 3-amino-1-methylaminopropane, OscC 3-amino-dimethylaminopropane, 3,3'-diamino N R dipropylamine, methyl-bis-(3-aminopropyl)-amine, 30 c? a,o-diamino-caproic acid methylester, hydrogenated y, thiodipropionic acid dinitrile, 3,3'- diaminodipropylether, propylene glycol polyethers in which R', R', Ra", R' and X" have the meaning al which contain primary amino end groups, which can be ready mentioned. obtained from oligomeric polymerisation of polyaddi 35 The following are mentioned as examples of alde tion products of propylene oxide (ethylene oxide) by hydes: Acetalydehyde, propionaldehyde, - reacting them with ammonia under pressure in the butyraldehyde, isobutyraldehyde valeric aldehyde, iso presence of nickel as catalyst, hydrogenated p valeric aldehyde, caproic aldehyde, oenanthaldehyde, phenylenediamine, hydrogenated 4,4'- formylcyclohexane, phenylacetaldehyde and hydrocin diaminodiphenyl methane, hydrogenated iamines of 40 namic aldehyde. 4,4'-diamino-diphenylether and 4,4'- The following are examples of suitable ketones: Ace diaminodiphenylthioether, m- and p-xylylene diamine, ton, methyl ethyl ketone, methyl-n-propyl ketone, di isophorone diamine, aromatic diamines such as 2,4- ethyl ketone, methylisobutyl ketone, methyl-n-amylke diamino-toluene, 2,6-diaminotoluene, 4-amino-2- tone, diisobutylketone, methyl-tertiary butyl ketone, acetylaminotoluene, dimethyl-(4-aminobenzyl)-amine, 45 methyl-n-heptyl ketone, aceylacetone, acetonyl ace 1,3-bisaminomethyl-4,6-dimethylbenzene, 2,4- tone, acetophenone, propiophenone, cyclopentanone, diamino-3,5-diethyltoluene, 2,6-diamino-3,5- cyclohexanone, 1-methyl-cyclohexanone-(2), 1 diethyltoluene, 2,4-diamino-1,3,5-triisopropylbenzene, cyclohexanedione-(1,4), acetylcyclohexanone and cy 4,4'-diamino-diphenylmethane, 4,4'-diamino clododecanone. diphenylether and -thioether, oligomeric polyamines 50 The Schiff's bases prepared from amines and alde which can be obtained by acid condensation of aniline hydes or ketones are particularly advantageous to use and formaldehyde, m- and p- phenylene diamine, 1,4- for the process according to the invention if they have and 1,5-napthylene diamine, 3,3'-diamino-3,3'- been partially cyanoethylated in the o-position to the dichloro-diphenylmethane, 4,4'-diamino-3,3'- azomethine group in known manner in a preliminary dichlorodiphenylether, 4,4'-diamino 55 reaction, e.g. with acrylonitrile. At least one hydrogen diphenyldimethylmethane, 1,1-bis-(4-aminophenyl)- atom which is reactive with formaldehyde should re cyclohexane, 4,4', 4'-triamino-triphenyl methane or main in the o-position to the azomethine group. Exam polyamines containing urethane groups or urea groups, ples of such Schiff's bases which are particularly pre which can be prepared e.g. by reacting p ferred are aldimines such as 2-(g-cyanoethyl)-N- nitrophenylisocyanate with low molecular weight poly 60 cyclohexylbutyral-dimine, 2-(6-cyanoethyl)-N- ols such as ethylene glycol, 1,4-butanediol, or hexane cyclohexyloenanthaldimine, 2-(6-cyanoethyl)-N-butyl diol or with diamines such as hexamethylene diamine butyraldimine, and 2-(6-cyanoethyl)-N-phenyl followed by hydrogenation. butyraldimine. These can be prepared e.g. by the pro Aminoalcohols and their derivatives may also be 65 cess in German Patent Specification 951,568. This pro used for preparing the Schiff's bases which are to be cess can also be applied to preparing many different cy used as starting material according to the invention, anoethylation products of different bisketimines of ali e.g. 2-aminoethanol, 3-aminopropanol, 4 phatic, cycloaliphatic, araliphatic or aromatic poly aminobutanol-(2), and the hydrogenation derivative of amines with aliphatic, cycloaliphatic or araliphatic ke

3,835,191 13 14 tones, or similarly, cyanoethylation products of mono in which ketimines such as N-cyclohexyl-2-((3-cyanoethyl)- Rs represents hydrogen or -CO-O-alkyl, cyclohexanoneimine, N-cyclohexyl-2,6-di-((3-cyanoe Rs represents a hydrogen, cyanogen or -CO-O-- thyl)-cyclohexanoneimine, N-n-butyl-2-(6-ctanoe alkyl radical and thyl)-cyclohexanoneimine, and N-phenyl-2-(6-cyanoe 5 X represents hydrogen or a methyl group attempera thyl)-cyclohexanoneimine. tures of between 10 and 150°C, optionally under The ketimines which are particularly advantageous pressure and optionally in an inert solvent. to use according to the invention are reaction products The Michael addition products of the above men of ethylene diamine, hexamethylenediamine, m- and tioned polarised vinyl compounds with bis-ketimines p-xylylene diamine, isophorone diamine, diethylene tri 10 obtained from the following compounds are of particu amine, triethylenetetramine and the diamine lar interest: Hexamethylene diamine and aceton, cyclo hexanone, methylisobutyl ketone and isophorone, and gll, ketimines formed from the same carbonyl compounds NH2-CH-CH-CH-N-CH-CH-CH-NH2 and diamines of trimethylhexamethylene diamine, m 15 and p-xylylene diamine, isphorone diamine, the methyl with acetone, cyclohexanone, isophorone and me ester of a,c-diaminocaproic acid, 2,4-toluylene di thylisobutyl ketone. amine, the tetramine of mol of formaldehyde and 2 Ketimines which have at least one or two hydrogen mols of toluylene-2,4-diamine, m-phenylene diamine, atoms in the a-position to the C atom of the C-N bond p-phenylenediamine, 4,4'-diaminodiphenylmethane are particularly suitable according to the process of the and 4,4'-diaminodiphenylether; also, the more strongly invention if the molecule contains several C=N groups. basic bis-ketimines of the above mentioned ketones Highly functional polyketimines and/or aldimines with (HN-CH-CH-CH), N-CH (= methyl-bis which contain hydroxyl groups can then be prepared. (3-aminopropyl) amine, or with aromatic polyamines In view of the preferred use of the products of the which contain more than three or four amino groups, process as reactants for mono and polyisocyanates, the 25 such as can be obtained by acid condensation of aniline most advantageous ketimines and/or aldimines to use and formaldehyde, and the higher molecular weight are those which are, in general, partially substituted in polyamines of polyepoxides, e.g. those based on 4,4'- the o-position to the azomethine group by Michael ad dihydroxy-diphenyldimethylmethane and epichlorohy dition, e.g. with acrylonitrile, methyl acrylate, ethyl ac dring after their reaction with aliphatic, cycloaliphatic rylate, propyl acrylate, buty acrylate, methylmethac 30 or aromatic polyamines. rylate, ethylmethacrylate, 6-hydroxyethylacrylate, One embodiment of the process according to the in (3-hydroxyethylmethacrylate, 6-hydroxypropylacrylate, vention which is often of advantage consists of carrying g-hydroxypropylmethyacrylate, acrylamide-N- out the hydroxymethylation reaction as a one-stage methylolmethylether, N,N-dimethylacrylamide, vinyl process together with the Micael additions of ethyleni chloride, methyl vinyl sulphone and diesters of maleic 35 cally unsaturated compounds; this may advantageously and furmaric acid and particularly their bis-hydroxy es lead to a great increase in solubility of compounds ters which may be prepared, for example, by known which contain several methylol groups. This coupling methods from 1 mol of maleic acid anhydride and 2 of the process according to the invention is possible mols of ethylene glycol or diethylene glycol, trimethy since anhydrous purified formaldehyde, of course, does lene glycol, 2,2-dimethylpropane-1,3-diol, glycerol, tri 40 not react with vinyl monomers under the conditions of methylolpropane or thiodiglycol. The above mentioned the process of the invention, and therefore, the hydrox compounds obtained by Michael additions, with the ymethylation reaction proceeds undisturbed in one exce-ption of the cyanoethylation products, can conve step, together with the particular addition of vinyl niently be obtained e.g. by reacting monoor polyimines monomer chosen. of the formula 45 Another important embodiment of the process of the invention which is particularly suitable for affecting the R. solubility and particularly the viscosity of the products of the process, consists of carrying out the hydroxymet hylation reaction coupled with the Michael addition, inL l, R. 50 with simultaneous addition of radical forming agents, for example employing the technique described in Ger in which man Patent Application P 17 20 747.5 of telomerisa R has the meaning given above, tion of ethylenically unsaturated compounds with poly R represents hydrogen, alkyl, cycloalkyl, aralkyl or isocyanates. In this method, the Michael addition is ac aryl radicals or, together with Rs form a tetrameth 55 companied by polymerisation which has the effect of ylene bridge between the carbon atoms to which greatly increasing the viscosity of the products of the they are attached process. Therefore, such telomerisations may be used R, R and R independently of each other represent for exerting a controlled influence on the levelling hydrogen, alkyl, cycloalkyl, aralkyl or aryl radicals properties, capacity for pigmentation and reduction in with the restriction that one of these radicals must 60 reactivity of the ketimines according to the purpose for be hydrogen, and which they are to be used and, thereby, also greatly in in represents an integer of from 1 to 2, with an elec crease their stability to atmospheric moisture in stor trophilic olefin of e.g. the formula age, which is very advantageous for many purposes. The present invention makes available for the first 65 time a large number of hydroxyl-containing aldimines and ketimines which cannot be prepared by other methods. They are important products. Thus, for exam ple, hydroxyl-containing polyaminophosphonic acid 3,835, 191 S 16 esters which are valuable flame-protective agents are mine has disappeared and a slight lightening of colour obtained by the action of diethylphosphite on the com and slight increase in viscosity are observed in the keti pounds according to the invention. In this reaction the mine which now contains hydroxyl groups. Another 30 diethyl phosphite is added in exothermic reaction to parts by weight of monomeric formaldehyde are intro the asomethylene double bond. Furthermore the action duced in the course of another hour. After 2 hours, a of carbon disulphide on the compounds according to moderately viscous bis-ketimine is obtained which is the invention leads to polymers which are also impor practically odourless and contains an average of two tant e.g. in the field of synthetic resins. Additional eth hydroxymethyl groups per mol of bis-ketimine. When erification, acetalisation and esterification reactions via another 60 parts by weight of monomeric formalde the hydroxymethyl groups are also possible. The prod 10 hyde are introduced into the reaction vessel, the reac ucts of the process are particularly important as start tion continuously progresses with a progessive increase ing compounds for the polyaddition of ethylene oxide in the viscosity of the bis-ketimine poly alcohol. In or propylene oxide, optionally after previous hydroge order to achieve a maximum degree of hydroxymethy nation of the azomethine groups, whereby a large num lation, the reaction mixture is now diluted with approx ber of new starting compounds become available for 15 imately 456 parts by weight of anhydrous xylene and a the preparation of basic polyols which are completely further 60 parts by weight of monomeric formaldehyde odourless and very stable in storage. are introduced, the temperature being kept at about According to another embodiment of the process of 552C. A clear, yellowish, approximately 50 percent so the invention, the compounds according to the inven lution of a hydroxymethilated bis-ketimine which has tion are not prepared in bulk or in solution in inert sol 20 the following theoretical constitution is obtained: vents such as methylene chloride, chloroform, butyl ac etate, dibutylether, cyclohexane, benzene, toluene, and xylene, but in linear or branched polyols such as poly CH2OH. CHOH ols which contain ester, ether, thioether or acetal groups, e.g. linear or branched propylene glycol poly 25 H >=N-(CH)-N={ H ethers, because then they can be used directly with these compounds for subsequent isocyanate polyaddi CHOH CH, OH tion reactions. Furthermore, when employing such a procedure, the removal of solvents after the hydrox When measured as a 50 percent solution in xylene, this ymethylation reaction may be omitted. 30 product has a viscosity at 21°C of 4200 cP. The compounds according to the invention are above all valuable chain lengthening agents which may be Example 2 used as such with polyisocyanates and optionally higher This example illustrates the high reactivity of the ke molecular weight polyols, to yield new soft elastomeric timine prepared from 2 mols of cyclohexanone and 1 polyurethanes which have valuable properties. Due to 35 mol of hexamethylene diamine towards formaldehyde their side chains the new compounds when used as even when the reaction is carried out under reduced chain lengthening agents act simultaneously as chemi pressure. cally linked plasticizers. The process is carried out as described in Example 1 The parts given in the following Examples are parts but using a monomeric formaldehyde which is pyro by weight unless otherwise indicated. 40 lysed at a total pressure of about 150 mm Hg at a tem Examples perature of about 120°C. On leaving the pyrolysis ves sel, the resulting nomomeric formaldehyde gas is di Example 1 luted with nitrogen and toluene vapour until the for The anhydrous formaldehyde required for carrying maldehyde partial pressure is about 100 mm Hg. This out the hydromethylation is prepared as follows: 45 gas mixture then flows through a scrubbing flask which Monomeric formaldehyde is obtained in known man is filled with toluene and kept at a temperature of 35°C, ner by thermal decomposition of paraformaldehyde, and from there it is introduced into the bis-ketimine of e.g. in o-dichlorobenzene and mixed in the pyrolysis Example 1. In this procedure, the inlets to the reaction vessel with pure, dry nitrogen as carrier gas. The for vessel and the washing liquid remain free from prepoly maldehyde is then conducted through an extensive 50 mers of formaldehyde. Although the process is carried cooling system of about -10° to -5°C and continuously out at a total pressure of only about 150 mm Hg, the introduced into the reaction vessel. formaldehyde introduced into the reaction vessel is im Monomeric formaldehyde is continuously introduced mediately absorbed by the bis-ketimine. When about 2 with vigorously stirring into 276 parts by weight of a moles of monomeric formaldehyde has been intro liquid bisketimine prepared from 2 mols of cyclohexa 55 duced, further supply of formaldehyde is stopped and none and 1 mol of hexamethylene diamine. Hydrox a pale yellow hydroxymethylated bisketimine of the fol ymethylation in the o-position to the azomethine group lowing theoretical constitution is obtained. sets in at once with exothermic reaction at a rate de pending on the rate at which the formaldehyde is intro duced. There is no formation of insoluble, high molecu 60 CH2OH. HOCH2 lar weight polyoxymethylenes from the start of the re action to the end of introduction of formaldehyde. The { H. :--en-ski> reaction temperature is kept at 40°C by cooling with water, and when 30 parts by weight of monomeric for This has a viscosity of 480 cp at 21°C and has excellent maldehyde have been introduced, a sample is removed 65 miscibility with all polyisocyanates, and when reacted for analytic determination of the HO contact. Even with polyisocyanates in equivalent quantities of OH after the introduction of only one hydroxymethyl group and ketimine groups it yields a highly cross-linked com the unpleasant amine-like odour of the starting keti pletely insoluble synthetic resin. 3,835, 191 17 18 Example 3 When this solution is treated with a biuret triisocya Anhydrous formaldehyde is produced as described in nate mixture of 1-methylbenzene-2,4-diisocyanate in Example 1 and introduced at about 40°C into 60% by an equivalent quantity as regards the hydroxyl groups, weight solutions in xylene of a completely cross-linked insoluble synthetic resin is a) 201 parts by weight of the ketimine formed from 5 obtained. 1 mol of benzylamine and 1 mol of cyclohexanone, Example 5 b) 187 parts by weight of the ketimine formed from Anhydrous formaldehyde is produced as described in 1 mol of aniline and 1 mol of cyclohexanone, Example 1 and is introduced continuously at about c) 386 parts by weight of the bis-ketimine formed O 50°C into a solution of 220 parts by weight of the poly from 1 mol of 4,4'-diamino-diphenylmethane and Schiff's base of 2 mols of butyraldehyde and 1 mol of 2 mols of cyclohexanone. hexamethylenediamine in 310 parts by weight of gly A total of 60 parts by weight of monomeric formalde col monoethylether acetate. A total of 3.1 mol of hyde is introduced and the reaction mixture is kept at formadehyde is taken up in the course of 4 hours. An 60°C for 3 minutes after the introduction of formalde 15 approximately 50 percent solution of a hydroxy hyde is terminated. Approximately 50 percent solution methylated poly Schiff's base which is hydroxy of hydroxymethylated ketimines which are hydroxyme methylated with an average of 3 mols of formalde thylated with an average of 2 mols of formaldehyde per hyde per mol and which has the following theoretical mol of ketimine and which have the following theoreti constitution cal constitutions are obtained: 20 H. H. H CHOH a) ------CHoH CH-CH---N-(CH)-N-(-)-CH-CH,&HOH &H,0H HOH 25 (naic: 198 cP in 50% solution) (n loc in 60% solution 230 cF) is obtained. b) CHOH Example 6 30 Anhydrous formaldehyde is produced as described in ( )-N-( ) Example 1 and is introduced continuously at about HOH 40°C into a mixture of 196 parts by weight of a bis (n loc in 60% solution 285 cF) ketimine formed from 2 mols of acetone and 1 mol of hexamethylenediamine and 265 parts by weight of xy c) CHOH CHOH 35 lene. When 60 parts by weight of formaldehyde have been introduced, the unpleasant odour of the starting material has completely disappeared. A partially hy {)--O-et-O- droxyalkylated ketimine of 2 mols of acetone and 1 mol (n loc in 60% solution 420 cp) <> of hexamethylene diamine is obtained which has the 40 following theoretical constitution: Example 4 Ho-Ho-Hic CH-CH2O Anhydrous formaldehyde is produced as described in C=N-(CH2)6-N=C Example 1 and is introduced continuously at about off, CH3 30°C into a solution of 250 parts by weight of the poly 45 Schiff's base formed from 1 mol of m-xylylene diamine (n loc: 210 cp in ca. 50% solution). and 2 mols of isobutyraldehyde in a mixture of When this is further worked up into polyurethane xylene/ethylglycol acetate (1:1). A total of 60 parts by resins, it has no amine-like odour. weight of monomeric formaldehyde is introduced and the reaction mixture is kept at 60°C for one hour after 50 introduction of formaldehyde is terminated. An ap Example 7 proximately 50 percent solution of the polyaldimine is The examples summarised here show that, even with obtained. The solution is completely free from formal slight partial oxymethylation reactions, it is possible to dehyde and the polyaldimine contains an average of 55 prepare mixtures of hydroxyalkylated ketimine or aldi two hydroxymethyl groups per molecule and has the mines with the starting materials, in which the amine following theoretical constitution: like odour has completely disappeared and which have great stability in storage and are compatible and misci H CH ble in solution with all industrially important polyisocy -CH-N-(-)-CH, OH 60 anateS. s Anhydrous formaldehyde is produced as described in Example 1 and 0.05 mol of this formaldehyde is intro duced into 0.1 mol of the following ketimines or aldi C mines: 65 a. Bis-ketimine formed from 1 mol of propylene-1,3- to diamine and cyclohexanone &H, b. bis-ketimine formed from m-xylylene diamine and (n 21°o in 50% solution=210 cB) cyclohexanone 3,835, 191 19 20 c. bis-kctimine formed from tetramethylene diamine ily pourable hydroxymethylated and cyanoethylated and cyclohexanone polyketimine mixture is obtained which has a viscosity d. bis-ketimine formed from isphorone diamine and at 21°C of 3820 cP, whereas the starting ketimine cyclohexanone which is not hydroxymethylated has a viscosity of 640 e. mono-ketimine formed from allylamine and cyclo 5 cP at the same temperature. It has the theoretical con hexanone stitution: f. mono-ketimine formed from cyclohexylamine and cyclohexanone (a) CHO g. bis-ketimine formed from 1 mol of hexamethylene diamine and 2 mols of acetone 10 h. bis-ketimine formed from 1 mol of hexamethylene diamine and 2 mols of methylisobutyl ketone HaOH i. bis-ketimine formed from 1 mol of hexamethylene (n 21cc in 60% solution 230 cp) diamine and 2 mols of methylethyl ketone j. bis-aldimine formed from 1 mol of hexamethylene 15 diamine and 2 mols of n-butyraldehyde (b) CHOH k. bis-ketimine formed from 1-methyl-2,4- diaminobenzene and 2 mols of cyclohexanone in 50 ( >-N-(E) percent xylene solution O l. bis-ketimine formed from 4,4'- 20 diaminodiphenylmethane and 2 mols of cyclohexanone (n loc in 60% solution 285 cP) in a 50 percent solution of xylene m. bis-ketinnine formed from 4,4'-diamino (c) CHOH CHOE diphenylether and 2 mols of cyclohexanone n. poly-ketimine formed from higher molecular 25 weight anilineformaldehyde condensates with 5 mols of cyclohexanone in 50 percent xylene/ethyl glycol ace (naic in 60% solution 420 cP). tate solution (1,1) A viscosity increase of about 3200 cF results from o. bis-ketimine formed from 1 mol of hexamethylene the hydroxymethylation reaction. Solutions of this cya diamine and 2 mols of cyclohexanone substituted with 30 noethylated and hydroxymethylated bis-ketimine in an average of 2 cyano ethyl radicals per molecule ethyl acetate, xylene, ethylglycol acetate and butyl ace p. bis-ketimine formed from 1 mol of diethylene tri tate are extremely stable in storage and compatible amine and 2 mols of cyclohexanone which is cyanoeth with any industrially important polyisocyanates. ylated predominantyl on its NH group, q. bis-ketimine formed from 1 mol of triethylene tet 35 Example 9 ramine and 2 mols of cyclohexanone substituted with The process is carried out in the same way as de an average of 2 cyano ethyl radicals on both its NH scribed in Example 8 and the semiacetal of formalde groups hyde is used for hydroxymethylating a cyanoethylated r. bis-ketimine formed from 1 mol of hexamethylene ketimine which has been prepared from 1 mol of hexa diamine and 2 mols of methyl isobutyl ketone substi 40 methylene diamine and 2 mols of methylisobutylketone tuted with an average of two cyanoethyl radicals in the o-position to the ketimine group. is known manner and has subsequently been cyanoeth Although in Examples a... to r. formaldehyde is intro ylated with 2 mols of acrylonitrile. 358 parts by weight duced in very much less than the equivalent quantity so of this bis-ketimine are reacted with a total of 60 parts 45 by weight of formaldehyde, and after complete removal that there are obtained only solutions of partially hy of methanol in a water jet vacuum a bis-ketimine is ob droxymethylated ketimines in an excess of bis tained which is substituted with hydroxymethyl and cy ketimines which have not reacted with formaldehyde, anoethyl radicals and which is easily pourable even in the unpleasant amine-like odour has practically disap the absence of solvents and which, even at a concen peared, or at least been very much reduced in experi 50 stration of 100 percent, has a viscosity of only 8500 cp ments a., b., c., g., h., ii., j., o., p., q., and r whereas in at 21°C. In its 100 percent form it has no unpleasant experiments d., f., m. and n. the colour of the ketimine odour and can be mixed with any industrially important solutions is observed to be very much paler. polyisocyanates and caused to undergo polyaddition. It Example 8. has the following theoretical constitution: 60 parts by weight of anhydrous formaldehyde which 55 CH-CH-CN has a water content of about 0.9 percent calculated CH-CH-CN &H-CHOH from the end groups are dipolymerised in methanol at CH &H-CHOH CH3 about 65°C, using catalytic quantities of sodium hy droxide. The monomeric formaldehyde is present Hi-CH-3-N-(CH) 8-N- -CH&H mainly as semiacetal in the methanolic solution. The 60 solution is filtered and then introduced dropwise in the course of 2 hour in an atmosphere of nitrogen and with vigorours stirring into 380 parts by weight of a ketimine Example 10 formed from 1 mol by hexamethylene diamine and 2 The procedure is carried out as described in Exam mols of cyclohexanone which has an average of one cy 65 ples 8 and 9, and the liquid semiacetal of formaldehyde anoethyl group in the o-position to the ketimine and methanol is used for hydroxymethylating a cyano groups. The reaction mixture is then stirred for 2 hours ethylated ketimine which has been prepared from 1 at 45°C and the methanol is completely removed in a mol of diethylene triamine and 2 mols of cyclohexa water jet vacuum under nitrogen. A golden yellow, eas none and has been subjected to subsequent cyanoeth

3,835,191 21 22 ylation with 3 mols of acrylonitrile and which is sub Example 12 stantially free from secondary NH groups. 421 Parts by The examples summarised below illustrate another, weight of this bis-ketimine are reacted with a total of technically simplified variation of the process by means 60 parts by weight of formaldehyde in accordance with of which a high degree of methylation can be achieved Example 9 and then worked up as described in Exam- 5 in the ketimines and aldimines which are reacted. ple 9. A hydroxymethylated, and cyanoethyl-containg In a three-necked flask equipped with stirrer, ther bis-ketimine is obtained which is easily pourable at mometer and nitrogen inlet and an azeotropic water room temperature even in the absence of solvents, and separator with additional reflux cooler, the following which has a viscosity of only 3700 cp at 21°C, and partially cyanoethylated bis-ketimines are reacted with which can be mixed and reacted with any polyisocya- 10 120 parts by weight of commercial, practically anhy nates withou precipitation. It has the following theoret drous paraformaldehyde at 90°C and freed from small ical constitution: quantities of water which are held by adsorption and from water which is formed on the end groups by para CHOH CHOH 15 formaldehyde decomposition: a. 434 Parts by weight of a bis-ketimine formed from m-xylylene and 2 mols of cyclohexanone which has H =N-CH-CH-N-CH-CH-N-(HC&H, an average of 2 mols of cyanoethyl groups. F. EI b. 412 Parts by weight of a bis-keimtine formed from ÖH,-CN E2 &H-CN isophorone diamine (=1-aminomethyl-5-amino 2 &N 2 20 1,3,3-trimethyl-cyclohexane) and 2 mols of me thylisobutyl ketone which contains an average of 2 Example 11 cyanoethyl groups per mol c. 406 Parts by weight of a bis-ketimine formed from The same procedure is employed as described in Ex- 25 1 mol of m-xylylene diamine and 2 mols of methyl ample 10 and the liquid semiacetal of formaldehyde isobutylketone which has an average of two cyano and ethanol is used for hydroxymethylating a bis ethyl groups per mol ketimine which has been prepared from 1 mol of m d. 380 parts by weight of a bis-ketimine formed from xylylene diamine and 2 mols of cyclohexanone and has 1 mol of hexamethylene diamine and 2 mols of cy then been cyanoethylated with an average of 2 mols of 3 clohexanone which has an average of two cyano acrylonitrile. 434 Parts by weight of this ketimine are O ethyl groups per mol. reacted with 60 parts by weight of formaldehyde (as its Sufficient xylene to produce approximately 50 per semiacetal dissolved in ethanol). The process is carried cent by weight solutions are added to ketimine a... to d., out as described in Example 10 under a nitrogen atmo and 120 parts by weight of commercial paraformal sphere, and, after removal of ethanol, an almost trans 35 dehyde are added to the bis-ketimines in each case. parent bis-ketimine, which is substituted with hydroxy The reaction mixture is rapidly stirred for about 10 methyl groups and with cyanoethyl groups, is obtained. minutes at room temperature and the reaction temper The 100 percent bis-ketimine has a biscosity of approx ature of the suspension is then increased to about 90°C imately 29,900 at 21°C and is soluble in any amount in under a completely nitrogen atmosphere. A slightly ethyl acetate, ethyl glycol acetate, butyl acetate, ben 40 exothermic reaction sets in at about 65° to 70°C, para zene and xylene and can be reacted with polyisocya formaldehyde slowly going into solution and mono nates to undergo a polyaddition reaction. It has the fol meric formaldehyde immediately having a hydroxyme lowing theoretical constitution: thylating effect. Due to the relatively large quantity of heat of depolymerisation required for paraformal 45 dehyde, the overall reaction is only slightly exothermic. CHOH The clear solution is stirred at 70 to 90°C for about 3 hours, and small quantities of water are removed azeo tropically under a slight vacuum, again in a nitrogen at mosphere. The readily soluble bis-ketimines which 50 have a high degree of hydroxymethylation are ob CH-ON tained. They have the theoretical constitution shown in Ha the Table and can be caused to undergo polyaddition with isocyanates both in solution and in bulk.

TABLE 1. Wiscosity, 50% soli tions in No. Theoretical constitution R xylene 1------HO CH, CHOE HOB,C CH2OH. 230 cp. ------. CH

NC-C-CH<-- H-CH2CNH > B 2 2------HC CEOH HO-Ca CH3 CH 380 cp. N / G H3C CH-ce Cs-N-R-N-C sc–ct CH3 C 3 : B NC-CH-CH-bH Hd-CH-CH-CN HobH, H2OH. CH, CH, 3,835, 191 23 24 TABLE 1 - Continued Viscosity, 50% solui tions ill No. Theoretical constitution xylene 8------IC CBOEI IOCEI. CEis 200 cp. Yo-off YoH-c? CH- p Hs c^ Yo-N-R-N-01 YoH, NC-CHCH-CH HC-CH-CH-CN Hot H, ÖH.OH &B, 4------HOC CHOI BIO CH2 CHOE 140 cp. N-(CH2)6-N-? X H-C-CN -C-CN

Example 13 droxymethylated polyketimines have the theoretical The procedure is carried out as described under a), constitution shown in Table 1 under Nos. 1, 2, 3 and 4. b), c) and d) in Example 12.60 Parts by weight of para 20 The solutions can be reacted with 1-methyl-benzene formaldehyde are used and the xylene used in these ex 2,4-diisocyanate, isomers and 4,4'-diisocyanato amples is replaced by a branched propylene glycol diphenyl methane without separation of the compo polyether for the preparation of which trimethylol nents or precipitation of the bis-ketimines, elastic, propane was used as starting compound. The hydroxyl cross-linked synthetic resins being obtained. group content is approximately 1.9 percent. Approxi 25 Example 15 mately 552 parts by weight of this polyether are used as solvent, and after carrying out the hydroxymethyla 590 parts by weight of bis-ketimine formed from 1 tion, the solution or mixtures are freed from small mol of isophorone diamine and 2 mols of cyclohexa quantities of water in a waterjet vacuum. The solutions none which has an average of 2 6-carbobutoxyethyl can be reacted with 1-methyl-benzene-2,4-diisocyanate 30 radicals per mol (prepared by the addition of butyl ac and its isomers without separation of the components rylate) are dissolved in 710 parts by weight of a poly or precipitation of the hydroxymethylated polyketi ether which has been prepared from glycerol and tri mines. Cross-linked, elastic synthetic resins are ob methylolpropane (1:1) as starting material and propy tained from the reaction. The hydroxymethylated poly lene oxide/ethylene oxide (10:1) (OH number 46, vis 35 cosity at 21°C = 654 cP). Hydroxymethylation was car ketimines have the theoretical constitution of the for ried out as in Example 13 with the following parts by mulae shown under No. 1, 2, 3 and 4 in Table 1. weight of paraformaldehyde: a. 60 Parts by weight of paraformaldehyde Example 14 b. 90 parts by weight of paraformaldehyde The procedures described in Example 12 under a), 40 c. 120 parts by weight of paraformaldehyde b), c) and d) are employed, using the parts by weight d. 150 parts by weight of paraformaldehyde of bis-ketimines indicated there, and the same parts by e. 180 parts by weight of paraformaldehyde. weight of paraformaldehyde but xylene is replaced by After hydroxymethylation has been carried out, small approximately 550 parts by weight of linear polyacetal quantities of water are removed in a water jet vacuum of diethylene glycol, bis-hydroxyalkylated butane-1,4- 45 at 90°C. diol and formaldehyde with hydroxyl content of 2.6 In all cases a) to e) solutions of partially to highly hy percent. After the formaldehyde addition, clear, ap droxymethylated bis-ketimines which are transparent proximately 50 percent solutions of hydroxymethylated at 20 to 60°C are obtained. The bis-ketinines have the bis-ketimines in linear polyacetal are obtained. The hy following theoretical constitutions:

(a)---- O CH-CH-C-O-CH HC Ns H HC OC 2 phot CH "-->H-CH-C-O-CH

(210 c. in ca. 48% solution 2,950 cp.). 3,835, 191 25 26 (b)---- O EC CH3 CH-CH-i-o CH X > X EI > HC gil, HOCEI CEO N O HC-O-C-CH-CH -CH2OH. B.

(1910 c. in ca. 49% solution 5,544 cp.). (c)---- O HgC CH CH-CH-8-0 CH

2 D-X)HOCH CEO l cho--CH-CH /\ CHOH H. : CHOH

(7210 c. in 50% solution 6,424 cp.). (d)---- O HC CH HOCH CH-OH,--0 CHg

H N H ph, Hoch, CHOH N ch,0--CH-CHO CH,OH H CHOH

(nzio c. in 51% solution 8,450 cp.).

(e)---- HOCH2 O HC CH3 CH-CH-6-0 Co N Z

(>{22 CH2OH. O HOCEI. CH-O-C-CH2-H2C(-CH-Hic CHOH HOCH-Yl a CH2OH. (7210 c. in ca. 53% solution 10,500 cp.).

When the solutions are reacted with equivalent quan none which has been modified by the addition of 2 mols tities of 1-methylbenzene-2,4-diisocyanate, 4,4'- 55 of dimethylmaleate are dissolved in 710 parts by weight diisocyanate diphenylmethane and or their commer of a polyether which has the composition described in cially available isomers of 4,4'-diisocyanato Example 15. Hydroxymethylation is then carried out as diphenylether, cross-linked synthetic resins are ob described in Example 13 with the following parts by tained. weight of paraformaldehyde: If the bis-ketimine of this example is replaced by the 60 a. 60 Parts by weight of paraformaldehyde corresponding 6-carbethoxy-ethyl- and b. 90 parts by weight of paraformaldehyde g-carbopropoxyethyl-substituted derivatives, the cor c. 120 parts by weight of paraformaldehyde. responding hydroxymethylated bis-ketimines are ob After hydroxymethylation with paraformaldehyde, tained. small quantities of water are removed in a water jet 65 vacuum at 90°C. Example 16 In all cases a) to c) solutions of hydroxymethylated 584 Parts by weight of a bis-ketimine formed from 1 bis-ketimines which have the following theoretical mol of m-xylylene diamine and 2 mols of cyclohexa constitution are obtained: 3,835,191 27 28 O-CH O (a) 2. The compound according to claim 1 having the o=(-CH-CH-8-0 CF formula on KD CHOI CHOE CHOH K H a-N-(CH2)6-N H O N CH-i-o-CH, OH OH HOCE B O 3. The compound according to claim 1 having the (-o CH3 formula

b. as a) with approximately 3 hydroxymethyl groups CHOH CEO and c) and 15 a. but with approximately 4 hydroxymethyl groups. When the solutions are reacted with equivalent quan tities of 1-methylbenzene-2,4-diisocyanate, 4,4'- diisocyanato-diphenylmethane of their commercially available isomers or 4,4'-diisocyanato-diphenylether, 20 4. The compound according to claim 1 having the cross-linked synthetic resins are obtained. formula if the bis-ketimine of this example is replaced by a bis-ketimine of the same diamine and ketone but which H CH has 2 mols of g-hydroxypropylmethacrylate of 6-hy droxypropyl acrylate per mol attached in the o-position 25 sportion&H, to the azomethine group, the corresponding hydrox H2 ymethylated bis-ketimines are obtained with parafor H CH3 maldehyde. N-b-c-CHOH What is claimed is: 1. A compound of the formula 30 5. The compound according to claim 1 having the formula 35 CH-CH--l-N-(CH)B. B. -N---CH-CH,CEO HOBI EOH

H2O2 6. The compound according to claim having the wherein R is (1) a divalent C-C saturated aliphatic formula radical obtained by removal of both primary amino groups from a member selected from the group consist CII-CIOE ing of ethylene diamine, propylene diamine, 1,4- / diaminobutane, hexamethylenediamine, trimethylhex 45 amethylenediamine, 1,2-diaminopropane, 3-amino-1- CH methylaminopropane, 3-aminodimethylaminopropane, 3,3'-diaminodipropylamine, methyl-bis-(3- 7. A process which comprises reacting a Schiff's base aminopropyl)-amine, a, co-diaminocaproic acid meth of the formula ylester, and 3,3'-diamino-dipropyl ether, (2) divalent 50 C-Co saturated alicyclic hydrocarbons,

(3) 55 O (4) wherein R is (1) an n-valent C-C saturated aliphatic 60 radical obtained by removal of each primary amino and wherein R and R4 are each selected from the group from a member selected from the group consist group consisting of hydrogen, C1-C1s alkyl, Ca-Co ing of methylamine, ethylamine, propylamine, iso cycloalkyl and hydroxymethyl; R and Ra, when taken propylamine, butylamine, isobutylamine, tertiary butyl separately, are each selected from the group consisting amine, amylamine, isoamylamine, dodecylamine, tet of hydrogen, C-Cls alkyl, Ca-Cio cycloalkyl and hy 65 radecylamine, 3-methoxy-propylamine, 3-ethoxy droxymethyl and R2 and R3, when taken together, form propylamine, 3-butyloxy-propylamine, myristylamine, a trimethylene bridge between the carbon atoms to hexadecylamine, stearylamine, ethylene diamine, prop which they are attached. ylene diamine, 1,4-diaminobutane, hexamethylene

3,835,191 29 30 diamine, trimethylhexamethylenediamine, 1,2- diaminopropane, 3-amino-1-methylaminopropane, 3 -CH-H-c O-OR4 or RO-C o-di-CH-C O-ORs aminodimethylaminopropane, 3,3'-diamino CH dipropylamine, methylbis-(3-aminopropyl)-amine, o, 00,000, wherein Rs is C-C, co-diamino-caproic acid methylester, 3,3'- 5 alkyl or Ca-Cio cycloalkyl, R's and R's are each se diaminodipropylether, 2-aminoethanol, 3 lected from the group consisting of hydrogen, C-Cls aminopropanol, 4-aminobutanol-(2), (2) n-valent alkyll and C-Cio cycloalkyl, R', and R's, when taken C-Co saturated alicyclic hydrocarbons, together, form a trimethylene bridge between the car bon atoms to which they are attached; X is hydrogen, - 10 cyanoethyl, -CH2-CH-CO-ORs, (3)

------ch- O-OR or RO-CO-CE-CH-CO-OR (4) Ha 15 wherein Rs is as aforesaid and n is an integer from 1 to 2, at -10 to 150°C. with a compound selected from (5) the group consisting of formaldehyde, semiacetals of formaldehyde, paraformaldehyde and oligomeric and high molecular weight polyoxymethylene, said com (6) pound having a maximum water content of 3 percent by weight. 8. The process of claim 7 wherein the reaction is car (7) -CH-CH-N-CH-CH ried out at a temperature of from 30 to 70°C. H 9. The process of claim 7 wherein anhydrous formal ch, 25 dehyde is used in the reaction with said Schiff's base. 10. The process of claim 7 wherein a semiacetal of formaldehyde obtained from formaldehyde and a mono- or polyalcohol is used. and wherein R', and R', are each selected from the 11. The process of claim 7 carried out in a hydroxyl group consisting of hydrogen, C-Cls alkyl, C-C cy containing solvent selected from the group consisting cloalkyl and substituted derivatives of said alkyl and of linear or branched polyethers, polythioethers, poly said cycloalkyl moieties wherein the substituent is cya acetals, polyesters and polycarbonates. noethyl, -CH2-CH-CO-ORs, ck k k k :