CA1047531A - Beta-amino carbonyl catalysts for polyurethane preparation - Google Patents

Abstract

BETA-AMINO CARBONYL CATALYSTS FOR
POLYURETHANE PREPARATION
ABSTRACT OF THE DISCLOSURE
Provided as catalysts for the formation of cellular urethane polymers ranging from flexible to rigid foams, are beta-amino carbonyl compounds wherein carbonyl is present as an amido or carboxylic acid ester group ant the beta-amino group is present as dialkylamino or an N- morpholino or N,N'-piperazino heterocyclic nucleus. Effective in the catalysis of the water isocyanate reaction, these beta-amino amides and beta-amino esters are used with particular advantage in the manufacture of water-blown flexible foams, both molded and free-rise, including high-resilience and flame-retarded foam. The beta-amino carbonyl catalysts allow for the formation of foam products essentially free of the odor associated with amines such as N-ethylmorpholine. In view of this highly desirable characteristic and their other beneficial properties, the catalysts of the invention are advantageously employed as direct replacements for N-ethylmorpholine in high-resilience and other foam formulations.
S P E C I F I C A T I O N

1.

Description

~04753~ 9149 BACXGROUND OF THE INVENTION
This invent~on pertaiDs to particular beta-am~no carbonyl compounds as cataly~ts for the formation of urethane polymers by the reaction of organic iso-cyanate~ with active hytrogen-containing compounds.
It is well known to the art that urethane polymers are provided by the reaction of organic poly-i~ocyaDates and active hydrogen-containing organic compcunds, usually in the presence of one or more acti-vators, and that blowing action i9 provitet when cellularprotucts incluting flexible, semi-flexible ant rigid foam~, are des1red. It is also known that a number of different chemical reactions occur during polymer formation ant expansion. For example, in addition to the chain-extenting, urethane-forming reaction between free iso-cyanate groups and active hydrogen, initially formet urethane linkages bearing secontary hytrogen may also function as a source of active hydrogeD and react with atdltional isocyanate to form cross-links between polymer chain~. Further, in water-containing systems such as those employed for the manufacture of flexible foams, i~ocyanate 19 also consumed by reaction with water, there-by generating carbon dioxite blowing agent in situ, and introducing further cross-links comprising urea groups.
The nature of the cellular structure and the physical and mechanical properties of ~he foam are lnfluenced by

2.

104'753i 9149 tha extcnt of such reactions, and the relativ~ rate~ ;
a~d po~nt i~ tlme at which they occur. Alth~ugh b~l~ncins the~e varlables 90 as to achieve a partlcular typ- sr grats o~ foam can be controlled to some extent by th functionality, molecular weight ant other struc-tural feature~ of the polyisocyanate and active hydrogen- ..
c~nt~ining reactaDts, the catalyst system also plays a ~igni~lcaDt role in this respect.
Among the relatively few ccmpounds that have achlsved widespreat ccmmercial application as catalysts in polyurethane ~anufacture are: ter~iary amlnes con-~lJting of carbon, hydrogen and nltrogen, as typically Jtrated b:y 1,4-diazabicyclo[2.2.2]octane ("tsi-~thylenediamine") ant N,N,N',N~-tetramethyl-1,3-butanedlamine; ant tertiary amines consisting of carbon, hytrogen, nitrogen ant oxygen wherein oxygen is present as other oxygen, a~ typlcally illu~tratet by bis[2-(N,N-dimethylamino)ethyl]ether ant N-ethylmorpholine. With p~rticular reference to the manufacture of flexible polyether polyol-ba3ed urethane foams, such tertlary a~ine~ are uJually c~ployed in combination with auxiliary catalysts c~mprising organic derivative~ of tin such as ~tanncu~ actoate and dibutyltin tilaurats, ia order to provide a synergistic activation of the chain-extending ~actlon.

A relatively rece~t advance in the area of flexibl- polyurethane foam technology which has triggered intenJive research effort to tevelop improved activators, is tha atvent of reaction mixtures having a sufficiently hi8h réactivity to provite more csmplete reactions during polyme~ formation and expansion, thereby eliminating the need in commercial practice to post-cure the foam at high temperatures (300-500~.) to obtain a product of satis-~actory overall properties. In addition to the saving in co~t which elimination of high temperature post-curing offers to the foam manufacturer, such highly reactive formulationJ al~o provite flexible foams of generally improved flammability characteristics, more linear and thu~ improved loat/deflection properties, l~w flex fatigue, and greater resiliency. In view of this latter characteristic, such products are referred to generally as high-re~llience foams. }n view of the aforesaid - combination of properties, high-resllience foam i~
- particularly suited as cushioning material in automotive interior~. In the production of at least a substantial proportion of high-resilience foam being manufactured at the present time, the aforementioned N-ethylmorphollne i9 u~ed a~ a ma~or component of mixed catalyst systems.
However, the usefulness of N-ethylmorpholine in the manu-factu~e of high-resilience foam as well as other types of cellular urethanes, i9 attented with certain dis-~ ~ 47 5 3 ~
atvaDtages. ~hu~, N-etkylmorpholine ~uffers the very seriou~ drawback of having a particularly strong amine otor. The large quantities of N-ethylmorpholine which are employed relative to other catalyst components of th~ foam formulation, causes an obnoxious atmosphere at and surrounding the foam manufacturing plant site and alsa provides foams having a strong residual amine odor.
- Thi~ compouDd i~ also associated with a number of seriou3 toxic effects; see, for example, Plastics Technolo~Y, '~atalyst~ Improve As Their Need Incre-ses" pages 47-49 (July 1972). Consequently, it i8 desirable and is a primary ob~ective of this invention to find a direct replacement for N-ethylmorpholine in the production of high-resilience foam in particular and cellular urethane manufacture generally ant thereby all~w for at least a sub~tantial reduction in the relatively large amounts presently employet. Various other ob~ects and advantages of the present invention will become apparent from the accompanying description and di3closure.
SU~MARY OF THE INVENTICW
In accordance with the teachings of the present invention, cellular polyurethanes are providet by effecting - reaction of active hydrogen-containin~ compounds and poly-isocyanates in the presence of a particular class of beta-amino carbonyl compounds as catalytic ccmponents of the urethane-forming reaction mixture. The catalysts employed 1()47 5 3~ 9149 i~ the practice of this invention consist of carbon-bonded nitrogen, oxygen and hydrogen atoms and contain at least one tertiasy nitrogen atom bonded to a carbon atom beta to th~ carbonyl group of an amido or carboxylic acid ester group. Tertiary nitrogen of the essential beta-amino carbonyl group i9 present in the molecule a-~ a dialkylamino gro~p or as a member of an N-heterocyclic nucleus which may contain additional hetero atoms such as oxygen or a second nitrogen atom. Overall, the beta-amino carbonyl compounds employed as described herein contain from 6 to 46 carbon atoms, from 1 to 4 nitrogen at~ms and fsom 1 to 4 oxygen atoms. Except for carbonyl oxygen, the remaining atoms are ~oined through single bonds and thus the catalysts employed in the psactice of this invention are free of multiple bond~ between ad3acent carbon atoms and ad~acent carbon and nitrogen atoms.
The aforesaid essential ~tructursl characteristics of the beta-amino amites and beta-amino esters employed as ~.
describet herein are conveniently expressed by the following general Formula I:

/ CmH2m+p\ ,, (Y) ~ / -CH-CH-C-Q ~I) ~ mN2m~P R3 R4 wherein, and as te~ined for the purpo~e of the entire specificatioD:
Y i8 an oxygen or nitrogen atom and, when Y i9 nitrogen, the remsiniDg valeDce thereof is satisfied by a bond to a ~econd -Ca(R3)CH(R4~C(O)Q group;

~0 ~7 5 3 ~

p and q each ha~ a value of zero or one, provided the sum ptq i8 one;
m i~ an integer having a valuè from 1 to 4, provided m ~ two when q i8 one;
a3 a~d R4 each represents hydrogen or a lower alkyl group and ma~ ~e the same as or different from one another; and Q i8 a member of the group consi~ting of an alkoxy group (-CR~) having from 1 to 8 carbon atoms, an N,N-dialkyl-amino group, -N~R5)(R6), where R5 and R6 each represent~
a lower alkyl group, or a 2-(N,N-dialkylamino)ethoxy group, -OC~2CH2N(R5)(R6)~ where R5 and R6 also represent lower alkyl radicals.
It i8 to ~e understood that the expression "lower alkyl" a8 used herein including the claims, denotes an alkyl ~adical having from one to four carbon atoms including linear and branched radicals (that i9, radicals of the series, CmH2m~p, wherein m is an integer frcm 1 to 4 and p is one).
lt has been discovered that the above-described beta-~mino carbonyl compounds are useful as catalytic components in the ~anufacture of a wide variety of cellular urethanes including products ranging from flexible to rigid foams. They are effective activators when used as the sole n~trogen-bearing catalytic component of fQam formulationQ, although their employment in combination with other tertiary a~ine~ i8 withi~ the scope of the present invention.
Especially effective in the catalysis of the water-iso-~ ~ ~7 5 3 ~

cyan~to reaction, these beta-amino amides and esters are used w;ith particular advantage in the manufacture of water-biown flexible foam~, both molded and free-rise, including hlgh-resillence foam. In addition to their versatility in this respect, they have the further highly to~irable characteristic of low residual odor and thus all~w for the formation of foam products essentially free of the poJt-cure odor associated with N-ethylmorpholine.
0ther beneficial properties include excellent mold-release characteristics, wide formulating latitude with respect to ccncentration of tin co-catalysts, ant ability to provite open-cell, porous foam from formulations containing an atted flame-retarting agent.
~ t i9 notet that, as a class, beta-amino amides and esters including specific compounts employed in the practice of thi~ invention are reported in the literature.
AJ far a~ i9 known, however, their ability to function as catalysts in cellular urethane polymer formation has not been previow ly reported. On the other hand~ certain of 2~ the beta-amino carbonyl compounts employed a~ catalysts in the practice of this invention are novel compositions.
The~e inclute: (1) the heterocyclic beta-amino amites encompas~et by ~ormula I, that i9, those compounds in which q is one and Q i9 an N,N-dialkylamino group;
(2) 3-dialkylamino-N,N-dialkylamides wherein the alkyl group~ bondet to amino nitrogen are different from those ~0~7S31 bonded to amido nitrogen; and t3) 3-dialkylamino-3-alkyl-N,N-dialkylamides wherein the various alkyL group~ ma~ be th- ~ame aJ or different fr~m one another.
The present invention also relates to particular Slend~ of the beta-amino carbonyl catalysts encompassed by Pormula I with other tertiary amines, the use of such ! blendJ a~ mixed amine catalyst systems for cellular poly- ;
urethane fonmation~ and to the cellular urethane polymers produced in the presence of the catalysts describet herein.
DETArLED DESC~IPTIoN 0~ THE INVENTIOW
AND PREFERRED EMBODIMENTS
(A) The Beta-Amino CarbonYl CatalYsts ~ ID generic Formula 1, the sum p+q is one and thus when q iJ zero, p must have a value of one. In the latt~r event, each CmH2m~p group shown in Formula I is a lower alkyl ratical, designated herein as Rl and R2, and the indicated valence of carbon which would otherwise ~e in a~ociation with Y i9 satisfied by the additional hydrogen atom present when p is one. The resulting saturated, acyclic beta-amino esters and amide~ have the moro ~pecific Formula 11:

1~ N-CH-CH-c-Q (II) ~ , ~
~2 When Q i~ an alkoxy group, the cataly~t~ encompassed by ~ormula lI sre alkyl beta-(dialkylamino)carboxylates .. . . ..

- 9149 .
~0 ~7 ~ 3 ~
haviDg the following Formula II-A:
o CH-CH-C-OR7 (II-A
2 ~3 R4 Whe~ Q o Formula. II is a 2-(N,N-di-lkylamino)ethoxy group, the catalysts are 2-(N,N-tialkylamino)eehyl 3-(N',N'-dlalkylamino)carboxylates having the following Formula II-B:

1~ N~cH-cH-c-o-cH2cH2N ~ (II-B) Purther, when. Q i9 an N,N-dialkylamino group, the cataly~t~
encompassed by Formula II, are beta-(dialkylamino)-N,N-d~alkylamides ant have the structure shown by the following Pormula II-C:
o 1~ N_cH_cH_c_N (II-C) ~2 ~ 6 In addition to the saturated, acyclic esters and amideJ shown specifically by Formulas II-A, II-8 and II-C, general Formula I also encompasses compounds wherein tertiary nitrogen is a memb;er of a morpholine or piperazine nucleu~. Such catalyst~ for use in the practice of this invention axe depictet by the following Formulas III and IV, respectively:
CH2-CH2\ '' 0 N-CH-CH-C-Q (III) \ CH2-CH2 ~ ~4 10.

~)4753i . .
O ~CH2'CH2\
Q-C-CH-CH-N N-CH-CH-C-Q (rV) /

wh~re~n the -C(O)Q group may be present as the ester groups 8~own ~n Formula~ II-A and II-B or the amito group shown in Formula Il-C. For example, when the Q radical of Formula~ -I~r and rv i8 a dialkylamino group, the respective compounds are 3-(~-morpholino)-N',N'-dialkylamides and ~,N'-piperazino-bi~[3-(N",N"-dialkylamides)]. These heterocyclic beta-amino ; 10 amide catalyst~ are novel compounds and have the following more specific Formulas III-A and rV-A, respectively:

/ CH2 C 2 \ " ~ R5 \ CN2-CN2 / R3 R4 R5 CH CH \ '' ~ RS
N-C-CH-CH-N N-CH-C,H-C N ~ R rV-A

~n the above formulas and as Qhown elsewhere in the present specification, Rl, R2, R5 and R6 represent lower alkyl radicals, R3 and R4 may be hydrogen or lower alkyl, and R7 represents an alkyl radical having from 1 to 8 carbon atoms including linear and branched radicals ant i9 more usually.lower alkyl. It is to be understood that the lower alkyl~ represented by Rl, R2, R5 and R6 and encompassed by R3, R4 and ~7~ may be the same . ~47531 . 9149 as or different from one another. The generally pre-ferred cataly~ts for use in the practice of the present invention are those compounds wherein ~ 2~ R5 and R6 are methyl or ethyl including any combination thereof ant wherein at least one of R3 and R4 is hydrogen and the other is either hydrogen, methyl or ethyl.
bn addition to the heterocyclic beta-amino amides encompassed by Formula~ A and rV-A, particular acyclic compounds defined by Formula II-C are also novel compounds.
Thus, when in Formula II-C, the alkyl groups represented by ~1 and R2 are different from those represented by R5 .. and ~6~ the resulting unsymmetrically N-substituted 3-dialkylam~no-N,N dialkylamides are new compositions includlng tho~e wherein R3 and R4 are hydrogen or alkyl, as previously defined. Al~o novel are the 3-dialkylamino-

3-alkyl-N,N-dialkylamides, that is, those compounds encompas~ed by Pormula II-C in whlch R3 is limited to an alkyl grOuQ and Rl, R2, R4, R5 and R6 are as previously tefined.
As between the various types of compounds employet in the practice of this invention, the catalysts encompassed by Formulas II and III are generally preferred i~ that they al~o offer the processing advantage of being normally liquid materials, whereas the piperazine derived catalyst~ (Formula IV) are solids. From this stantpoint, th~ acyclic catalysts having Formula II are e~pecially 12.

~47S3~ 9149 preferred in thae they are generally les~ vi~cou8 than the morpholine derivative~ and thu~ can be handled and pumped more readily without dilution.
Typical example~ of ~uitable catalysts for us~
ia tho formation of cellular urethane polymer~ in accordance with the teaching~ of thi~ invention are the follcwing compounds which, for clarity, are groupet according to the structural formulas within which they 3pecifically fall, all such cataly~ts being within the scope o~ generic Formula I.

Formula II-A: -methyl 3-(N,N-dimethylamino)propionate;
ethyl 3-(N,N~dimethylamino)propionate;
ethyl 3-~N,N-diethylamino)propionate;
n-butyl 3-(N,N-diethylamino)propionate;
i-butyl 3-(N,N-dimethylamino)butyrate;
2-ethylhexyl 3-(N,N-timethylamino)propionate;
ethyl 2-methyl-3-(N,N-dimethylamino)proplonate;
propyl 3-~N,N-diethylamino)hexanoate;
ethyl 3-tN-methyl-N-ethylamino)propionate; and methyl 3-butyl-3-(N,N-dimethylamino)heptanoate.

- ~ormula II-B: ~
2-(N,N-dimethylamino)ethyl 3-(N',N~-dimethylamino)propionate;
2-(N,N-tiethylamino)ethyl 3-(N',N'-diethylamino)propionate;
2-(N,N-diethylamino)ethyl 3-(N',N'-dimethylamino)propionate; -13.

~(~47S3~. 9l4g 2-(N,N-dimethylamino)ethyl 2 methyl-3-(N',N'-dimethylamino)propionate;
2-(N-methyl-N-ethylamino)ethyl 3-(N',N'-dimethylam~no)propionate; and 2-~N,N-die~hylamlno)ethyL
3-(N'-methyl-N'-ethylamino)butyrate.

Formula ~I-C:
3-timethylamino-N,N-dimethylpropionamide;
3~iiethylamino-N,N-dimethylpropionamide;
10 3-diethylamino-N,N-diethylpropionamide;
3-dimethylamino-N,N-di-n-propylpropionamite;
3-diethylamino-N,N-di-s-butylpropionamide;
3-~N-methyl-N-eth~lamino)-N'-n-butyl-N'-methylpropionamite;
3-dimethylamino-2-methyl-N,N-dimethylpropionamide, 3-dimethylamino-N,N-dimethylbutyramide;
3-dimethylamino-N,N-dimethylpentamide; and 3-diethylamino-N,N-dimethylhexamide.

~ormula III includin~_Formula III-A:
methyl 3-(N-morpholino)propionate;
ethyl 3-(N-morpholino)propionate;
ethyl 2-methyl-3-(N-morpholino)propionate;
methyl 3-(N-morpholino~butyrate;
2-(N,N-timethylamino)ethyl 3-(N'-morpholino)propionate;
3-(N-morpholino)-N',N'-dimethylpropionamide;
3-(N-morphoLino)-2~methyl-N',N'-dimethylpropionam~te; and 3-~N-morpholino)-N',N'-dimethylbutyramide.

914g lr~47s3l :
Pormul- N includin~ Formula IV-A
timethyl 3-(N,N'-piperazino)dipropionate;
tiethyl 3-(N,~'-plpertzino)dipropionate;
t~-2-(N,N-d~methyla~ino)ethyl 3-(N',N"-piperazino)tipropionate; ant N,N!piperazino-bis[3-(N",N"-dimethylpropionamide)3 Th above-de~crlbed beta-amino carbonyl compounds mployet aa c~talyst~ in accordance with the present invention ar- readily prepsred by a number of different types of re~ctionJ A particularly facile method comprises the - reaction of (A) secontary amines and (B) e~ter or amido t-rivat~ves of alpha,beta-unsaturated carboxylic acids -With Jpeclfic reference to ~ormula I, the overall reaction ~y whlch ~uch compounda aro provided i~ a~ follows ~C~IH2"~ 0 )q N-H + CH-C-C-Q-~ Compounds of (S) / ' ' Formula I
C~H25tp R3 R4 R4actant A Reactant B
Con~iJtont with the structure of the compounds oncompassed by For~ula I, Reactant A may be a ti(lower)alkylamine [~l)(R2)NH] a9 typically illuJtrated by dimethylamine, ~i~thyl~mln~, tl-n-propylamine, di-i-propylamine, d~butyl~mi~o, methylethylam~ne; or the heterocyclic smines, ~orphollna ant p~pc~azine Also wlth reference eo the ~tructu~- of tho compound~ encompassed by Formula I, aee~nt B m~y be an alkyl (R7) or 8 2-(~,N-tialkyl-a~lno)0~hyl [-CH2CN2N~Rs)(R6)] e9ter terivative of an ~04753~

alpha,beta-unsaturated carboxylic acid having the ~ormula, CH(~)-C~R4)C(O)OH; or an alpha,beta-unsaturated N,N-di~lower)alkylamide having the formula, CH(~3)'C(R4)CtO)N(Rs)(R6). Typical examples of suitable unJaturated esters included within the definition of Reactane B are: methyl, ethyl, n-propyl, n-butyl, ~-butyl, 2-ethylhexyl, 2-(N,N-dimethylamino)ethyl, 2-(N,N-diethylamino)ethyl and 2-(N-methyl-N-ethylamino)ethyl ester terivatives of acrylic, methacrylic, crotonic, 2-methylcrotonic (tiglic), 2-ethylpropenoic, 2-pentenoic, 2-ethyl-2-pentenoic, 2-hexenoic and 2-heptenoic acids.
Illustrative of suitable unsaturated amide reactants encompassed by the definition of Reactant B are the corresponding amides containing the CH(R3)-C(R4)C(0)-nucleus of the aforesaid acids such as N,N-dimethyl-acrylamide, N,N-diethylacrylamide, N-methyl-N-ethylacrylamide, N,N-dimethylmethacrylamide, and N,N-dimethylcrotonamide.
Encompassed by the overall reaction of equatlon (1) i9 the direct 1:1 addition of the reactive H-N ~ group (or groups as in piperazine) of Reactant A
. across the double bond of Reactant B to form the corre-- sponting beta-amino ester and amide adducts, as illus-trated by the following equations (2)~(6):

16.

~047S31 o N-H + CH-C-C-OR1 > Compounds of (2) ~2~ ' ' Formula II-A
~ R4 N~H + CH~C-C-OCH2CH2N - > Compounds of (3) R2~ ~ ' ~R6 Formula II-B
~ 4 l~N~ + CH-C-C-N/ 5 > Compound~ of (4) R ~ ' ' \ R6 Formula II-C
~ R4 0 . O
~-H + CH-C-C-OR7~ 0v-CH-CH-C-OR7 (5) a3 ~l4 R3 R4 O
H-N~p-H + 2 CH~C-C-OR7 >

. .
O O
20R70-C-CH-CH-~31-CH-CH-C-OR7 (6) It is to be understood that replacement of the e~ter reactant shown in equation t5) with the unsaturatet ester reactant shown in equation (3), provides the c orre ~ pond ing 2- (N, N-dialkylamino)ethyl 3-(N'-morpholino)-17 .

- ~)4'~5 3 ~ 9149 ca~boxylates, such compound~, as well as the ester protucts of equation (5), being encompassed by 'For~ula II~. It also i9 to be understood that when morpholine is reacted with the unsaturated amide rcactants shown in equation (4), the products are ehe corresponding 3-(N-morpholino)-N',N'-dialkylamides which are also encompassed by Formula III and defined specifically by Formula III-A. Simllarly, when the ester reactant shown in equation (6) is replaced with the unsaturated ester reactant shown in equation ~3), the corresponding di-2-(N,N-dialkylamino)ethyl 3-(N',N"-piperazino)dicarbo~ylates are provided, such products a~'well as those of equation (6) being encompassed by ~or~ula lV. Likewise, reaction of 1,4-piperazine with the alpha,beta-unsaturated amides shcwn in equation (4) pro~ites the corresponding N,N'-piperazino-bis[3-(N",N"-tialkylamides)] which are also encompassed by Formula IV
ant tefinet specifically by Formula IV-A.
The addition reactions illustrated by eq~ations (2)-(6) ar~ effectet at temperatures within the range from about minus 15C. to about 120C. and proceed at sati~factory rates at ambient or sub~tantially atmo~pheric pressurs~. Reactions based on dimethylamine are generally ~o~e highly exothermic than those based on higher homo-logues and thus are usually effectet at the lower temperatures within the aforesaid range. As required, 18.

` 9149 ~t~47531 tempcrature control is achieved in conventional manner such a~ by cooling or appropriate ad3ustment of the rate at which the reactants are fed to the reactor.
Th~ relative proportions of reactants are such to at lea~t satisfy the indicated stoichio~etric require-ments of the addition, although either reactant may be employed in excess of stoichiometry to favor completion of the reactions. Usually, no more than a 125 per cent molar exces~ of either reactant is employed.
As illustratet by the reaction of equation (4), tho beta-amino amide catalysts can be prepared by the atdition of secondary amines to alpha,beta-unsaturatsd, N,N-tialkylamites. These catalysts can also be provided by the following application of the overall reaction of equation (1):
2quatlon 7 O O
2 ~ N-H + CH~C-C-OR7 ~ ~ N-CH-CH-C-N~ + R70H
R3 R4 ~ R4 This reaction may be viewed as an extension of the addltion reaction of equation (2) in that it proceeds through intermediate format~on of the alkyl beta-(dialkylamino)carboxylates (Formula II-A) followed by amidation which i3 an endothermic reaction. Thus, for any given combination of dialkylamine and alkyl alpha,beta-unsaturated carboxylate reactants, higher severity con-19 .

~'~)47531 ditions ar~ employed when it i9 desired to recover theamidated product. Generally, tho amidation reactions encompas~ed by equation (7) are effectet at temperatures wlthin the range from about 100C. to about 250C. and at elevated pressures from about 50 to about 1200 p.9.i.g.
In order to favor completion of the reaction, the amine reactant i8 preferably employed in excess of stoichiometry, amounts up to about a 100 per cent molar excess usually bein8 suitable for this purpose. The reaction of equation (7) may be carried out in batchwise fashion by initially charging total reactants to the reactor and applying the aforesaid high temperature-elevated pressure conditio~s.
Alternat~vely, the reaction may be carriet out as an essentially two-stage process. In accordance with the latter method, a portion of total amine reactant i9 fed to the unsaturated ester under the less severe addition reaction condition~ to form the 1:1 adduct, followed by reaction of the intermediate with the remainder of amine under the aforesaid more sevare amitation conditions.
It is to be understoot that the amine fed to the first stage may be different from that fed to the second stage, therebj providing amino and amido groups having a different ~ombination of Rl and R2 groups, that i9, compounds encompassed by Formula II-C wherein the alkyl groups represented by Rl and R2 are different frc~ the ~lkyl8 represented by R5 and R6.

20 .

~47S3~ 9149 In order to minimize formation of by-product~
by retro-addition reactions and hydrolysis of ester reactants as well as ester products, it i9 recum~ended practice to effect the above-described reactions under anhytrous or substantially anhydrous conditions. Thu~, the reaction media should contain less than about 5 weight per cent water, expressed on the ba~is of amine reactant. Formation of by-products such as alpha,beta- !
unsaturated amides may also be formed during the reactions. Minor amounts of compounds which have an inhi~lting effect on polymerization of ~uch by-products mar be added to the reaction media. Illustrative of suitable inhibitors are phenothiazine, p-methoxyphenol ant hydroquinone. The reaction metia may also contain solvents or tiluents such as, for example, ethanol, butanol, diisopropyl ether, dioxane ant other such compounts which are inert under the reaction conditions.
The techni~ue by which the beta-amino amide ant ester catalysts are recovered depend~ largely on their physical nature and propertie~. Thus, the normally liquid product~ encompassed by Formulas II and III are recoveret by distillation or as residue products remaining - after removal of more volatile components. Recovery as residue productR i9 usual practice in the case of the higher molecular weight compounds such a~ the morpholine-derived compounts and acyclic compount~ in which the 21.

~ 0 4 7 5 3 ~ gl4~

var~ous alkyl group~ are propyl and butyl. The piperazine-der~vet catalysts are recovered by conventional liquid-solid separation techniques.
The effectiveness of the beta-amino carbonyl compounds as catalysts for cellular urethane manufacture as described herein~ toe~ not depend on their u~e in a rigorouJly pure state. Included within the scope of the pre~ent iDvention, therefore, is the use of the catalyst3 as either substantially pure compounds, in combination with one another, or in association with impurities which may form during their manufacture.
(B) THE FQAM FORMULATIOWS
In producing cellular urethane polymers in accordance with the teachings of this invention, the reaction mixture or foam for~ulation contains, in addition - to the beta-amino carbonyl cata}y~ts, an organic polyi90-cyanate and an active hydrogen-containing organic compound having aD average of ~t least two ~nd usually not more than eight active hydrogen atoms present as hydroxyl groups.
Such organic polyol reactants include compounds consisting of carbon, hydrogen and oxygen as well as compounds which contain these elements in combination with phosphorus, - hsloge~ and/or nitrogen. Suitable classes of organic polyol reactant for use in the method of this invention are polyether polyols, polyester polyols, polylactone polyols, nitrogen-containing polyols, phosphorus-containing 22.

polyols, phenolic-baqed polyols, and polymRr/polyol~
produced by polymerizing an ethylenically un~aturated monomer in one of the afore~aid polyols in the presence of a free radical initiator It is well known to the polyurethane art that : the particular polyol reactant or combination of polyols employed depends upcn the end-use of the polyurethane product wbich in turn determines whether the product i9 to b~ provided a~ a flexible, semi-flexible or rigid materlal. For this purpose, the polyol reactant i9 u~ually characterized by it~ hydroxyl number which i~
determined by and defined as the number of milligrams of potas~ium hydroxide required for the complete neutralization of the hydrolysis product of the fully acetylated derivative prepared from 1 gram of polyol or mixture of polyol~. The hydroxyl number i9 also defined by the following equation which reflects i~s relationship with the functionality and molecular weight of the polyol reactantO
OH - S6.1 x 1000 x f M. W.
wherein ~H - hydroxyl number of the polyol;
f ~ average functionality, that 18, average number of hydroxyl groups per molecule of polyol; and M. W. - average molecular weigh~ of the polyol.
The beta-amino carbonyl compound~ de~cribed herein are suitably employed as catalytic component~ of foam formu-.. .. ... . ..... ...... . .... .

'lS)47531 lation~ containing polyols having hydroxyl number~ from about 20 to abou~ 1000. In producing flexible foams, polyols having relatively l~w hydroxyl numbers such as f~cm about 20 to about 100 are generally employet. In protucing semi-flexible materials, the hytroxyl num~er i~ usually from about 100 to about 300. Polyols having relatively high hydroxyl numbers of from about 300 to about 1000 are u~ed in rigid foam formulations.
Suitable polyethers that can be employed include linear and branched polyethers preferably hsving a plurality of ether linkages and containiDg at least two hydroxyl groups and being subqtantially free from functional groups other than hydroxyl. For convenience, this class of polyether polyols are referred to herein as Polyol I. These compounds include alkylene oxide adduct~ of water such as polyethylene glycols having average molecular weights from about 200 to about 600, polypropylene glycols having average molecular weights from about 400 to about 2000J and polyoxyalkylene polyol~ having a combination of different alkylene oxide units. Other suitable polyol3 encompassed within the tefinition of Polyol I are the alkylene oxide adduct~
of polyhydric organic initiators, the nature of which determines the average hydroxyl functlonality of the polyoxyalkylated product. Illustrative of ~uitable polyhydric organic initiator~ are the following which 24.

. . .

1047S3~
can be employed individually or in combinaticn with one another: tl) diol~ such a~ eth~lene glycol, tiethylene glycol, propylene glycol, 1,5-pentanediol, hexylene glycol, dipropylene glycol, trimethylene glycol, l,2-cyclohexanediol, 3-c~clohexene-1,1-dimethanol and 3,4-dibromocyclohexane-l,l-dimethanol; ~2) triols such as glycerol, 1,2,6-hexane-triol, },l,l-trimethylolethane, l,l,l-trimethylolpropane, 3-(2-hydroxyethoxy)- and 3-(2-hydroxypropoxy)-1,2-propane-diols, 2,4-dimethyl-2-(2-hydroxyethoxy)methyl-pentanediol-1,5, 1,1,1-tris~2-hydroxyethoxy)methyl]ethane and 1,1,1-tris~(2-hydroxypropoxy)methyl]propane; (3) tetrol~ such a~ pentaerythritolj ~4) pentol3, hexols, heptanols and octanols such 89 glucose, 30rbltol, bis(29292-tri- -- methylol)ethyl ether, alpha-methyl glucoside, sucrose, mannose and galactose; (5~ compounds in whi~h hydroxyl groupa are bonded to an aromatic nucleus such as --resorcinol, pyrogallol, phloroglucinol, di-, tri- and tetra-phenylol compounds such as bis(p-hydroxyphe~yl)-methane and 2,2-bi3(p-hydroxyphenyl)propane; and ~6) alkylene oxide adducts of ~he afore~aid initiators such as propylene or ethylene oxide adducts of glycerol having a relatively lcw aver~ge molecular weigh~ up to about 600. Particul~rly useful in the prep~ration of flexible foams generally are polyether polyols having an average hydroxyl functionality of from ~bout 2.1 to about 4. Such polyols are provided by the employment of either trihydsic or tetrahydri starters, mixtures thereof, or appropriate m~tures containing diol 2.~.

~ )4753~
starters. The more highly functional polyether polyol~
are usually employed in providing the semi-flexible and ri8id foams.
The above-describet polyether polyols are - normally li~uid materials and, in general, are prepared in accordance with well known techniques compri~ing the reaction of the polyhytric start~r and an alkylene oxide in the pre~ence of an oxyalkyl~tion catalyst. Usually, the catalyst is an alkali metal hydroxide such as, in particular, potassium hydroxide. The oxyalkylation of the polyhydric initiator is carried out at temperatures ranging from about 90C. to about 150C. and u3ually at an elevated pressure up to about 200 p.s.i.g., employing a sufficient amount of alkylene oxide and adequate reaction time to obtain a polyol of desired molecular weight which is conveniently followed during the cour3e of the reaction by standart hydroxyl number determinations~
as defined above. The alkylene oxites most commonly employet in providing the reactants encompassed by Polyol 1, are the lower alkylene oxides, that i9, compountg having fr~m 2 to 4 car~on BtCm8 including ethylene oxid~, propylene oxide, butylene oxides ~1,2- or 2,3-) and combi-~ation~ thereof. When more than one type of oxyalkylene unit i9 desiret in the polyol product, the alkylene oxide reactants may be fed to the resction sy~tPm se~uentially to provide polyoxyalkyl~ne chains containing respective 26.

~)47S3~ 9149 blocks of different oxyalkylene units or they may be fed simultaneously to provide substantially randcm di3tribution of units. Altern~tively, the polyoxy-alkylen~ chains may consist essentially of one type of oxyalkylene unit ~uch a~ oxypropylene capped with oxyethylene units.
A second class of polyol~ that are ~ultable for use in prepar$ng polyurethane foams in accordance with the present invention aro polymer/polyols which, for convenience, are referred to herein as Polyol II.
Such reactants are produced by polymerizing one or more ethylenically unsaturated monomRrs dissolved or tisperset in any of the other type~ of organic polyol reactants described herein, in the presence of a free ratical catalyst. Especially suitable as the substrate polyols for producing such compositions are any of the above-de~cribet polyether polyol~ encompas3ed by the definition of Polyol I. Illustrative of suitable ethylenically unsaturated monomRrs are vinyl compounds having the general formula, B.

where: R i9 hytrogen, methyl or any of the halogens (i.e., fluorine, chlorine, bromine or iotine); and ~ ~9 ~, cyano, phenyl, methyl-substitutet phenyl, carboalkoxy, or alkenyl radicals having from 2 to 6 :27.

~)47S3~

carbon atDms such as vinyl, allyl ant isopropenyl groups.
Typical examples of such polymerizable monomers are the following which may be employed individually or in combi-nation: ethylene, propylene, acrylonitrile, methacrylo-nitrile, vinyl chloride, vinylidene chloride, styrene, alpha-methylstyrene, methyl methacrylate, and butadiene.
These and other polymer/polyol compositions which are suitably employed either individually or in combination with Polyol I are those described in British Patent No.
1,063,222 and United States Patent Nos. 3,304,273, 3,523,093 and 3,383,351. Such compositions are prepared by polymerizing the monomers in the polyol at a temperature between about 40C. and about 150C. employing any free radical-generating initiator including peroxides, persulfates, percarbonates, perborates and azo compounds.
Illustrative of suitable initiators are: hydrogen peroxide, dibenzoyl peroxide, benzoyl hydroperoxide, lauroyl peroxide and azobis(isobutyronitrile).
The polymer/polyol compositions usually contain from about 5 to about 50, and more usually from about 10 to about 40, weight per cent of the vinyl monomer or monomers polymerized in the polyol. Especially effective polymer/polyols are those having the following composition:
(A~ from about 10 to about 30 weight per cent of a copolymer of (1) acrylonitrile or methacrylonitrile, 28.

: 9149 i~l4753~
and (2) styrene or alpha-methylstyrene, the said copolymer containing from about 50 to 75 and from about 50 to 25 weight per cent of monomeric units of (1) and (2), respec-tively; and (B) from about 90 to about 70 weight per cent of one or more of the polyols encompassed by Polyol I as the medium in which said component (A) is polymerized, the trifunctional polyols such as alkylene oxide adducts of glycerol being especially suitable.
These polymer/polyol compositions containing components (A) and (B) are the sub;ect of Belgian Patent No. 788,115.
Other types of suitable polyol reactants for use in producing cellular polyurethanes as described herein are polyester polyols provided as the reaction products of:
(1) a polyfunctional organic carboxylic acid, and (2) one or more of the aforesaid polyether polyols or one or more of the aforesaid polyhydric organic compounds which are reacted with alkylene oxide to produce such polyether polyols. Among the suitable polycarboxylic acids that can be employed in producing such polyester polyolQ are: the aliphatic acids which are usually free of reactive un-saturation such as ethylenic and acetylenic groups, such as, for example, succinic acid, adipic acid, sebacic acid, azelaic acid, glutaric acid, pimelic, malonic, and 29.

1 ~ 4 7 S 31 9149 suberic acids; cycloaliphatic acids such as chlorendic acid; and aromatic poly basic ~cids 3uch as phthalic, te~ephthalic, isophthalic acits and the like.
Also contemplated for use as a polyol reactant - of the foam formulations employed in the practice of this inve~tlon are nitrogen-containing polyols Such polyol~
include lower alkylene oxide Adducts of the follcwing amine~ which may ~e employed individually or in combi-nation: primary and secondary polyamines such as ethylene-diamine, tiethylenetriamine ant toluenediamine; and ~mino- ~
alkanols such as ethanolamine, diethanolamine, triethanol-amine and triisopropanolamine Also suitable are mixet starters containing one or more of the afore~aid poly-functlonal amines, aniline, ant/or one or more of the polyhydric initiators employet to produce Polyol I such - as dipropylene glycol, glycerol and sucrose. Al30 illus-trative of suitable nitrogen-~cntaining polyols are aniline/formaldehyde and aniline/phanol/formaldehyte conden3ation products. Such amine-ba~ed polyols are usually employet in rigid foam formulation~.
Other 3uitabls polyols for use in protucing polyurethane foams as t~scribed herein are: lactone-ba~ed polyols prepared by reacting a lactone such as epsilon-caprolactone, or a mixture of epsilon-csprolactone and an alkylene oxite, with 8 polyfunctional initiator such a~ a polyhydric alcohol, an ~mine, or an aminoalcohol;

~04753~ 9149 phosphorus-containing polyols ~uch as the alkylene oxide atducts of phosphoric acid, polyphosphoric acids such as tri- and tetra-phosphoric acit~, organo-substituted pho~phoric acids such as benzenephosphoric acid; and other polyol reactants kncwn to the polyurethane art.
The beta-amino carbonyl compound~ described herein are used with particulsr advantage a~ cataly~ts in the manufacture of high-resilience flexible foam. Such foams usually have a re~iliency of from about 55 to about 70 per cent, as measured by ~tandard test procedure ASTM D-1564-69. In accordance with a preferred embodiment of thls aspect of ~he present invention, the beta-amino carbonyl compounds are employed as catalytic components of high-resilience foam formulations wherein at least 40 weight per cent of the totsl polyol content is constituted of a polyether triol having the following ~dditional characteristlcs: (a) an average primary hydroxyl content of at least 40 mole per cent (or no more than 60 mole per cent of the le93 reactive 3econdary hydroxyl groups); and (b) an average molecular weight of from about 2000 to about 80Q0. For convenience, this particular class of polyols are referred to herein as Polyol I-A. Preferably, such polyether triols for use as components of high-resilience formulations contain from about 60 to about 90 mole per cent of primary hydroxyl groups and have an a~erage molecul~r weight of from about 4000 to about 7000.

31~

~(~4753~

Con~istent with their trifunctionality ant the aforesaid respective ranges of molecular weigh~, such polyether triol~ have hydroxyl number~ from 84 to 21, preferably from 42 to 24. These highly reactive polyether triol~
ar- provided by oxyalkylation of one of the aforesaid trihydric starters such as glycerol~ with propylene oxide and ethylene oxide. Usually9 the total ethylene oxide content of the polyether triols encompassed by the defi-nition of Polyol I-A i9 betweon about 7 and about 20 weight per cent, expressed on the basis of total alkylene oxide fed during the oxyalkylation reaction. The high primary hytroxyl content i9 introtuced by capping of the polyoxyalkylene chain3 with at lea~t a portion of the total ethylene oxite feet.
In providing high-re~ilience foams, ~he poly-ether triols includet within the definition of Polyol I-A
may be used as e~sentially the sole type of polyol in the formulation or they may be employed in combination with other polyols to control the tegree of softne~s or firm-ne~s of the foam and to vary the loat-bearing propertiPs.
For exEmple~ when ~ofter grade high-resilience foams are desired, Polyol I-A may be used in combination with polyether diols such a3 the above-de3cribed lower alkylene oxite adduct3 of a dihytric initiator such as tipropylene glycol. When firm grade~ of high-re3ilience foam~ having enhanced load-~earing propertiPs are desiret, Polyol I-A

3~.

104753~ 9149 i8 used in combination with up to about 60 parts by weight per 100 parts by weight of total polyol reactant (p.p.h.p.) of a polymer/polyol encompasset within the definition of Polyol II. In this latter respect, particularly effective mixtures of polyols are thQse containing:
(1) from about 40 to about 80 p.p.h.p. of the -polyether triols, designated hereinabove as Polyol I-A; and (2) from about 60 to about 20 p.p.h.p. of polymer/polyols, designated herein as Polyol II-A, prepared by the in situ polymerization of a monomer mixture containing from sbout 50 to ab~ut 75 weight per cent of acrylonitrile ant from about 50 to about 25 weight per cent of styrene, in Polyol I-A, the said monomer mixture constituting from about 10 to about 30 weight per cent of the combined weight of the monomers ant Polyol I-A.
The polyisocyanates used in the manufacture of polyurethane~ are known to the art and any such reactants are suitably employed in producing polyurethane foams in the presence of ~he beta-amino carbonyl catalysts describet herein. Among such suitable polyisocyanates are thos~ represented by the general formula-Q'(NCO)i ~wherein: i has an average value of at least two and is usually no more than 9iX, and Q' represents an allphatic, cycloaliphatic or aromatic radical which can be an unsub-33.

1~47S3~

stituted hydrocarbyl group or a hydrocarbyl groupsub~tituted, for example, with halogen or alkoxy.
~or example, Q' can ~e an alkylene, cycloalkylene, arylene, alkyl-sub~titutet cycloalkylene, alkarylene or aralkylene radical including corresponding halogen-and alkoxy-substituted radicals. Typical examples of polyisocyanates for use in preparing the polyurethane~
of this invention are any of the following including mixtures thereof: 1~6-hexamethylene diisocyanate, 1,4-tetramethylene tiisocyanate, bis(2-isocyanato-ethyl)fumarate, l-methyl-2,4-tiisocyanatocyclohexane, bis(4-isocyanatophenyl)methane, phenylene diisocyanates such as 4-methoxy-1,4-phenylenediisocyanate, 4-chloro-1,3-phenylenediisocyanate, 4-bromo-1,3-phenylenediiso-cyanate, 5,6-dimR~hyl-1,3-phenylenediisocyanate, 2,4-tolylene diisocyanate, 296-tolylene diisocyanate, crude tolylene diisocyanate~, 6-isopropyl-1,3-phenylenediiso-cyanate, durylene diis~cyanate, triphenylmethane-4,4',4"-triisocyanate, 2nt other organic polyi30cyanates known 23 to the polyurethane artO Other suitable poLyisocyanate reactan~s are ethylphosphonic diisocyanate and phenyl-phosphonic diisocyanate. Of the aforesaid types of polyisocyanates, those containing aromatic nuclei are generally preferred.
Al~o useful as the polyisocyanate reactant are polymeric i~ocyanates having units of the formula:

34.

1'~4753~
~ CH2 ~

wherein R "' is hydrogen and/or lower alkyl and ; has an average value of at least 2.1. Usually, the lower alkyl radical is methyl and ~ has an average value no higher than about 4. Particularly useful polyiso-cyanates of this type are the polyphenylmethylene poly-isocyanates produced by phosgenation of the polyamineobtained by acid-catalyzed condensation of aniline with formaldehyde. Polyphenylmethylene polyisocyanates of this type are low viscosity (50-500 centipoises at 25C.) liquids having average isocyanato functionalities in the range of about 2.25 to about 3.2 or higher, and free -NC0 contents of from about 25 to about 35 weight per cent, depending upon the specific aniline-to-formaldehyde molar ratio used in the polyamine preparation.
Also useful as polyisocyanate reactants are polymeric tolylene diisocyanates obtained as residues from the manufacture of the diisocyanates and having a free -N~0 content of from about 30 to about 50 weight 35.

~ 7531 per cent. Other useful polylsocyanate reactants are combinations of diisocyanate~ with polymeric iso-cyanate~ containing more than two isocyanate grO~'p8 per moleculo. Illustrative of such combinations are:
a mixture of 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate and the aforesaid polyphenylmethylene polyisocyanates and/or the aforementioned residue products.
Of the aforesaid polyisocyanates, those employed with particular advantage in proviting high- -resilience foams are mixtures containing from about 60 to about 90 weight per cent of the isomeric tolylene diisocyanates and fro~ about 40 to about 10 weight per cent of the polyphenylmethylene polyisocyanates, in orter to enhance the average -NCO functionality and thuJ th~ reactivity of the reaction mixture. When the high-resilience formulations contain diisocyanates as essentially the sole source of reactive -NCO, it is often de~irable to include minor amounts, such as up to about 1.5 p.p.h.p., of cross-linking agents. Suitabl~
additive~ for thi~ purpose ar~ diethanolamine, methyldi-ethanolamine and triethanolamine.
On a combined basi~, the polyol reactant and org~nic polyisocyanate usually constitute the ma~or pro- -portion by weight of the polyurethane-forming reaction mixture. In general, the polyisocyanate and polyol 36.

~.047531 reactants are employed in relative amounts such that the ratio of toSal -NC0 equivalents to total active hydrogen equiYalent (of the polyol and any water, when used) is from 0.8 to l.S, u~ually from 0~9 to 1.20, equivalents of -NC0 per equivalent of active hydrogen. This ratio - i9 known as the Isocyanate Index and i8 often also expressed a~ a per cent of the stoichiometric amount of polyisocyanate requiret to react with total active hydrogen. When expre3~ed a~ a per cent, the I~ocyanate Intex may be from 80 to 150, and is usually within the range from about 90 to about 120.
M~re usually, the Isocyanate Index is no more than about 115.
The ~eta-amino carbonyl catalysts may be employed individually or in combination with one another and are present in the foam formulation ~n catalytically effective amounts. Thus, the total concentration thereof may vary over a relatively wide range such as from about 0.01 to about 5 or more parts by weight (exclusive of any carrier sol~ents or other additi~es) per 100 parts by weight of the total polyol reactant contained in the reaction mixture.
Usually, thi~ catalytic component i~ present in an amount from about 0.05 to about 3.0 p.p.h.p. In flexible foam formulations, it is u3ually adequate to employ the beta-amino carbonyl catalysts in an amount up to about one p.p.h.p., whereas in rigid formulations, higher concen-tra~ions are usually used.

37.

` 1.0 ~7 5 31 The beta-amino earbonyl catalysts may be employed as the sole type of smine catalyst of the foam formulations described herein or they may be employed in combination with one or more tertiary amines convention~lly employed as catalysts in producing polyurethanes. Such additional catalyst~ include amines coDsisting of carbon, hydrogen and nitrogen, as well as amines consi3ting of the~e three elements and oxygen wherein oxygen i9 present solely as ether or hydroxyl groups. Although these auxiliary amine catalyst~ can contain up to 24 carbon atom~, the more commonly employed compounds contain no more than 12 carbons. Illu~trative of such tertiary amiDes for use in combination with the beta-amino carbonyl catalysts areo trimethylamine; triethylam~ne; tributyl~mine;
N,N,N',N'-tetramethylethylenediamine; N,N,N',N'-tetramethy.l-- l,3-butanediamine; N,N-dimethylcyclohexylamine; N,N-dimethyl-benzylamine; bis~2-(N,N-dimethylamino)alkyl]ethers such a3 bis[2-(N,N-timethylamino)ethyl~ether; triethylenediamine~
N-methylmorpholine; N-e~hylmorpholine; N-~2-hydroxyethyl)-piperazine; N-methyldiethanolamine; N,N-dimethylethanol^
amine; and other such conventional tertiary amine poly-urethane catalysts. Of the sforesaid tertiary amines, - tho~e containing reactive hydroxyl are oft~n used to serve the additional function of cross-linking agents. Such alkanolamines are often used in the manufacture of rigid foams, or to enhance cross-linking density of high-resilience foams ba3et on dii30cyandtes.

. 9149 ~ 0 47 5 3 1 When used, the 3upplementary tertiary amine catalyst~ may be pre3Pnt i~ the foam formulation in an amount within the aforesaid ranges defined with re~pect to the beta-amino carbonyl catalysts, although usually the total amount of supplementary amine i9 no more than about one p.p.h.p. It is to be understood that the beta-amino carbonyl catalyst ant the supplementary tertiary amine, when uset, may be added to the formulation as separate streams or in preblended form.
Illustrative of 3uitable blended catalysts provited by the present invention and whlch are especially u~eful as components of wster-blown, flexible foam formu-lations includlng high-resilience systems, are those con-taining from about 10 to about 90 weight per cent of the beta-amino carbonyl compounds ant corre3pontingly from about 90 to about 10 weigh~ per cent of either bis~2-(N,N-timethylamino)eth~l~ether, triethylenediamine~ or the bis-amino ather plu3 triethylenediamine. It i9 to be unterstood that the ~aid weight percentages are based on the total weight of the blended catalysts, exclusive - of carrler solven~s or other adtitives. These blents are added to the foam formulations in an amount 3uffi-cient to provide the beta-amino carbonyl cataly~t ant auxiliary amine within the aforesait respective ranges of concentration~ that is, between about 0.01 and about 5 p.p.h.p.

39.

914g 104753~
~ rom the standpoint of providing aa effective caSalyst system, the beta-amino carbonyl catalyst may be used, as included in the foregoing description, in combi-nation with N-alkylmorpholines ~uch as N-ethylmorpholine.
The latter compound is presently used in ccmmercial practice in relatively hi8h concentrations (up to about 2.0 p p.h.p.) as a catalytic component of molded high-resilience formu-_ lations in order to provide foams having good molt-release characteristics. In view of the pre~ent disc~very ~hat ~uch foams can be produ~ed by employing the beta-amino carbonyl catalysts described herein without the neces~ity of using N-ethylmorpholine~ the latt~r catalyst may be completely eliminated, thereby avoiting the obnoxious re~idual foam odor a~sociated therewith. It is to be unterstood, however, tha~ N-ethylmorpholine may be used as a component of the foam formulations described herein without departing from the scope of this invention. Whe~
used, the level of such N-alkylmorpholine catalys~s is de~irably kept to a minimum such as no more than abous 0.30 p.p.h.p.
It is to be undarstood that the beta-amino carbonyl catalysts employed in accordance with the prPsent invention, as well as blends b~sed thereon~ may be in~ro-tuced to the foim for~ulations in undiluted form or as solut~ons in suitabl~ carrier ~olvents such as diethylene glycol, tipropylene glycol and hexylene glycol. The supplementary amine catalysts are also oftan employed in such carrier solvents.
40.

0 ~'~5 3 ~ther us~ful c~rr~er 301vents for the catalyst~
descr~ed herain are lower ~lkylene oxide adducts of mono-hydric or Folyhydric starters such as butanol, d~propylene glycol and glycerol. Such solvents (or dlluents) generally lnclude attucts c~ntaining from about 3 to about 30 oxy-ethylene or oxypropylene units, mixtures of such adducts, a~ well as adducts provided by reaction of the starter with ethylcn~ ~xide and propylene oxide, fed either as a mixed feed or sequentially. Among the suitable organic carrier ,~ 10 solvents of thi~ type are the ethylene oxide-propyleDe oxide adducts of butanol having the average formula, C4Hg(OC3H6)u(0C2H4)90H~ wherein 9 and u may each have an average value from about 3 to about 30. Preferably, the values of ~ and u are such that th~ average molecular weight of these fluits i9 not substantially greater than about 2000 ant the oxyethylene content is from about 20 to about 80 weight per cent, bssed on total polyoxyalkylene content. U~ually, the waight per cent of oxyethylen~ ~9 a~out the same as the weight per cent of oxypropylene.
20 Also $ncluded wlth~n the ~cope of the present invention is the use of the beta-amino carbonyl catalysts in comblnation with organic surfactants. When used, the - organic surfactant i3 usually a non ~onic surfactant sueh as: the polyoxyalkylene ethers of higher alcohols h~ving fr~ 10 to 18 carbon atom~ including mixtures thereof;
and polyoxyalkylene ethers of slkyl-substituted phenols 41.

.. . . . ... , .. ..... .. . ... ... . . , ., ., .. . . , ",, . . . .. ~ .. .... ~. ........ . .. . . . .. ... .
. .

~n which the alkyl group can have from 6 to 15 carbon atoms. The length of the ether chain i8 ~uch that appropriate hydrophilic character is provided to balance the hydrophobic portion derived from the alcohol or phenol and render the compount mlscible with water.
The chsin may contain oxyethylene units either as essentially the sole type of un~t or oxyethylene in combination with a minor amount of oxypropylene. It i8 preferred that the hydrophilic portion of the non ionic surfactants be composed essentially of oxyethylene ~onomeric units. Usually the average number of such -OC2H4- unit~ ranges from about 4 to about 20, although upwards of 30 ~uch units can also be present.
Typical examples of non ionic surfactants which can be used in combination with the beta-amino carbonyl catalysts employed in the practice of this invention are the adducts produced by reaction of from about 4 to about 30 moles of ethylene oxide per mole of any of the following hydrophobes including mixture~ thereof: n-undecyl alcohol, myri~tyl slcohol, lauryl alcohol, trimethyl nonanol, tri-decyl alcohol, pentadecyl alcohol, cetyl alcohol, oleyl alcohol, ~tearyl alcohol, nonylphenol, dodecylphenol, tetradecylphenol, and the like. Especially suitable for u~e as the carrier medium for the beta-amino carbonyl cat~lyst~ described herein are the ethylene oxide adducts o~ nonylphenol having the average composi~ion, CgHlg~C6H4~(0C2H4)h~0H~ whereln h ha~ an average value from about 4 to about 20, inclw ive of whole and fractional numbers, ~uch as 6, 9, 10.5 and 15.
42.

The above-described ~olution compositions ma~ contain from about 10 to s~out 90 weight per cent of total beta-amino carbonyl cataly~t (inclusive of ~upplementary tertiary smine catalyst, when used), based on the combined weight of catalyst, solvent and/or organlc surfactant, depending upon whether the catalyst 1~ employed in comblnatlon with elther one or both of tha ~olvent and organic surfactant.
It i~ often desirable to include as a further component of the foam formulation a minor amount of certai~ metal catalysts, particularly organic derivatives of tin including stannou~ and stsnnic compounds. Such metal co-catalysts are well known to the art ant are usually employed in producing polyether polyol-based polyurethanes. Illustrative of suitable organic tin compounds are the follcwing which may be employed indi-vidually or in combination: 3tannous salt~ of carboxylic acids ~uch as stannous octoate, st~nnous oleate, ~tannous acetate and stannous laurate; dialkyltin dicarboxylates such as tibutyltin dilaurate, dibutyltin diacetate, dilauryltin diacetate, dibutyltin di(2-ethylhexanoate) and other such tin 3alts as well as dialkylein oxides, tr~alkyltin oxite~, tin mercaptides ~uch as, for example, di-n-octyl tin mercaptide, and the like. When used, the amou~t of such metal co-catalyst3 ranges from about 0.001 to about 2 parts by weight per 100 parts by weight of 43.

.. . .. . . ... .... . ... .

1~34753~

total polyol reactant. }n flexible foam formulations, the metal co-catalyst i~ prefPr~bly used in an amount - from about 0.01 to about 0.6 p.p.h.p., and most prefer-ablr in an amount no more than about 0.5 p.p.h.p.
Foaming i9 accomplished by the presence in the reactisn mi~ture of varying amount3 of a polyurethane ~lowing agent such a3 water which, upon reaction with isocyanate, generates carbon tioxide in situ. or through the use of blcwing agents which are vaporized by the exotherm of the reaction, or by a combination of the two methods. These various methods are known in the art. Thw, in additlon to or in place of water, other blowing a8ents which can be employed in the process of thiJ invention include methylene chloride, liquefied ga~es which have boiling poiDts bel`cw 80F. and above -60F., or other inert ga~es such as nitrogen, carbon dloxide adted as such, methane, helium and argon.
Suitable liquefied gases include aliphatic and cyclo-aliphatic fluorocarbon~ which vaporize st or belcw the temperature of the foaming ma9~. Such gases are at least partially fluorinated and may al30 be otherwise halogenated. Fluorocarbon agents sui~able for w e in - foaming formulations of this invention include: tri-chloromonofluoromethane; dichlorodifluoromethane; 1,1-dichloro-l-fluoroethane; l,2,2-trifluoro-1,1,2-trl-chloroethane; 1,1,1-trifluoro-2-fluoro-3,3-di n uoro-44.

~ ~ 47 5 3 1

4,4,4-tsifluorobutane; hexaf~uorocyclobutene; and octa- ;
fluorocyclobutane. Anothor useful clas~ of blowing agents include thermally-unstable compounds which liberate gases upon heating, such as N,~'-dimethyl-N,N'-dinitrosotere-phthalamide, and the like.
Generally, the blowing agent is omployet in an amount from about 1 to about 45 parts by weight per 100 parts by weight of total polyol reactant, the particular blowing agent and amount thereof depending upon the type of foam product desired. ~lexible foam formulations including tho~e which favor formation of high-resilience foam, ar~ most u~ually water blown, although a minor proportion such as up to about 10 weight per cent of total blowing agent may be constitutet of a fluorocarbon such as trichlorofluoromethaneO Flexible foam formulations usually contain no more than sbout 10 p.p~h.p. of water.
For rigid formulations, blowing action i9 usually supplied L . employing a fluorocarbon in a relatively high proportion su6h as frcm about 10 to about 45 p.p.h.p., either as the sole type of agent or in combination with a minor amount of water such as up to about 10 weight per cent of total blowing agent. The selec~ion and amount of blowing agent in any particular foam formulation is well within the sklll of the csllular polyurethane art.
In producing cellular polyurethanes in accordance with the method of this invention, a minor amount of an organosilicone ~urfactant may al30 be present as an additional 45.

~)47531 9149 component of the polyurethane-fonming reaction mixture.
When used, sueh surfactant3 are usually present in amounts up to about 5 parts by weight per 100 parts by weight of total polyol reactant.
Among the suitable clas~es of surfactant are the polysiloxane-polyoxyalkylene block copolymers wherein the respective blocks are ~oined through silicon-to-carbon or - silicon-to-oxygen-to-carbon bonds and the respective poly-oxyalkylene blocks are bonded to different ~ilicon ato~s of the poly~iloxane backbone to fonm a comb-like structure.
Usually, the polysiloxane blocks are trialkysiloxy-endblocked.
ln adtition to the siloxy units to which the pendant poly-oxyal blene chains are bonded, the polysilo~ane backbone i~ formed of difunctional siloxy units wherein the respective two remaining valences of silicon are satisfied by bonds to organic radicals. Illustrative of such organic radicals are the hydrocarbyl group~ having from 1 to 12 carbon atoms including alkyl, aryl, aralkyl, bicycloheptyl ant halogen-substituted derivatives of ~uch groups. The polyoxy-alkylene blocks are usually constituted of oxyethyleneUDit~, oxyprowlene units or a combination of such units, and the polyoxyalkylene chains are hydroxyl-terminated or capped with a ~onovalent organic group such as alkyi, aryl, aralkyl, acyl, carbamyl and the like. Espec~ally u~eful as 3tabilizers of flexible polyether-baset poly-urethane foams are the block copolymers describet in 46.

104753~
United States Patent 3,505,377, now United States Reissue Patent No. 27,541. The copolymers of the latter patent contain from 40 to 200 dimethylsiloxy units as essentially the sole type of difunctional unit, and from 15 to 60 weight per cent of the oxyalkylene cDntent of the polyoxyalkylene blocks is constituted of oxyethylene.
Also useful as stabilizers of flexible, polyether-based :
polyurethane foam including flame-retarded foam, are the block copolymers described in United States Patent 3,657,305. The polysiloxane backbone of the organosilicones of the latter patent, contains an average of from 10 to 200 dimethylsiloxy units in combinatiDn with from 1 to 50 methyl-aralkylsiloxy units such as, in particular, methyl-phenylethylsiloxy units [(CH3)(C6H5CH2CH2)SiO].
Other useful foam stabilizers for flexible polyether-based foam are the block copolymers described in United States Patent 3,686,254. Particularly useful stabilizers of flexible polyester-based polyurethane foam are the surfactants described in United States Patent 3,594,334.
A second type of foam-stabilizing component which can be present in the formulations described herein are the branched block copolymers described in United States Patent 2,834,748. Organosilicone foam 47.

i~)47531 stabilizers described in the latter patent include those containing a trifunctional siloxy unit to which three polyoxyalkylene blocks are bonded through dialkyl-substituted siloxy units. A preferred group are those having the formula, MeSi[(OSiMe2)x(OCaH2a)vOX]3, wherei Me is methyl, x has a value of at least one, a is from 2 to 3, v has a value of at least 5, and X is hydrogen or a monovalent hydrocarbyl group such as lower alkyl, butyl being especially suitable.
Particularly useful as foam-stabilizing components of flame-retarded flexible polyurethane formulations are the block copolymers wherein the polysiloxane blockc are trialkylsiloxy-endblocked and contain reoccurring difunctional dialkylsiloxy mono-meric units in combination with reoccurring difunctional cyanoalkyl-alkylsiloxy or cyanoalkoxy-alkylsiloxy mono-meric units, the mole ratio of the dialkylsiloxy units to the cyano-substituted siloxy units being about 10-200:3-100, and wherein the polysiloxane and polyoxy-alkylene blocks are ~oined through an Si-C or an Si-0-C
linkage, and from about 20 tD about 65 weight per cent of the oxyalkylene content of the polyoxyalkylene blocks is constituted of oxyethylene units. These block co-polymers are described and claimed in United States Patent No. 3,846,462. A preferred class of such surfactant~ are the cyanopropyl-substituted 48.

~47531 9149 block copolymer~ having the average formula, Me3sl0(Me2siO)x~esiO~ r MeSiO ~ SiMe3 l(CH2)~ ~~Ca~2~10)bC3 wherein: Me represents methyl; W represents a monovalent hydrocarbyl group (R'-), an acyl group ~R'C(O)-I or a carbamyl group lR'NHC(O)-l, wherein R~ has from 1 to 12 carbon atoms; x has an average value of from about 20 to about 100; y has an average value of from about 4 to about 30; z has an average value of from about 2 to about 10; a has a value of from 2 to 4, provited from about 20 to about 65 welght per cent of the oxyalkylene unit~ of the polyoxyalkylene chain, -(CaH2aO)b-, are constitutet 2 of oxyethylene; and b has an average value such that the average molecular weight of the polyoxyalkylene chain is from abo~t 1000 to about 6000.
Because of the high reactivity of high-resilience foam formulations, the foams are generally self-stabilizing and can be obtained without the use of stabilizing agent3.
However, it is usually desirable to include a silicone surfactant as an additional component of such formulation8 in order to minimize the tendency of the foam to settle and to control cell uniformity. Par~icularly effective for this purpo~e are the relatively luw molecular weight polyoxyalkylene-polysiloxane block copolymers described 49.

1~47~3~
and claimed in United States Patent No. 3,741,917.
Especially suitable as components of high-resilience formulations are the block copolymers described therein having the formula, Me Me3SiO(Me2SiO)x~R''O(CaH2aO)yCdH2dSiO]zSiMe3 wherein:

x has an average value of from 2 to 7; y has a value from 3 to 10; z has an average value from 2 to 6; a and d each has a value from 2 to 4; and R" is a monovalent hydro-carbon radical such as alkyl, aralkyl and aryl radicals,or an acyl group.
Also suitable as organosilicone components of high-resilience foam formulations are the relatively low molecular weight aralkyl-modified polymethylsiloxane oils described and claimed in United States Patent No.
3,839,384.
When used, the organosilicone component is usually present in high-resilience formulations in an amount be~ween about 0.025 and about 2 parts by weight per 100 parts by weight of total polyol reactant.
Illustrative of suitable surfactant components of rigid foam formulations are copolymers wherein the polyoxyalkylene blocks are hydroxyl-terminated such as those described in United States Patent 3,600,418.

50.

~0 47 5 3~ 9149 The beta-amino carbonyl catalysts described herein are also effective catalytic components of flame-retarded foam formulations. The flame-retardants can be chemically ~ombined in one or more of the other mater~als wed (e.g., iD the polyol or polyisocyanate), or they can be used as discrete chemical compounds added as such to the foam formulation. The organic flame-retardants preferably contain phosphorus or halogen, or both phosphorus and halogen. U~ually, the halogen, when present, is chlorine and/or bromine. Flame-retardant~ of the discrete . chemical variety include: 2,2-bis(bromomethyl)-1,3-propane-diol (also known as dibromoneopentyl glycol); 2,3-dibromo-propanol; tetrabromophthalic anhytride; brominated phthalate ester diols such as those producet from tetrabromophthalic anhydride, prow lene oxide and propylene glycol, tetrabromo-bisphenol-A; 2,4,6-tribromophenol; pentabromophenol; bromin-ated anilines and dianilines; bis(2,3-dibromopropyl)ether of sorbitol; tetrachlorophthalic anhydride, chlorendic acid; chlorendic anhydride; diallyl chlorendate; chlorinated maleic anhytride; tris(2-chloroethyl)phosphate l(ClC~2CH20)~P(0)1; tris(2,3-dibromopropyl)phosphate;
tri~(l,3-dichloropropyl)phosphate; tris(l-bromo-3-chloro-isopropyl)phosphate; tris(l,3-dichloroisopropyl)phosphate;
bis(2,3-dibromopropyl) phosphoric acid or 9alt~ thereof;
oxypropylatet phosphoric ant polyphosphoric acids; polyol phosphites ~uch as tris(dipropylene ~ ycol)phosphite;

, .. ....... ,. ,, . . .. , .. ... , . . , .. . .. , .. ... .. .. " ,. .... ., . . , . .. , . . , . . ~

9149 .
1S)47531 polyol,phosphonates such as bis(dipropylene glycol)hydroxy-methyl phosphonate; di-poly(oxyethylene)hydroxymethyl phosphonate; ti-poly(oxypropylene)phenyl phosphonate; di-poly(oxypropylene)chloromethyl phosphonate; di-poly(oxy-propylene)butyl phosphonate and'0,0-diethyl-N,N-bis(2-hydroxyethyl)aminomethyl phosphonate. Al~o suitable are compounds having the formulas:
O

(ClcH2)2clcH~op(ocH2cH2cl)2]2 ant 100 I o _ I O
,. .. ll ClCH2CH20-1_0_jH----P o-fH- _p(OCH2CH2Cl)2 ClCH2CH2 l CH3 ' OCH2CH2Cl i n Other suitable flame-retardants comprise halogen-containing polymeric resins such as polyvinylchlor~de. resina in combi-nation with antimony trioxide and/or other inorganic metal oxide~ such as zinc oxide, as described in United States Patents 3,075,927; 3,075,928; 3,222,~305; and 3,574,149.
It is to be understoot that other flame-retardants known to the art may be u~ed and that the aforesaid compounds may be employed indivitually or in combination with one another.
When used, the flame-retarding agent can be present in the foam formulations described herein in an amount f~om about 1 to about 30 parts by weight per 100 52.

.... .. . ..... .. .. . . .... .. ......... .. . .... .. . . . ...... . ..... . ....... .... . . ... . . . . . . .
... . .

914g 104753`1 parts by weight of the polyol reactant, the particular amount employed dopending larg~ly on the efficiency of any given agent in reducing fl~mmabillty.
lf desired, other additional ingredients can be employet in minor amounts in producing the polyurethane foa~ in accordance with the process of this invention.
lllustrative of iuch additives that can be employed are:
the aforementioned cross-linking agents ~uch as glycarol, diethanolamine, trlethanolamine and their oxyalkylene adducts; additives to enhance load-bearing propertie~
such as methylene-di-ortho-chloroaniline (MOCA); 89 wel}
a~ fillers, dyes, pigments~ snti-yellowing agents and the like.
The cellular urethane polymers of the invention may be formed in accordance w~th any of the processing techniques known to the polyurethane art 3uch as the "one-~hot", quasi-prepolymer ant prepolymer techniques.
For exanple, in accordance with the "one-shot" proces~, foamed product~ are produced by carrying out the reaction of the polyisocyanate and the polyol reactan t9 in the presence of the beta-amlno carbonyl-con~aining catalyst - s~stems tescribed herein, 3imultaneously with the foaming operation. This one-step process is usually employed in producing flexible fosm incluting high-resilience fos~, although it is al~o applicable to rigids. In preparing foamed products in accordance with the qua~i-prepolymRr S3.

` 1~)4753~
technique, the polyisocyanate i~ first reacted with a portion of the polyol reactant to give a product having a high percentage of free -NC0 groups (e.g., from 20 to 50 per cent), and the protuct is subse~uently foamed by reaction with atditional polyol and foaming agent ~n the presence of the beta-amino carbonyl catalysts.
In the prepolymer techni~ue, the polyisocyanate is reacted with a ilightly less than stoichiometric quantity of the polyol reactant to form a prepolymer having ~ low percentage (e.g., from 1 to 10 per cent) of free -NC0 groups, followed by reaction of the prepolymer with a blowing agent such as water in the presence of the catalyst s~stem~ tescribed herein to form the cellular material. These various mul~ tage methods are more u~ually applied to rigid formulations.
In general, final or post-curing of the foam products is achieved by allowing the foam to stand at ambient temperature~ until a tack-free product i9 obtained or bq sub~ecting the foam to elevated temperatures up to about 500F. in order to achieve more rapid curing. In view of the higher reactivity of the combination of reactants employed ~n producing high-resilience foams, however, a sufficiently high degree of curing i9 achieved during foam formation without the necessity of sub~esting the foam to conventional high temperature (e.g., 300-500~ ) po~t-curing procedure~ which are otherwise applied in the commercial msnufacture of flexibl~ foam~ from less highly reactive flexible foam formulationR.
54.
.. . . . . . . . .. .. . . . . .. . ..... ..... .. . . . ... .. . . . .. . .. . . .... .. . . . .
. .

5 3 1 In the specific application of the beta-amino amides and beta-amino e3ter~ described herein a~ catalytic components of molded, high-resilience foam formulations, the mold is charged with the foamable reaction mixture either at ambient temper-ature or pre-heated to a temperature of from about 70F. to about 200P., in an amount sufficient to at least compl~tely fill the mold. The molt is then closed and the reaction mixture is allowed to foam ant cure itself. In view of the excellent mold-release characteristics of the high-resilience foams produced in accordance with the pre3ent invention, th~ foamed product i9 readily removed from the molt without sub~tantial damage to the foam surface.
The temolded foam is suitable for end-u~e application without further curing. It i8 to be understood, :
however, that such foam may be sub~ected to further curing, as desired.
The end-use applications of cellular polyurethanes are well kncwn. Thus, the poly- -urethahe foams produced in accordance with ~he present invention are useful as textile inter-l~ners, cushioning material, mattresses, paddings, carpet underlay, packaging~ gasksts, ~ealers, thermal in~ulators and the llke.

.. ~ . . .. , ~ , .. .... . ... .. .. . ... . .. .. . . . .... .. ... ..... . . .. .. .. .. . . . ... . . .
.

The follawing examples are offered as further illustrative of the present invention and are not to be construet as undul~ limiting.
Examples 1-10 describe the preparation of illu~trative beta-amino carbonyl catalysts, designatet herein as Amine Catalysts I-X, respectively, which were employed a~ cataly~t components in the polyurethane foam preparation~ of the remaining examples. Of these, Amine Cataly~ts rv, V, VI and VII are novel compounds. In Examples 1-10, the amine reactant was substantially anhydrous and the reaction media contained less than about S weight per cent water, expresset on the basis of amine reactant. The yields of protuct are based on the number of moles of reactant present in the limiting amount.
EXAMP~ES 1-4 In accordance with these examples beta-dialkyl-amino-N,N-dialkylamide~, designated herein as Amine Catalyst~ I-IV, re~pectively, were prepared by the reaction of ~econtary amines (Reactant A) and alkyl esters of alpha,beta-unsaturatet carboxylic acids (React~nt B) in the presence of phenothiazine (0.7 gram) ant p-~ethoxyphenol (0.7 gram) as inhibitors, under elevated temperature and pressure conditions in a stain-less ~teel rocker bomb. The particular reactants, relative proportion3 thereof ant reaction contitions of 56.

~47 5 31 temp~rature, pressure ànt time are given in Table I.
Afte~ the indicated reaction time, the reactor~ w~re cooled and the respective reaction mixtures were tran~-^ ferret to a still except that, in Example 1, the reaction ~ixturo was partially stripped of volatile~ after dis-charge from the pressure reactor and a portion (200 grams) of the partially strLpped material was ccmbinet with phenothiazine (1.0 gram), p-methoxyphenol (0.5 gram) and .Humble 1243 oil as a-pot-boiler (20 grams). In each 10 example, the respective products were recovered by distillation under the temperature and reduced pressure conditions specified in Table I. Of these products, Amlne Catalysts I, I~ and II~ are kncwn compounts and were produced in a purity of about 75-98 per centl as inticated by gas chromatographic analysis. Amine Catalyst rv i8 a novel compound and its structure was verified by infrared and nuclear magnetic resonance spectro~copy.

57.

i.()4753~

~ a ¦ a ~ ~ ~ Y

~! ; ; ;
i ~ j ~

~0 4~5 3 Preparation of 3-Dieth~lamino-N N-DimethYlPro~ionamide In accordance with thi~ example, anhytrous diethylamine (44 grams) and N,N-dimethyla~rylamide (60 gram~) were heated at reflux temperature (about 56-60C.) for 48 hours. After this period of time, the reaction mixture was sub~ected to distillation to Jeparate unreacted amine and amide followed by recover~
of product in 86 per cent yield at 70C. and 2 mm.
mercury pressure. The liquit product (purity - about 95 per cent) i9 designated herein as Amine Catalyst V, and has the formula, (C2H5)2N-cH2cH2c(O)N(cH3)2- The structure of this novel product was confirmed by infrared functional analysis and purity by gas-liquid chromatographic analysis.

PreParation of 3-(N-MorPholino)-N',N'-DimethvlProPionamide Morpholine (45 grams) was added dropwise to a stirret reaction flask containing N,N-dimethylacrylamide (50 grams). After the addition was completed, the reaction mixture was stirred for 24 hours at 30-70C. After this pe~iod of time, the reaction mixture was heated at 110C.
and 10 mm. mercury pressure to remove unreacted starting materials. The remainin8 material was a viscous liquid and was recovered in a 95 per cent yield. This residue protuct contains about 98 weight per cent of the novel compount, .. . . . . .. . . .... . . .. .. . .. ..

g ~CH3 ~ N-CH2CH2-C N \CH3 and is designated herein as Amine Catalyst VI. A ~ample o~ thi~ material was tistilled at 114-115C. and 1 mm.
mercury pressure wlthout appreciable decomposition. The structure was verifiet by infrared and nuclear magnetic - resonance spectroscop~.

PreParation of N.N'-Pi~erazino-bis~3-(N",N"-dimethYl~roPionamide~ 1 To a stirred solution of piperazine ~25.0 grams) di~olvet in ethanol (30 grams), N,N-timethylacrylamide (59.4 grams) was added. After the adtition, t~e reaction mixture was stirret at 30-40C. for 2 hours. The precipi-tated material was filtered, washed with ethanol and tried unter vacuum. The solit protuct (76 per cent yield) has a melting point of 137-138C. ant the structure:

CH3~ NCCH CH -N ~ ~ ~CH3 c~3~ 2 2 \__J CH3 as determined by infrared ant nuclear magnetic resonance spectro~copy and elemental analysis. Anal. Calcd. for - C14H2gN402: C, 59.1; H, 9.9; N, 19.7. Found: C, 58.~
and 58.4; H, 9.59 and 9.52; N, 19.5 and 19.4. This novel product ~8 deslgnatet herein as Amine Catalyst VII.

60.

.~)47 5 3 i Preparation of Eth~l 3-(NIN-DimethYlamino)Propionate To a chilled (-15C.) reaction vessel there was adted: anhydrous timethylamine (100 grams); ethyl acrylate (250 grams); phenothiazine (0.5 gram); and p-methoxyphenol (0.5 gram). The mixture was maintained at -13C. for two hours with stirring after which the temperature was all~wed to rise to about 25C. Uhreacted timethylamine and ethyl acrylate were removed by dis-tillation. The product was recovered by distillation at58C. and 10 mm. mercury pressure in a yield of 97 per cent. The product, designated herein as Amine Catalyst VlII, has the formula, (C~3)2NCH2CH2C(0)0C2Hs, a9 verifiet analytically ~y lnfrared spectroscopy.
EXA~Pl.E 9 Pre~aration of EthYl 3-(N.N-DiethYlamino)ProPionate The following materials were charged to the reaction vessel: anhydrous diethylamine (292 grams);
ethyl acrylate (200 grama); phenothiazine (1.0 gram);
and p-methoxyphenol (1.0 gram). This mixture was heatet at reflux (about 56-60C.) for 24 hours. At the end of this periot, unreacted amine was removed by dist~llation. The product was recovered at 80-81C.
and 10 mm. mercury pressure in a yield of 96 per cent.
Th~ product i9 de ignated herein as Amine Catalyst IX
and ha~ the formula, (C2Hs)2N-CH2CH2-CtO)0C2Hs. a9 verified analytically by infrared 3pectroscopy.

61.

... . . . . . . . . . . . . . . .. . ..

753i EXAMP~E 10 e~aration of 2-(N.N-dimethYlamino)ethY1 3-(N'.N'-dimethYlamino) ProPionate ~ nhydrous dimethylamine (19.8 grams) was added dropwise to 2-(N,N-dimethylamino)ethyl acrylate (31.5 grams) in a magnetically-stirred, ice-cooled reaction ve~el at such a rate that the temperature d~d not exceed 40C, The addition of dimethylamine was complete ~n about 10 minutes. After allGwing the reaction mixture to stir overnight at room temperature, it was sub~ected to reduced pressure (about 20 mm. Hg) to remove unreacted timethylamine. Gas-liquid chromatographic analysis indicatet that the resldue product was 96.5 per cent pure. The Jtructure of the product, CH3~ ~ ,CH3 ~ N-cH2cH2-c-ocH2cH2 N~cH

wa~ verified spectroscopically (nuclear magnetic resonance and infrared) and by elemental analysis. Anal, Calc'd.
for CgH20N202: C, 57.4; H, 10.6; N, 14.9. Found: C, 57.3;
H, 10.5; N, 14.8. This product is designated herein a~
Amine Cataly~t X.
~n the e~amples which follow, molded and free-rise cellular polyurethanes were prepared employing the ab~ve-described Amine Catalysts I-X as catalytic com-ponents of a variety of foam formulations. In some exa~ples, these beta-amino am~de and ester catalyst~ were 62.

S.047531 usQd as the ~ole tertiary amine catalytic component of the reaction mixtures whereas in other instance~ they were used a~ component~ of mixed catalyst ystems. In preparing the molded foams of Examples 11-16, the pro-cedure employed was that described below as Foam Procedure I. The manipulative steps involved in the preparation of the free-ri~e foams of Examples 17-46 were as described under Foam Procedure II.
FQAM PROCEDURE I
An aluminum mold (4" or 2-1/2" x 15" x 15") i9 prepared by first waxing lightly with Brulin Permamold Release Agent and then pre-heating in a 140C. oven for about 10 minutes to raise the temperature of the molt to 175-200~F. Excess mold-release agent i3 wiped off and the mold is allowed to cool to 120F. before foaming.
The initial mixing of the component3 of the foam formu-lation is started when the mold i9 cooled to about 130F.
Th purposa of pre-heating the mold to the initial hi8h temperature i9 to remove ~olvent from the mold-release 2~ agent. All components of the reaction mixture, except thQ polyisocyanate reactant, are measured or weighed into a one-half gallon, five inch diameter, cylindrical, card-board carton and mixed 60 seconds with a 2-1/2 inch,

6-blade turbine at 4000 revolutions per minute. The poly-isocyanate reactant i9 then weighed into the mixture of other component~, stainless-steel baffles designed for 63.

~ ~ 47 5 3 ~

tha l/2-gallon carton are insertet, and mixing is continued for 5 seconds. The carton i~ then lowered to allow the mixer to drain, and the contents are quickly poured into the mold. The mold lid 18 closed and clamps are placed around the molt to permit flash-out. '~xit time" i9 obse N ed and defined as the t~me when all four top holes of the mold are full, that i9, when the foam begins to exude from all four holes of the mold. "Pop time" i9 observed and defined as the time when extruded parts stop bubbling. The 4" mold i~ demolted after standing at room temperature for 10 mlnutes whereas the 2-1/2" mold i8 demolded after 8 minutes. After trimming around the edge~ with scissors, the foam sample i~ weighed before running through rollei3 four times to crush cells open, and i9 then allowed to cure for three days at room temperature before being submitted for physical property measure-meDt~ .
FoAM PROCEDURE II
The polyol and polyisocyanate reactants and ~urfactant (and, when employed, the flame-retardant and cro~s-linking agents) are weighed into a 1/2-gallon, five-inch tiameter, cylindrical cardboard carton. The water and catalytic amine components are measured and blended together in a small beaker. The t~n catalyst i~ measured in~o a hypodermic syringe. Eleven stainless-64.

0~7S31 steel baffles are insertet into the carton and centered on 8 drill press equipped with a 1.65-inch, 4-blade turbine. A tlmer is pre-set for a total of 90 second~.
The mixer is started at 2400 revolutions per minute and continued for 60 seconds, except that in those formu-lations containing polymer/polyols, the mixer is started - at 3000 revolution~ per minute. The mixer is stopped manually for a 15-second de-gassing period. At 75 seconds on the timer, mixing i9 continued for 5 seconds before adding the aqueous amine premix. ~ixing is continued 5 seconds and the tin catalyst is added after an additional 5 seconds of mixing. The blended contents sr~ poured into a 14" x 14" x 6" cardboard box. 8Oth the "cream time" and "rise time" are recorded which term~ denote the interval of time from the formation of the complete foam formulation to: (1) the appearance of a creamy color in the formulation, and (2) the attainment of th~ maximum height of the foam, respec~ively. The foam is allowed to stand at room temperature for about one day before being submitted for physical property measurements.
The phy~ical properties which were determined for the fle~ible foams produced in the examples and con~rol run~ were measured in accordance with the stand-ard~zed test procedures given below.

65.
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. . . . .....

~Q47S31 PorositY (Air), which is a comparative measure-meant of the tegree of openness of the cells of flexible foamJ, was tetermined in accordance with the following test procedure: The test specimen of foam (4" x 4" x 1/2") i~ compres3ed between two pieces of flanget plastic tubing - (2-l/4" I.D.) of an air porosity assembly maintained under an air pressure of 14.7 pounds. Air is trawn through the thickness (1/2") of the foam specimen at a velocity contsolled to maintain a dif~erential pressure of O.L inch of water across the thickness dimension. The air flcw necessary to develop the requisite preqsure differential i8 recorded and the air fl~w per unit area of the foam specimen is reported as the porosity of the foam.
ResiliencY of both the molded and free-rise foam~ was determined in accordance with ASTM D-1564-69.
nsitY~ Tensile Stren~th, Elon~ation, Tear Resistance and Compression Set were measured as described under (1) AS M D-2406-68 for ths molded foam~ produced in accordance with Foam Procedure I, and (~2) ASTM D-1564-69 for the free-rise foams produced in accordance with Foam ~rocedu~e II.
Indentation Load Deflection (ILD Values) to 25%
ant 65% deflections were measured in accortance with (1) ASTM D-2406-68 for the molded foam ~amples, the thick-nes~ of the sampte being 2-~2" or 4" depending upon whether the 2-1/2" or 4" mold was used, and (2) ASTM D-1564-69 for the free-rise foams, the te~t sample being 66.

cut to a 4" ehicknes~. Return Vaiue i8 the percentage ratio of the load required to support the return 25%
indentation after one minute a~ compared to the load required to support the initial 25% indentation after one minute. Loat Ratio i~ the ratio of the 65Z ant 25Z lLD values, respectively.
The following Examples 11-16 demonstrate the e~ficacy and advsntage~ of beta-amino amide and ester catalysts described herein when employed aq direct replacement~ for N-ethylmorpholine in high-resilience foam formulations.
EXAMPLES 11 and 12 Molded foams were prepared employing 3-dimethyl-amlno-N,N-dimethylpropionamide (Amine Catalyqt I) in Example 11, 2-(N,N-dimethylamino)ethyl 3-dlmethylamino-propionate (Amine Cstalyst X) in Example 12, and N-ethylmorpholine in Control Run K-l, as catalytic com-ponent~ of a high-resilience foam formulation, designsted herein a~ Foam Formulation A. The composition of thi~
reaction mixture a~ employed in Example~ 11 and 12 and Control ~un K-l i8 given in Table II which follows.

67.

.... , . ,.. . ,.. , ., .. _ . .. .. ~... . . ..... . ...... .. ....... . . . . ... . .. . .... . .. . . .

~.~47531 9149 ~~ ~
Parts Bv Wei~ht Control Examples Comzonent ~-1 11 aod 12 Polvol A AD ethylene oxide-c-pped, glycerol- 60 60 t-rted poly(oxypropyl-ne) trlol h vlng a ~gdroxyl No of bout 34, a mol-cular weight of bout 5000, nd a primary hydroxyl content of ~0-75 mole per ceDt Pol~ol B: A polymer/polyether polyol having 40 40 a Hydroxyl No of bout 28 and based on (parts by welght) styrene (10), acrylonitrile (10) and Polyol A (80), produced by polymerizing said moDomers in Polyol A
PolYisoc~anate A: A mixture of (1) 80 weight per 36 45 36 45 ceDt of the 2,4- and 2,6- lsomers of tolylene dilsocyanate, the weight ratio of said i~omers being 80 20, respectively; and (2) 20 weight per cent of a polyphenylmethylene polylsocyanate having an average -NC0 functionality of 2 7 and free -NCO content of 30 5-32 3 weight per cent W-ter 3 0 3 0 Amine Catal~sts Amine C-talvst A: A 70 weight per cent solution 0 08 0 08 of bl~2-(N,N-dimethylamino)ethyl]ether in dipropylene glycol Amine CatalYst B A 33 weight per cent ~olution 0 25 0 25 of triethylenediamine in dipropylene glycol N-EthylmorpholiDe 0 80 None Amlne Catalysts 1 and X, respectively None 0 20 Dibutyltin dilaurate 0 03 0 03 Surf ctant A /1/ 0 07 --Surfactant B /2/ -- 0 05 /1/ A phenylethyl-modified polymethyl~iloxanc oil haviDg the average compositioD, ~e3siO(~e2sio)X [ (C6H5C2H4) (~1e)sio~ysiMe3 wherein ~e repre0ents methyl and the average values of x Dd y are 3 0 nd 1 5, re~pectively;
/2/ Same as Surfact~Dt A, except average values of nd y re 3 8 0 d 1 9, respectively ~ 0 4 7 5 3 ~

Th~ foam~ of Examples 11 and 12, designated for con-venience as Foam Nos. 1 and 2, respectively, as well as Control Foam K-l, were prepared following Foam Proc-ture I, employing the 4" x 15" x 15" aluminum mold heated to 120F. Upon completion of foam formation, Control ~oam X-l was ea~ily removed from the mold after 10 minutes residence time and foam surface and freedom fr~m ~endency to ~hrink were excellent. However, the odor level emanating from the freshly demolded foam was very high and, although diminishing in intensity with time, this odor persisted for several hours. With respect to Foam No. 1, demold characteristics were also excellent and the cellular structure wa~ fine (as opposed to coarse). In the case of ~oam No. 2, demold charac-teri~tics were good and, although the foam surface structure was not as good as that of Control Foam K-l or Foam No. 1, lt was satisfactory. With respect to bot~ Foam Nos. 1 and 2, the odor level emanating from th~ fre~hly demolded foam was very low and clearly an improvement over the control foam. ~hese and other results as well as phy~ical property data of the re~pec-tive foams are given in Table III.

69.

9~4g ~04753~

TABLE III - HIGH-RESI~IENCE FOAM (M~lded) Example No. -- 11 12 Control Run K-l ~~ ~~
Foam No. K-l 1 2 Foam Formulation A
N-Ethylmorphollne, p.p.h;p. 0.80 None None Amine Catalyst 1 /1¦~ p.p.h.p. None O.20 __ Amine Cataly~t X-/2/, p.p.h.p. ~N~ne -- 0.20 2 Exit Time~ seconds 61 53 59 Po~ Time~ seconds 121 100 110 Hot Foam Odor High Low Low Foam ProPertie~
Baqal cell structure Good Good Fair Resilience, % ball rebound 63 64 64 Poro~ity, ft.3/min./ft.2 61 53.1 50.6 Density, lbs./ft.3 1.96 1.90 1.93 ILD ~4"), lb~./50 in.2 25% deflection 22.3 20.3 24.2 65% teflection 62.0 56.0 63.0 25% return 17.3 16.0 19.0 Return value, % 77.6 78.8 78.5 Load Rat~o 2.78 2.76 2.62 t`
Compres~ion Sets, %
75% 13.0 12.6 13.0 50% After Humit Aging /3/ 26.5 24.9 24.2 Tensile s~rength, p.s.i. 24.0 22.6 21.8 Elongation, % 199 204 192 Tear Resistance, lbs./in. 2.41 2.22 2.17 aumid Age Load Loss, % /3/ 22.4 20.6 . 20.2 /1/ 3-Dimethylamino-N,N-dimethylpropionamide.
/2/ 2-(N,N-Dimethylamino)ethyl 3-Dimethylaminopropionate.
/3/ Five hcurs at 120C. in 1007. relative humidity.

70.

. 9149 1 0 47 ~ 3 1 `
The result~ of Table III show that the improve-ment of low residual foam odor afforded by the catalysts of this invention is achieved withou~ sacrifice of the good overall combination of physical properties possessed b~ the control foam. Further, as evinced by the interval of time requlred for the foam to exude from the mold, the reactivity of the respective reaction mixtures containing - Amine Catalysts I and X was excellent even though the concentration of these catalysts was only one-fourth the concentration (on a weight basis) of N-ethylmorpholine.
In fact, as reflect~d bq comparison of the respective exit time~, the reactivity of the formulation contain~ng 3-dimethylamino-N,N-timethylpropionamite (Example ll) in an amount of 0.20 part per 100 parts of total polyol (p.p.h.p.), was 12-14 per cent higher than that of the control formulation containing 0.80 p.p.h.p. of N-ethylmorpholine.

In accordance with these examples, moldet foams were preparet employing Amine Catalysts II-V, respectively, as direct replacements for N-ethylmorpholine tControl Run K-2) in a high-resilience foam formulation, de~ignatet herein a~ Fosm Formulation B. The composition of thi.Q
reaction mixture 19 given in the following Table IV.

. ~ .. . . .. ... . .. .. .. . . .. . .. ......... ... . . . . . . .

~.~ 47 5 31 9149 TAB~E rv - FQAM FORMUIATION 8 Part~ Bv Wei~ht ~ Contsol Examples Component K-2 13-16 Polyol A /1/ 60 60 Polyol B /lt 40 40 Poly~socyanate A /1/ 34.38 34.38 Water 2.80 2.80 Amine CatalYsts Amine ~ataLyst A /1/ 0.08 0.08 Amine Catalyst B /1¦ 0.30 0.30 N-Ethylmorpholine 0.80 None Amine Catalysts II-V, respectively. None 0.15 Dibutyltin dilaurate 0.03 0.03 Surfactant C l2/ 1.50 1.00 /1/ Same as in Foam Formulation A of Table II.
/2/ A polysiloxane oil having the average composition, Me3SiO(Me2SiO)4[MeO~C2H40)3C2H4SiMeO]2.gsi~e3 where Me is methyl, employet as a 10 weight per cent solution in Polyol A.

The foams of Examples 13-16, tesignatet for convenience as Foam No~. 3-6, respectively, as well as Control Foam K-2 were preparet following Foam Procedure I, employing the 2-112" x L5" x 15" aluminum mold heated to 120F. Upon completion of foaming, it was found that in each instance demold characteristics were excellent as reflected by lack of foam tenderness and ease of demolding. The surface s~ructure of Control Foam K-2 and Foam Nos. 3-6 wa~ also goot. ~owever, the odor level emanating from the freshly demolted control foam was high. Uith respect to Foam Nos.
3-6, on the other hand, hot foam otor was low and clearly an improvement over that of the control foam. Other results and foam physical property data are given in Table V.
, t2.

.

~.047531 U~ o~
~ l :~ O ~ CU i ~Y3~ C'J N
., . ..

U~ o~ o ~j . ~ ~ I 0 Y~ ~3i ~ ) N ~æ ~ N i ~ cu aJ

_ ~ ~ l~ N ~ U~ U~
.8 ~i l :~ ~ O ~ ~

~ a~ ~ ~ I u~:t O ~O u~
~ ~o' ~ 3 ~ ~

æ
Y O ~ N ~ ~JY~ ~N ~ . ~ ~ .

~1 ~1 .... . ;~
.~ Z,~

P~ c 0~ O ~a ~~ ~ Z~

g~' ~ 3~ æ~æ3 ~

73 .

.. ... . ....... , . ~ .. ... ...... .......... .. . .. ... .. ... ........ . ... .. . . . ... . ..... . .... ... .. . .

~.~ 475 ~
The results of Table V shcw that the improve- ;
meDt in hot foam odo~ realized by u9e of Amine Catalysts l~-V in place of N-ethylmorpholine was achieved without impairment of the overall combination of physical properties poJsessed by the control foam. Thus, the resiliency and porosity of Foam Nos. 3-S, were at least as good as that o~ the controi foam and their load-bearing, compression ~et and other properties were also good. In addition to the improvement in ho~ foam odor, the humid age load 1089 of Foam Nos. 3-6 was at least 12 per cent less than and thw-superior to that of the control foam.

In accortance with this example, 3-dimethylamino-N,N-timethylpropionamite (Amine Catalyst I) was employed in combination with bis[2-(N,N-timethylamino)ethyl]ether as the amine catalysts of a free-rise, high-resilience foam formulation containing trist2,3-dibromopropyl)phosphate as an added flame-retarding agent. A control foam wa~ also prepared (Control Run K-3) employing the same formulation except that a 33 weight per cent solution of triethylene-diamine was employed as the 301e amine catalyst. The c~mposition of the respective reaction mixtures (Foam ~ormulation C) i9 given in Table VI. The foam of this example and the control foam were preparet following f~ee-rise Foam Proceduse II. The results and foam physical property data are also given in Table VI.

74.

.... . ....... .. . ..

~.047531 T~BLE VI - HlGH-RESILIENCE FCAM tFree-Rise) ~xamDle No -- 17 Control Run No ~-3 ~~
ro m No ~-3 7 Fo m Formul-tlon C Pcrta by Welght Polyol B /1/ 50 50 Polvol C An thylene oxlde-capped, glycerol 50 50 at-rted poly(oxypropylene) triol havlng a Hydroxyl No of bout 27, molecular welght of about 6000, nd a prlmary hydroxyl content of 80-85 mole per cent PolYlsocYanate B A mlxture of the 2,4- and 2,6- 28 3 28 3 isomers of tolylene dlisocyanate, the welght ratlo of sald lsomers being 80 20, respectively ~Index - 110) Dlethanolamine 0 8 0 8 Water 2 0 2 0 Amlne CatalystJ
~mlne Cataly~t B A 33 welght per cent solution 0 40 None oi trlethylenediamine in dipropylene glycol Bls[2-(N,N-timethylamino)ethyl]ether (undiluted) None 0 06 ~mlne Catalyst I /2/ None 0 24 Stsnnous octoate 0 06 0 06 Trlo(2,3-dibromopropyl)phosphate 2 0 2 0 Surfactant C /3/ 1 0 1 0 Crcam Time, ~econds 6 6 ~18e Tlme, -coDds 155 185 Foam ProDerties ~esiliency, Z ball rebound 62 61 Poroslty, it 3/min /ft 2 37 ~enclty, lbs /ft 3 2 98 2 96 ILD (4"), lbo /50 ln 2 - 25Z deflectloD 35 2 34 3 65% deflectlon 79 3 77 2 25Z return 28 8 27 0 2eturn value, Z 81 8 78 8 Load Ratio 2 25 2 25 Compression Sets, Z

Senail- ~trength, p s i 21 1 20 6 Elongation, Z 187 177 Tear ~eslatance, lbs /in 2 71 3 05 Humid Age Load Loss, Z /4/ 35 6 34 5 502 Compression Set Aft-r Humid AglDg, Z /4/ 11 9 13 4 /1/ A~ defined in Table II5 /2/ 3-DlmethylamiDo-N,N-dimethylpropionamide /3/ ~J ldentif$ed iD Sable N
/4/ Aged flve hours st 120 C in lOOZ relatlve humidity ~047531 The results of Table VI indicate that Foam No. 7 and Contsol Foam K-3 had excellent resiLlency and about the ~ame overall combination of physical properties. Both foams wer~ also of fine cell structure. Although formulation reactivity, as reflected by rise time, was higher in the case of the control reaction mixture, reactivity of the reaction mixture employet in Example 17 was good. The higher reactivity observed for triethylenediamine is offset by a number of advantages offered by use of 3-dimethylamino-N,N-dimethyl-propionamide in combination with bis[2-(N,N-dimethylamino)-ethyllether~ One such advantage is that the latter catalysts are both normally liquid materials whereas triethylenediamine, although an excellent catalyst, has the processing tisatvantage of being a solid. Perhaps more significantly, triethylene-tiamine i~ also associated with a relatively strong amine odor which wa~ noticeable as a resitual odor in the freshly pre-pared control foam. On the other hant, freshly prepared ~oam No. 7 wa~ completely free of any amine odor.
EXAMPLES 18 and 19 In accordance with these examples, 3-(N-morpholino)-N~,NI-dimethylpropionamite and N,N'-piperazino-bis[3-(N",N"-dimethylpropionamide)], designated herein as Amine Catalysts VI and YII, were employed as the respective sole amine catalyst~ of a reaction mixture (Foam Formulation D) which otherwise contains components employed commercially for th~
manufacture of free-rise (slabstock) flexible polyurethane foam. The foams were prepared following Foam Procedure II.
The composition of Foam Formulation D and the results are given in Table VII which follows.

.... . . .. ... . . .. . . ... . . . . ......... .. . ...... . . .. . .. ...

~0~7 TABI,E VII
ExamPle No. 18 19 Foam No. 8 9 Foam Formulation D, Parts By Weight Polvol D: A glycerol-started poly(oxy- 100 100 propylene) triol having a Hydroxyl No.
of about 56.
PolYisocYanate B: A mixture of the 2,4- 49.75 49.75 and 2,6- isomers of tolylene tii90-cyanate present in a weight ratio of 80:20, re~pectively. (Index ' 105) Water 4 Stannous octoate ~ 0.275 0.30 Surfactant D /1/ 1.0 1.0 Amine Catalyst~:
Amine Catalyst VI /2/ 0.40 --Amine Cataly~t VII /3/ -- 0.40 Cream Time, ~econds 13 13 Rise Time, seco~ds 111 110 Foam ProPerties Resiliency, % ball rebound 41 42 Poro~ity, ft.3/min./ft,2 84 65.5 Density, lbs./ft.3 1.79 1.71 ILD (4"), lbs./50 i".2 25% te~lection 37.0 38.0 65Z teflection 80.0 73.5 2S% roturn 25.4 23.9 Return value, Z 68.7 62.9 Load R~tio 2.16 1.94 Compre~sion Sets, %
90X 5.11 5.28 50% After Humit Aging /4¦ 7.17 7.6 Ten~ile ~trength, p.s.i. 16.7 15.2 Elongation, % 217 202 Tear Resistance, lbs./in. 2.47 2.34 Humid Age Load Lo~s, Z /4/ 15.4 12.9 .
/1/ A polyoxyalkylene-polysiloxane block copolymer having the average compo~ition:
MeSil(OSi~e2)6 .4(C2H4)l9(c3H6)140c4H9]3 wherein ~e i9 methyl.
/2/ 3-(N-~orpholino)-N',N'-dimethylpropionamide.
/3/ N,N'-Piperazino-bis[3^~N",N"-dimethylpropionamide)].
¦4/ Five hours at 120C. in 100% relative humidity.

~0 475 31 ThQ data of Table VII demonstrate that Amine Catalysts VI and VII are catalytically active in pro-motlng the isocyanate-water reaction, as reflected by ri~e time and the highly porous nature of the foam products. The data also indicate the efficacy of these catalysts in allowing for th~ formation of flexible foams - having a good combinstion of physical properties including lo~ c pressioD set values and low load losses after humid aging. These foam~ were also completely odorless.
EXAMP~ES 20-23 ~ n accortance with these examples, 3-dimethyl-amino-N,N-timethylpropionamide (Amine Catalyst I) and 2-(N,N-timethylamino)ethyl 3-timethylaminopropionate - (Amine Catalyst X) were employed as the respective sole amine catalysts of ~oam Formulation D (Table VII) in place of Amine CataLysts VI and VII. The foams were prepared following free-ri3e Foam Procedure II. The concentration of amine cataly~t and ~tannous octoate employed in these examples and the results are given in Table VIII which follows.

78.

1(.~4753~
T~BLE VIII - YLEXIBLE FoA~S (Free-~i~e) Ex-m~le No. 20 21 22 23 ~04m No. 10 11 12 13 roam Formulation D /1/
St-nnous octo te, p.p.h.p. O.3 0.425 0.25 0.275 ~mino Cat-ly~t I /2/, p.p.h.p. 0.1 0.20 -- --k~ino Cataly~t X /3/, p.p.h.p. -- -- 0.40 0.20 Cr-am Time. ~-conds 11 11 12 13 ise Time. ~-conds 90 70 100 103 - Poam Prooertles ~asillency, Z bell rebound 45 44 45 46 Porosity, ft.3/min./ft.2 97 61 93 93.5 DenJity, lbs./ft.3 1.62 1.55 1.56 1.62 ILD (4"), lbs./50 in.2 25Z deflection 38.5 38.5 33.0 40.9 65Z deflection 70 65.8 58.4 76.1 25Z return 26.7 26.4 21.4 26.2 ~eturn value, % 69.4 68.6 64.9 64.0 Lo~d ~atio 1.82 1.71 1.77 1.86 Co~pression Sets, Z
75~ 4.1 4.6 -- --90% __ -- 7.32 5.15 T nslle strongth, p.8.i. 17.3 19.3 15.4 15.2 Elongation, Z 204 232 215 173 T-ar Resistance, lbs./in. 2.63 2.72 2.43 2.07 Hurid Age Load Loss, 2 /4/ 6.8 8.17 9.18 14.7 /1/ Except for the variation in stannous octoate concontration aDd the amine catalyst employed, the composltion of this for~ulation i8 as defined in T-ble VII.
/2/ 3-Dimethylamino-N,N-dimeehylpropionamide.
/3/ 2-(N,N-dimethylamino)ethyl 3-dimeehylaminopropionate.
/4/ Aged five hours at 120-C. in lOOZ rolative humidity.

1~47S31 The results of Table VIII further indicat~ that the cataly~ts described herein are effective promoter~ of the water-isocyanate reaction and, as reflected b~ the relatively short rise time, Amine Catalyst I has particu-larly good reactivity in this respect. The data also indicate that the flexible foam protucts were highly porous and had a good overall combination of properties. For the purpose of comparison, it is noted that when 0.1 p.p.h.p.
of a 70 weight per cent solution of bis[2-(N,N-dimethyl-amino)ethyl]ether (i.e., Amine Catalyst A) is employed as the sole amine catalyst of Foam Formulation D at the same sta~nous octoate level (0.30 p.p.h.p.) employed in Example 20, the resulting formulation provides a cream time of 10 seconds and a rise time of 80 second~, and the flexible foam protuct ha~ the following properties (expresset on the basis of the sam~ unit~ shown in Table VIII)~ porosity - 58.7; resiliency 46; denJity ~ 1.45; 25% ILD - 39.1, loat ratio - 1.72;
90Z compression set - 3.36; tensile strength - 17.4;
elongation - 235; and humid age load 1099 ' 14.1.
EXAMPLES 24^30 A series of free-ri~e, flexible foams was prepared employing reaction mixtures containing the beta-amino carbonyi catalysts of the invention in combination with bis[2-(NJN-dimethylamino)ethyl]ether. The particular beta-amino carbonyl compounds employet were Amine Catalysts I-V, VIII and rx, respectively. The composition of the reaction mixtures, designa~et Foam Formulation E, i9 given in Tabls rx.

810 .

.. . . ... .. . . .. .. .......... . . .... . ....... . . .. . ... .. . .. . . . . . ..... . .

1 ~47531 TABtE rx - FOAM FORMULATI~N E
Parts BY Wei~ht Control Examples ComPonent R-4 24-30 PolYol E: A polyether triol having a 100 100 Hydroxyl No. of 46 and containing less than S mole per cent of primary hydroxyl groups, derived frcm glycerol, prowlene cxite and ethylene oxide, about 14 weight per cent of total oxide bein~
ethylene oxide.
PolYisocyanato B: An 80:20 mixture of 48.2 48.2 ,6- isomers of tolylene diisocyanate, re~pectively. (Index - 105) Water 4.0 4.0 Stannous octoate 0.25 0.25 Surfactant D /ll 1.0 1.0 Amine Catal~sts Amine CatalYst A: A 70 weight per cent 0.1 --solution of bis[2-(N,N-timethylamino)-eth~llether in dipropylene glycol.
Blend: A 67/33 parts by weight blend -- 0.1 of Amine Catalysts I-V, VIII or rx and bis~2-(N,N-timethylamino)ethyl]-ether.
/1/ As defined in Table VII.
. .
A~ inticatet in Table rx, th~ cataLysts employed in the examples were added as blends (0.1 part) containing 67 and 33 part~ by weight of the beta-amino carbonyl compound and bis-ether, respectively, thereby providing 0.067 and 0.033 part byweight of each type of catalyst per 100 psrts of polyol reactant (p.p.h.p.). As further indicated in Table rx, th~ control formulatlon employet in Control aun K-4, contained the bis-ether (0.070 p.p.h.p.) as the sole amine catalyst, atded as 0.1 part of a 70 weight per cent solution thereof. The variou~ foams were prepared following Foa~ Psocedure II.
Ths results are given ia Tabls X.

~047531 ~ 2 ~ o o ~ oO~ ~0 o~ ~ ~ 0 CU

~ 0 ~ o~ ~ U~l o~
N I ~ ~ O O ~~ t~ D N~ ~1 ~ rl ~I CN ~1~1 D ~ N 0~ 0 ~ ~0 ~
1 0 0 cr~rl`.D N~0 rl 0 rl ~I N ~)~1 ,~ ~ 0. ~ ~ ~ ~ ~0 H

0 o~00~
N ~1-1 0 0 O~0~N r--~ ~

O~D 0 ~ ~ ~ ~ N ;~ :
~CN t ~ 1 O Orl ~ ~ ~i t0'~1~ NI ~O ~i l~`.O ~ N ~ N ,~
~ . ~ .
O t-CU ~ 0 ~0 ~ 0 .:t~a o . u~. - - -~ U~N ~1 x a~ D ~ ~ O t~
O O~t u~ ~1 ~ N ~ rl Ir~ N N ~ N ;~
P4 ~
~ :

b o ~ .

82.

~.0 475 3~
The results of Table X indicate that the blended amine catalyst~ employet in Examples 24-30 provided f~exible foams having an overall good combi-natio~ of physical properties as comparet with Control Foam K-4 and that certain individual properties were ~uper~or. Thus, in each instance, Foam Nos. 14-20 were markedly more porous than the control foam; particularly out~tanting in this respect were Foam No. 14 based on Amine Catsly~t I (3-timethylamino-N,N-dimethylpropionamite), 10 Poam No. lg based on Amine Catalyst VIII [ethyl 3-(N,N- -timethylamino)propionate], and Foam No. 20 based on Amine Catalyst rx [ethyl 3-(N,N-dlethylamino)propionate]. In addition to their enhanced poro~ity, Foam Nos. 14-20 al~o exhibited lower load 1099 values after humit aging than tho control foam; especially outstanding in this respect were Foam Noq. 15-18 based on Amine Catalysts ~I-Y, respectively. Of further ~ignificance is the realization of these improvements without the necessity of employing catalysts associated with the odor charac-teristic of amines; freshly prepared Foams 14-20 were otorless.
EXA~PLES 31-37 Ia accordance with these examples, another ~eries o foam~ was prepared employing respective re~ction mixture baset on ~he blends of Amine Catalysts I-V, VIII and ~X described under Example~ 24-30. The compo~ltion of the reaction mixtures (Foam Formulation F) incluting that employed ln Control Run K-5 is given in Ta~le XI.
~3.
,,,,, ,, ~ ~ ., . 1 ., ., , ... . . .. .. .. . . .. ... , . ... , . . .. ,. . .. ~ .. . .

` 9149 ~0~753~

~ABLE XI - FQAM FORMULATION F
.
Parts 3Y Wei~ht Control Examples Component X-5 31-37 Polyol E /1/ 100 100 Polyisocyanate B !1/ (Index - 105) 37.9 37.9 Wster 3~0 3.0 Stannous octoate 0.275 0.275 `
Surfactant E /2/ . 1.0 1.0 A~ine CatalYsts Amine CatalY~t A: A 70 weight per 0.1 --cent ~olution of bis~2-(N,N-dimethylamino)ethyl]ether in dipropylene glycol.
Blend: A 67/33 parts by weight blend -- 0.1 of Amine Catalysts I-V, VIII or IX
and bis[2-(N,N-timethylamino)ethyl]-ether.

/1/ As defined in Ta~le rx.
/2/ A polyslloxane-polyoxyalkylene block copolymer having the average composition Me3sio(Me2sio)72[~Ro(c3H6o)29(c2H4o)2oc3H6siMeol5~lsiMe3 where Me is methyl, employed as a 55 weight per cent active sol~tion.

- .
~he foams of the~e examples as well as the control foam were preparet following Foam Procedure II. The results are given in Table XII.

84.

~1~)4753~
~ ~ O u~ N N
O O ~1~ N ~1 ~i ;~ N CU N

O O N ~' J' ~) ~ ~ 8 N ~ o 8 N:~ O O~ r~ N~:t ~i u~ ~ O ~

y~ o 0 ~~ ~
o ~~O O ~ No N ~S t~) t~ N

~ o N. Z~ o ~ o~ ~ 0 ~ ~ 8 8 0 J? O O~1--I ~ ON~ ~i~ O N~ 0 0~1 0 ~) S

0 ~ ~ ~ ~ 0N 0 ~
0 NH O O~ ~1 ~ ~ ~i0~ N ~0 ~1 ~0 0 ~ N N N

N ~ 0 ~ ~ 0 t_~; ~I N
~) ~ N~-I O O ~ 0 N~ Oæ ~

~ o t~ O ~ 0 ~ ~ 0 ~ ' ¦ ~) N~-1 O O ~ t F~ N~O ~i ~ 1 ~S , ~O ~ o t--Y;~ D ~ cr~ 0 ~0 ~ æ 0~N ~i 85.

~.~47S31 9149 As indicated by data of Table XII and as recognized in its use, Foam Fonmulation P i9 a difficult reaction mixture to prepare as a commercially open, porous product. Thus it was not surprising that Control Poam X-S, as well as Foam Nos. 229 23, 26 and 27, had porosity values less than 20. On the other hand, it wa~ unexpected to find that under this unfavorable condition, Foam Nos. 21, 24 and 25 based on Amine Catalysts I, rv and V, had scceptable open, porous ~tructures as reflected by their respective porosity values of 41.7, 29.2 and 30.8.

The purpose of these examples is to illus^
trate the efficacy of the beta-amino carbo~yl compounds a~ catalytic components of flame-retarded foam formu-lations (Examples 38-43) and their operating latitude with respect to variation in concentration of tin co-catalyst in such formulations a~ well as in non flame-retarded systems ~Examples 44-46). The compo~itions of the reaction mixtures are given in Table XIII. In Examples 38-45, the ~mine catalysts were added to the formulation as an 80:20 parts b~ weight blend of Amine Cataly~t I and bis[2-(N,N-dimethylamino)ethyl]ether, respectively. A 67/33 parts by weight blend of thesQ
catalysts was used in Examyle 46. Based on lO0 parts of polyol inclusive of flame-re~ardant when present, ~.0 4 ~ 5 3 1 -............. either 0.1 or 0.2 part o~ the respective blend~ were w ed. The foams were formed following Foam Procedure II~ The re~ults are given in Table XIII wherein "SE"
indicate~ that the foam sample qualified for a self- -extingui~hing rating under flammability test ASTM D-1692-67T.
Table XIII also includes data, as Runs A and B, by way of illu~trating a common effect that flame-retartant~ often have oa flexible foam porosity.

~7.

~47S3~ `

, ~ o. ~ o o o ~ ~ ~ o V~ o ~ ~n ~ ~ ~ ~ ~o ~ ~ ~o ~ o ~ . ~ ~o ~ ~ o ~ ~ o ~ o~
o .o.~ ~o_ .~ .... ~_ .~
,. _: : ~ ~, o o o o o~ ~ ~ ~o _ ,. ~o ~ ~ _ o ~ _ ~ ~ .. o C

.~ ~ ~, ~ ~oo~o~ ,.......... ..
O .0~ .JOO_.~ . ~ ~ 0~ o _ : : ~ ~ . o . o o o _ ~ ~ .o _ ~ ~ ~ ~ _ ~ o~ _ ~ ~ g .~ o .~ ~ _~o~ ~o ~,~
I ~O ~ I ~ . ~ O ~ 0 ~ ~ ~ `
~ ~ o~.~o ooo__ ~_ ~o~_~_~

. o ~ O ~o ~ ~ . . ~ . 0 . . . ~ o~
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~ ~ ~ ~ ~ m ~ ~ o 1 0 0 0 _ ~ ~ ~ _ r~
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' -~047S31 - The results of Example~ 38-43 indicate that tho present discoverg of amine urethane catalyst~ which are capable of providing very high porosity polyurethane foam iJ of particular value in the preparation of highlg porou~, flame-retarded foams. ~he more u~ual result is illustrated by Run No~. A and B wherein the inclusion of the reactive flame-reeardsnt, dibromoneopentyl glycol, provided foams that shrank completely~ It should be understood that the excellent flammability properties 1~ of the foams produced in Examples 38-43 is in large measure attributable to the particular cyanopropyl-modified silicone surfactant (Surfactant ~) employed.
Thus, when the beta-amino carbonyl catalysts of this invention are employet in combination with this surfactant, particularlg effective formulations are provided for preparing open, highly porous flexible foam~ having excellent flame-retardant character. The data of Table XIII also show that these desirable results are realizet under a variety of contitions and ~hat ~ncreasing the tin co-catalyst (~tannous cctoate) levels to up-grade foam physical properties can ~e accomodated and ~till retain foam proce3sabilitg.
- The versatility of the beta-amino carbonyl compounds as effective catal~tic components of a wide varietg of reaction mixtures i8 further demonstrated by th~ follswing Examples 47 a~d 48 drawn to the preparation ~4753i of ri8id polyurethane foams. In preparing these foam~, all components except the polyisocyanate reactant were mixet for 15 seconds and, after appropriate ad~ustment for 10~8 of fluorocarbon blowing agent, mixing was conti~ued for an additional 15 seconds. The orga~ic polyisocyanate was then added and, after mixing the complete formulation for 5 seconds, it wa~ poured into an open box (12" x 12" x 12'~ se was measured until thc rate of rise was less than one millimeter per 10 seconds.
EXAMP~ 47 The rigid foam formulation employed in this example contained (on a weight basis): (a) 100 parts of a Jucrose-based polyol having a hydroxyl number of about 400 prepared as a mixed adduct of sucrose, diethylenetriamine and aniline; (b) 108 parts of a tolylene diisocyanate produced as a resid~e protuct in the manufacture of the 2,4- and 2,6- isomers of tolylene diisocyanate and having a free -~C0 content of about 38.5 weight per cent (Index ^ 108); (c) 1.6 parts of water; (d) 44 parts of inhibitet trichlorofluoromethane blowing agent; (e) 1.5 parts of a tin catalyst; and (f) 2 part~ of 3-dimethylamino-N,N-timethylpropionamide (A~ine Catalyst I). For the purpose of comparison, a control formulation was employed containing the afore-said component~ (a)-(e) and, aY amine catalyst component ~.

90.

~ ~ 47 5 3~
(f), 2 part~ of timethylethanolamine in placo of Amine Catalyst I. Formulation reactivity is indicated by tho following results, the value~ within parenthesis appLy~ng to tho control formulation: Cream time - 10 (8) ~econds; Gel time ~ 25 (35) second~; Tack-free time -35 ~S0) seconds; and Rise time - 35 ~55) seconds. Th~
lowe~ gel, tack-free and rise times indicate that the.
formulation containing Amlne Catalyst I was the more reactive formulation. In both instances r~gid foams of satisfactory ~uality were obtained.
EXAMPL~ 48 In accordance with this example, a rigid foam .. was prepared employing the following components (on a woight basis): (a) 85 parts of a sorbitol-based polyol h~vi~g a Hydroxyl No. of about 490 and a molecular weight o about 700, derived from sorbitol, dipropylene glycol and propylene oxide; (b) 13 parts of an amine pentol having a Hydroxyl No. of about 700, terived from diethylenetriamine and propylene oxide; (c) 2 parts of glycerol; (d) 148 parts of a polyphenylmethylene poly-isocyanate having an average -NC0 functionality of 2.7 and a free -NC0 content of 30.5-32.3 ~eight per cent (~ndex - 115); (e~ 41 parts of trichlorofluoromæthane blcwing agent; (f) 4.2 part~ of flame-retardant [0,0-tiethyl-N,N-bls(2-hydroxyethyl)aminomethyl phosphonate];
~g) 1.6 parts of surfacta~t (Union Carbide Corporation ~ .....

~ 047~3~
Silicon~ Surfactant L-5420); (h) 0.4 part of N,N,N',N'-tetramethylbutanediamine; and (i) 1.2 parts of 3-dimethyl-amiDo-N,N-dimethylpropionamide (Amine Catalyst I). For the purpose of comparison, a control foam was prepared employing the above formulation except that in place of Amine Catalyst I, 1.2 parts of Amine Catalyst B was used (that i8, a 33 weight per cent solution of triethylene-diamine ~n tipropylene glycol). Formulation reactivity was a~ follow~ wherein corresponding data for the control are given in parenthesis: Cream time - 60 (35) seconds;
Gel time - 100 ~85) seconds; Tack-free time - 190 (110) seconts; Rise time - 200 (130) seconds. These data ~how that, although reactivity of the control formulation was higher, Amine Catalyst I provited satisfactory results in this respect. In both instances, rigit foams of satisfactory ~uality were obtained.

92.

Claims (3)

WHAT IS CLAIMED IS:

1. A compound selected from the group consisting of 3-diethylamino-N,N-dimethylpropionamide and 3-dimethylamino-N,N-dimethylbutyramide.

2, 3-Diethylamino-N,N-dimethylpropionamide.

3. 3-Dimethylamino-N,N-dimethylbutyramide which has the formula, .