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