CA1095489A - Catalyst systems containing dimethylamino ether mono- ols for polyurethane foam formation - Google Patents

Abstract

9919-C-l CATALYST SYSTEM CONTAINING DIMETHLYAMINO
ETHER MONO-OLS FOR POLYURETHANE FOAM FORMATION

ABSTRACT OF THE DISCLOSURE
Cellular urethane polymers are provided by effect-ing the reaction of an organic polyol reaction comprising a polyether polyol and an organic polyisocyanate reaction in the presence of a blowing agent and a catalyst system com-prising a tertiary-dimethlamino ether mono-ol. In the dimethylamino ether mono-ols employed as catalysts in the practice of the invention, the tertiary-dimethlamino group and the hydroxyl group are positioned beta to a common acyclic ether oxygen atom or to different acyclic ether oxygen atoms which in turn are positioned beta to one another. The said dimethylamino ether mono-ols are versatile, low odor catalyst and are uSeful in forming cellular urethane polymers ranging from all water-blown flezible polyether foam to all fluorocarbon-blown rigid foam including semi-flexible and high-resilience foam products. Especially preferred for use in the practice of the invention are 2-(2-dimethlaminoethoxy)ethanol and 2-[2-(2-dimethylaminoethoxy)ethoxy]ethanol either as such or in combination with other catalyst including other tertiary-amine components and/or organic compounds of tin.
Also provided are blended catalyst systems comprising said dimethylamino ether mono-ols.

S P E C I F I C A T I O N

1.

Description

~t ~
1~95489 g~C-l B~C~GRO~iD OF THE IN~NTION
Thi~ ~nvention perl:ains to the use of a 2articular class of tertiar~--amino ether mono-ols a8 catalysts in the for~tion of cellular urethane polymers by the reaction of organic polyisocyanates and active hydrogen-contain5ng compounds in the pre-sence of a blowing agent. The invention also relates to particular blended catalvsts co~prising the said tertiary-amino ether mono-ols including the use there-of for polyurethane foam formation.
It is we;l kr.own to the art that cellularurethane polymers are provided by the reaction of organic polyisocyanates and active hydrogen-containing organic compounds such as in particular organic polyols, in the presence of a source of blowing action and one or more activat:ors. It is also known that a number of different chemical reactions occur during polymer for-mation and expansion. For example, in addition to the chain-extending, urethane-forming reaction between free isocyanate groups and active hydrogen, initally formed urethane linkages bearing secondary hydrogen may also function~as a source of active hydrogen and react with additional isocyanate to form cross-links between polymer chains. Further, in systems wherein the blowing agent comprises water such as, for example, flexible, semi-flexible and many rigid foam formulations, isocyanate is also consumed by reaction with water, thereby gener-ating carbon dioxide blowing agent in situ, and intro-ducing further cross-links comprising urea groupsO The nature of the cellular structure and the physical and ~La~ls489 g~lg-c-l mechanical properties of the foam are influenced by the extent of such reactions, and the relative rates and point in time at which they occur. Although balancing these variables so as to achieve a particular type or grade of foam can be controlled to some extent by the functionality, molecular weight and other struc-tural features of the polyisocyanate and active hydrogen-containing reactants, the catalyst system also plays a significant role in this respect.
Among the types of compounds that have achieved long-standing widespread comme-cial application as ctalysts in polyurethane foam manufacture are: tertiary-amines con-sisting of carbon, hydrogen and amino nitrogen, as typically illustrated by 1,4-diazabicyclo[2.2.2]octane ~"triethylene-diamine"), N,N,N',N'-tetramethyl-1,3-butanediamine and N,N-dimethylcyclohexylamine; tertiary-amines consisting of carbon, hydrogen, amino nitrogen and oxygen wherein oxygen is present as ether oxygen, as typically illustrated by bisl2-tN,N-dimethylamino)ethyl]ether and N-ethylmorpholine;
and tertiary-a~ines consisting of carbon, hydrogen and oxygen wherein oxygen is present as hydroxyl as typically illustrated by N,N-dimethylethanolamine.
More recent advances in cellular urethane manu-facture include the utilization of low odor tertiary-amines consisting of carbon, hydrogen, amino nitrogen and oxygen where oxygen is present as carbonyl of either a carboxylate or dimethylamido group, as described and claimed in U.S.
Patent No. 3,821,131, granted June 28, 1974. An especially effective catalyst of this latter type is 3-dimethylamino-N,N-dimethylpropionamide. Another relatively recent advance 9 S~ ~ 9 9919-C-l ~n the catalysis of ceIlular urethane manufacture ~6 the use of amine catalyst 8y8te~s col~prising 3-dimethylamino-propionitrile which is ~180 a low odor catalyst. This particular advance is described and claimed ~n United States Patent No. 3,925,268, granted December 9, 1975.
From the standpoint of catalytic activity for the H20/-NC0 reaction, the more potent of the afore-mentioned specific amines are triethylenediamine and biæl2-oN,N-dimethylamino)ethyl]ether. Such catalysts, which are also relatively expensive, are usually supplied and utilized in dilute form as solutions in catalytically inactive diluents such as glycols. Illustrative of such diluents are diethylene glycol and dipropylene glycol.
Of the aforementioned amines, one of the least ; expensive to manufacture is N,N-dimethylethanolamine ~`DMEA"~ which is readily prepared as the 1:1 molar adduct . of dimethylamine and ethylene oxide. Another attractive feature of DMEA is that it is less odorous than many other conventional amines such as N-ethylmorpholine, and those consisting of carbon, hydrogen and amino nitrogen such as, in particular, triethylenediamine and N,N,N',N'-tetramethyl-1,3-butanediamine. Relative to triethylenediamine and bis[2-oN,N-dimethylamino~ethyl]ether, DMEA exhibits moder-ate activity as a catalyst for water-blown, flexible slab-stock. It is often necessary, therefore, in its use in the manufacture of conventional flexible slabstock, to employ DMEA at enhanced concentrations relative to more potent catalysts, in order to meet particular activity and ~954~3 9919 -C-l foam property specifications of the foam manufacturer. The use of higher concentrations in turn may enhance any poten-tial deleterious effects of residual amino nitrogen on foam properties. In view of its low cost and low odor, DMEA is typically used in combination with other amines either as a catalytically active diluent for more potent and expensive amines or to "spike" the activity of less potent but more expensive catalysts.
Further in regard to DMEA as well as certain amines of the catalytically potent variety such as tri-ethylenediamine and N,N-dimethylcyclohexylamine, it is found that, whereas they may be suitable for forming con-ventional flexible and rigid foam, they are unsatisfactory catalysts over a broad range of concentration for the manu-facture of void-free, semi-flexible molded foam.
It is also found that certain amines which have widespread application in the manufacture of flexible poly-ether slabstock such as bisl2-(N,N-dimethylamino)ethyl]ether, have limited application as catalysts in the manufacture of rigid foam blown with fluorocarbon or a combination of fluorocarbon and water.
It is desirable, therefore, and is a primary o~-~ect of this invention to advance the art of polyurethane foam manufacture by the employment of relatively low cost, _ low odor tertiary-amino mono-ols which can be used with advantage from the standpoint of: (1) enhanced catalytic activity relative in particular to N,N-dialkylalkanolamines as typified by N,N-dimethylethanolamine; and/or (2) greater versatility in a wide variety of foam formulations including semi-flexible systems, rigid systems blown with fluorocarbon l~9i,~9 99l9 or a combination of fluorocarbon and water, as well as ~ater-blown flexible polyether foam. Various other objects and advantages of this invention will become apparent to those skilled in the art from the accompanying description and disclosure.

SUMMARY OF THE INVENTION
In accordance with one aspect of the teachings of the present invention, cellular poly-urethanes are provided by the method which comprises simultaneously reacting and foaming a reaction mixture containing: (l) an organic polyol reactant comprising a polyether polyol having an average hydroxyl function-ality of at least two; (2) an organic polyisocyanate reactant having an average isocyanato functionality of at least two; (3) a blowing agent; and (4) a cata-lytic system comprising a tertiary-dimethylamino ether mono-ol as more particularly described hereinafter.
The particular amino ether mono-ols employed in the practice of the present invention are character-ized by the presence of a tertiary-dimethylamino group, one or more ether oxygen atoms and one hydroxyl group, the said amino and hydroxyl groups being positioned beta to either a common or different acyclic ether oxygen atoms. In those compounds having a plurality ~ of ether linkages, the ether oxygen atoms are also - positioned beta to one another. Overall, the amino ether mono-ols employed as described herein_have from one to five acyclic ether oxygen atoms and at least six and no more than 26 carbon atoms, no individual 9919 -C-l ' 1~9~489 continuous carbon chain bonded to ether oxygen having more than four carbon atoms.
The aforesaid essential structural character-istics of the amino ether mono-ols employed ~n the practice of this invention are conveniently expressed by the following general Formula I:

CH3~
~ N-CH-CH-O-(CH-CH-O~n-H (I) Rl R2 R3 R4 wherein and as defined for the purpose of the entire specification:
Rl and R2 each represents hydrogen, methyl or ethyl provided that, cumulatively, Rl and R2 have no more than two carbon atoms;
R3 and R4 each represents hydrogen, methyl or ethyl provided that, cumulatively, R3 and R4 have no more than two carbon atoms; and n has an average value from one to about five.
In the compounds encompassed by Formula I, the Rl, R2, R3 and R4 groups may be the same as or different from one another.
` The above-described dimethylamino ether mono-ols are useful as catalysts in the manufacture of a wide variety of cellular urethanes ranging from water-- blown flexible polyether foam to fluorocarbon-blown - rigid foam including semi-flexible and high-resilience foam. Accordingly, in the method of this invention the blowing agent can be water, a fluorocarbon or a combination cf water and fluorocarbon. Suitable organic 1~95~89 9919-c-l polyol reactants for use in the practice of this invention are polyether polyols having an average hydroxyl function-ality of from two to about 8 including polymer/polyether polyols produced by the in 8itU polymerization of an ethylenically unsaturated monomer in a polyether polyol.
Illustrative of the polyisocyanates that can be employed are aromatic diisocyanates, polymeric aryl isocyanates, and polyfunctional isocyanates produced as residue products in the manufacture of aromatic diisocyanates.
In addition to their catalytic versatility, the said dimethylamino ether mono-ols have the further highly desirable characteristic of low residual odor and thus allow for the formation of foam products essentially free of the post-cure odor associated with many other tertiary-amines.
Particularly versatile catalyst systems for use in the practice of the present invention are those comprising at least one of the following compounds within the scope of Formula I which compounds, for the sake of brevity, are also referred to herein by the abbreviations, DMEE and DMEEE, as indicated:

DMEE ~ 2-(2-dimethylaminoethoxy)ethanol which has the formula, - ~N-CH2CH2-0-CH2CH2-OH

`DMEEE = 2-~2-(2-dimethylaminoethoxy~ethoxy]ethanol which has the formula, ~~

CH ~ ~-CH2CH2-O-CH2CH2-O-cH2c~2-oH

9 S ~ 9 9 ~n ddi~on to thelr ver-atil$t~ ant, ~ di~cu~ed nd ~emonserated ~ith pecific reference to foam tata ~re-aented herein, ~MEE and DMEEE ~re used w$th particular dvantage and exhibit unexpected catalytic activity in the formation of one-shot, water-blown, fle~ible poly-urethane foam derived from a polyether polyol and in the format~on of rigid foam blown with 8 blow*ng agent com-pri6ing water. Other beneficial and unexpected proper-ties include ability to provide water-blown flexible 1~ foam of enhanced poro6ity and void-free semi-flexible foam.
The amino ether no-016 may be employed in sub6tantially pure form or in combination with di~tillable residual by-product6 produced in their manufacture. They are effective activator6 when used as the sole type of nitrogen-bearing catalytic component of polyurethane foam-producing reaction mixtures, although their employment in combination with other tertiary amines and/or organic compour.ds of t~n is found to be beneficial in a number of foam-produc~ng reaction mirtures.
Thus the present invention al60 provites for the formation of cellular urethane polymers in the presence of ~mine cataly6t systems comprising the ethers encompas6ed by Formula I in combination with one or re other types of tertiary-amines. Such additional amines include: bis[2-(N,N-dimethylAm;no)alkyl]ether6 such as in part$cular bisl2-(N,N-dimethylamino)ethyl]ether; re6idue product formed in the manufacture of the latter bi6-ether by the method described and claimed in U~ited States Patent No.
3,9~7,B75, g~ànted May 18, 1976, of J. L. Ferrell and A

~` f ~ ~

~954~9 9919-C-l F. Poppelsdor~, as discussed in greater detail hereinbelow;
3-dialkylamino-N,N-dimethylpropionamides such as in par-ticular 3-dimethylamino-N,N-dimethylpropionamide; N,N-dimethylcyclohexylamine; 3-dialkylaminopropionitriles;
and hydrocarbyl polyamines including triethylenediamine, N,N,N',N'-tetraalkylethylenediamines, 1,1,4,7,7-penta-alkyldiethylenetriamines and N,~,~',N'-tetraalkyl-1,3-butanediamines.
Also contemplated is the formation of polyether polyol-derived urethane foam in the presence of the amino ether mono-ols encompassed by Formula I in combination with organic compounds of tin such as, in particular, tin car-boxylates and dialkyltin dicarboxylates either as ~he sole type of co-catalyst or in further combination with an additional tertiary-amine such as the aforementioned mono and polyamines.
Also included within the scope of the present invention are catalyst blends comprising at least one amino ether mono-ol encompassed by Formula I such as in particular the aforementioned DMEE and DMEEE, a second amine component and/or an organic compound of tin such as in particular dibutyltin dilaurate.
DETAILED DESCRIPTION OF THE INVENTION
AND PREFERRED E~BODIMENTS
(A) The DimethYlamino Ether Mono-ols ._ Typical examples of suitable amino ether mono-ols - for use in the formation of cellular urethane poly~ers in accordance with the teachings of this invention are the .
following compounds:

10 .

~, ! ``
9919 -c -l~9S489

2-(2-dimethylaminoethoxy)ethanol ("DMEE"),

3~ N-CH2CH2-o-CH2CH2-oH (1) 2-[2-(2-dimethylaminoethoxy)ethoxy]ethanol ("DMEEE") CH
3 ~N-CH2CH2-O-cH2cH2-o-cH2cH2-oH (2) 1-(2-dimethylaminoethoxy)-2-propanol, ~ N-CX2CH2-O-CH2-CH-OH ~3) CH~
' CH3 l-(l-dimethylamino-2-propoxy)-2-propanol, CH
3 ~N-cH2-cH-o-cH2-cH-oH (4 2-(1-dimethylamino-2-propoxy)ethanol, ~H3 CH >N CH2-,CH-O-CH2CH2-OH (S) The catalyst systems of the invention may also comprise the following dimethylamino ether mono-ols within the scope of Formula I:

CH
3 ~N-CH2CH20-(CH2CH20~2-CH2CH2-OH (6?

__ ~_. t' -~
9sl~C-and ~ ~-CH2CH2O-CH2CH2O-CH2t'H-OH C7) ~H3 Of the compounds encompassed by Formula I, the preferred catalysts for use in forming polyurethane foam as described herein are those in which Rl through R4 are hydrogen or methyl. Most preferably, Rl through R4 are hydrogen. From the standpoint of the number of ether linkages, n preferably has an average value no more than about three and is most preferably from one to about two.
Accordingly, the particularly outstanding dimethylamino ether mono-ols for use in forming cellular urethane polymers as described herein are the aforementioned 2-(2-dimethylaminoethoxy)ethanol (DMEE) and 2-[2-(2-dimethylaminoethoxy)ethoxy]ethanol (DMEEE) which are known compounds.
The dimethylamino ether mono-ols employed in the practice of the invention may be prepared by a number of different types of known reactions. One such method comprises reacting dimethylamine and an alkylene oxide in accordance with the following equation 1.

Equation`l:

CH / \
3 ~N-H + (n+l) HC CH

Rl R2 3~N-CH-CH-o-(CH-CH-O)n~H
Rl R2 R3 R4 12.

1~95~89 gglg-c l w~erein: R3 and R4 are the same as R' and R2. Con-sistent with the structure of the compounds encompassed by Formula I, the alkylene oxide may be ethylene oxide, propylene oxide, 1,2-butylene oxide or 2,3-butylene oxide. It is evident that the employment of more than one alkylene oxide in the reaction of equation 1 pro-~ides products in which R3 and R4 are different from Rl and R2. For example, ethylene oxide and propylene oxide may be added to the reaction either individually or sequent.ally to provide adducts or mixtures of adducts h~ving a combination of oY~Jethylene and oxy-propylene units. In general, the reactions encom-passed by equation 1 are autocatalytic and exothermic, and are effected by adding the alkylene oxide to di-methylamine. Suitable operating conditions include a temperature from about 10C. to about 1~0C. and a pressure from about 0 to about 1000 pounds per square inch gauge. In the employment of ethylene oxide, the reaction is carried out under autogenous pressure and usually at temperatures less than about 60C.
Another method for preparing the dimethyl-amino ether mono-ols encompassed by Formula I com-prises oxyalkylation of the parent alkanolamines, that is, compounds having a general formula corres-ponding to Formula I except wherein n is zero. This method is iilustrated by the following equation 2.-. ~

~95~8~ 99l9-c-l Equation 2:

CH3 ~ ~/ \
N-CH-CH-OH + n HC- CH >

Rl R2 R3 R4 CH3 ~ N CH CH O-~CH-CH-O)n H

Rl R2 R3 R4 wherein Rl, R2, R3 and R4 may be the same as or different from one another.
In general, the oxyalkylation reactions encom-passed by equation 2 are effected at a temperature from about 70C. to about 250C. Suitable pressures range from substantially atmospheric (0 p.s.i.g.) up to about 2000 p.s.i.g. Oxyalkylation of alkanolamines is usually an autocatalytic reaction although it may be effected in the presence of other basic catalysts such as alkaline metal compounds as illustrated by sodium alkoxides, sodium and potassium hydroxides, and the like. For example, in forming adducts wherein n is greater than two, the addition of an extraneous catalyst may be beneficial in enhancing the rate of reaction. The rate of reaction may also be accelerated by operating at increased temperatures within the aforesaid range. The . alkanolamine reactant is preferably employed in a relat-ively large molar excess relative to alkylene oxide such as from about a three to fifteen-fold molar excess over the desired stoichiometric reaction, that is, the desired value of n. The oxyalkylation may be effected employing a single alkylene oxide reactant (that is, 14.

l~9S'~89 gglg-c-l ethylene oxide, propylene oxide or a ~icinal butylene oxide~, or a combination thereof added as a mixture or sequentially.
It is to be understood that the reactions encompassed by equation 2 may be effected in controlled sequence, that is, by reaction and recovery of the initially formed one mole adduct (n = 1), followed by reaction thereof with additional alkylene oxide and.
recovery of the two mole adduct (n = 2), and so forth.
These individual reactions are shown by the following equations 2a and 2b which illustrate the preparation of the preferred amino ether alcohols, DMEE and D~IEEE, respectively, for use in the practice of the present invention.

Equation 2a: .

CH3 ` / \
CH ~ N-CH2CH2 OH + H2C CH2 >

DMEA

CH3 ~
~N-CH2CH2-0-CH2CH2 -OH
DMEE

Equation 2b:

_ /0\
DMEE + H2C - CH2 CH3~ __ 30CH3~ N CH2cH2-o-cH2cH2-o-cH2cH2-oH
DMEEE

1~9~489 9919-C-l In providing the dimethylamino ether alcohols by the above-described oxyalkylation of hydroxy:L groups of alkanol-amines, in addition to the intended adduct such as DMEE, higher adducts such as D~EEE as well as other products may also for~. It is to be understood, therefore, that the amino ether alcohols may be employed in the formation of cellular urethanes as described herein as single com-pounds in substantiall~ pure form (about 95 percent and higher), in combination with one another, as well as in ]0 combination with by-products formed during their prep-aration such as by oxyalkylation of an alkanolamine or by oxyalkylation of a lower adduct such as DMEE or DMEEE to ~orm an adduct in which n has a higher value. For example, in the continuous produc~ion of DMEE by the oxyethylation of DME~ at a temperature from about 110C. to about 190C., a pressure from about 800 to about 2000 p.s.i.g. and a mole ratio of DMEA:ethylene oxide from about 3:1 to about 15:1, it is found that DMEEE is also formed together with other by-products. Product DMEE is recovered from the process in substantially pure form (95+ percent) by distillation under reduced pressure. Typically, DMEE is recovered as distillate having a boiling range of 90-110C. at 25 millimeters (Nm.) of mercury pressure, or 115-120C. at 35-45 mm. Such recovery of the DMEE product by distillation leaves a heavier distillable residue product comprising DMEEE. In general, distillation of said residue product allows for recovery of a fraction boiling within the range from about 90C. to about 160C. at about 5 mm. mercury pressure which fraction contains, on the average, from about 50 to about 80 weight percent of DMEEE, and varying . .
16.

991~C-l ~9~i~89 amounts of ~MEE such as trace amounts (< 2 percent) up to about 15 weight percent, as well as minor amounts of other components. The D~E content of the distilled residue depends largely on the efficiency of the recovery of D~E
from the original reaction product. The DMEEE content of the distilled residùe depends primarily on whether the re-covered distillate is taken as the aforementioned full boiling range fraction (gO-160C./5 mm.), as a narrower cut (e.g., 120-140C./10 mm.), or as a further refined fraction. In any event, it is found that this distilled residue, which for convenience is referred to herein as "D~EE-P~", is a catalytically effective material for use in forming urethane foam in accordance with the teachings of the present invention. The nature of the other compo-nents which are present in D~E~E-R has not been fully elucidated. It appears, however, that the most likely com-ponents are various linear ethoxylated derivatives of dimethyl and monomethyl amines. Analysis by gas chromato-graphy snd nuclear magnetic resonance indicates the presence of varying amounts (up to about 40 weight percent) of monomethyl-substituted material which may comprise met.7nyl-diethanolamine, an ethylene oxide adduct of methyldiethanol-amine or a combination thereof, and minor amounts of other unidentified components.
In addition to the reactions of equations 1 and 2, the amino ether mono-ols employed in the practice of the present invention can be prepared by the reaction of alkali metal salts of N,N-dimethylaminoalkanols wit~~alkylene halo-hydrins. This method is illustrated by the following equation 3.

- 17.

~95~89 99l9-c-l Equation 3:

3~ N-CH-CH-OM + n X-CH-CH-OH
CH3 1 1 l I
Rl R2 R3 R4 c~3~

N-CH-CH-O-(CH-CH-O)n-H
Rl R2 R3 R4 wherein M is alkali metal such as sodium and potassium, X is halogen such as chlorine or bromine, and R3 and R
- may be the same as or different from Rl and R2. The reactions encompassed by equation 3 are suitably effected at temperatures from about 2~C. to about 150C.
A further method comprises the reaction of an alkylene halohydrin and an alkylene oxide in the presence of a strong acid such as sulfuric acid, followed by re-action of the resulting adduct with an excess of dimethyl-amine as an acceptor of hydrogen halide by-product. This two-stage method is illustrated by equations 4a and 4b.

Equation 4a:

X-CH-CH-OH + HC ~ CH
Rl R2 R3 R4 X-CH-CH-O-(CH-CH-O)n-H
Rl R2 R3 R4 Equation 4b:
-Product of equation 4a + 2 (CH3)2N-H

~ N-CH-CH-O-(CH-CH-O)n-H + ~ NH.HX
CH3 Rl l2 R3 R4 CH3 18.

1~95489 9919 -C-l The reactions encompassed by equation 4a are effected at temperatures from 0C. to about 200C. (more usually from 20 to 120C.) and at autogenous pressures up to about 1000 p.s.i.g. Suitable conditions for the reactions en-compassed by equation 4b include temperatures from about 50 to about 150C. and pressures from atmospheric up to about 500 p.s.i.g.
A-fifth method for preparing compounds within the scope of Formula I comprises the reaction of an alkali 10 metal salt of either an N,N-dimethylalkanolamine or an alkali metal salt of an oxyalkylated N,N-dimethylalkanolamine containing one less oxyalkylene unit than is desired in the intended product, with an appropriate alpha-halogen sub-stituted carbonyl compound, followed by reduction of the intermediate amino ether carbonyl product. This method is illustrated by the following equations 5a and 5b.

Equation 5a:

CH3 ~N-cH-cH-o-(cH-cH-O) lM
CH3 ~ ' ' ~ n- + X-CH-C=O
Rl R2 R3 R4 R R

~ N-CH-CH-O-(CH-CH-O)n_l-CH-C=O + MX
, Rl R2 R3 R4 R3 R4 Equation 5b:
Product of equation 5a + H2 CH
3~ N-CH-CH-o-(CH-CH-O)n-H __ CH ~
Rl R2 R3 R4 wherein, as previously defined, n has a value from one to about five.

19 .

1~954~9 The reaction of equation 5a is suitably effected at temperatures from a~out 30C. to about 150C. and pressures from atmospheric to 500 p.s.i.g. The hydro-genation reaction of equation 5b may be carried out at temperatures from about 50C. to about 200C. and ``
pressures from 50 to about 1000 p.s.i.g.
(B) THE FOAM FORMULATIONS
In producing cellular urethane polymers in accordance with the teachings of this invention, in addition to the c~talyst systems comprising the dimethyl-am;no ether mono-ols described herein, the reaction mix-ture or foam formulation contains an organic polyiso-cyanate and an organic polyol containing a polyethcr polyol having an average of at least two and usually not more than eight 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, halogen and/or nitrogen. Suitable classes of organic polyol reactants for use in the method of this in~ention are polyether polyols including nitrogen-containing polyether polyols and polymer/polyether polyols produced by polymerizing an ethylenically unsaturated monomer in a polyether polyol in the presence of a free radical initiator.
It is well known to the cellular polyurethane art that the particular polyol reactant or combination of polyols employed in any given formulation depends in large measure upon the end-use application of the cellular product, 20.

. ~95489 9919_C-l and that the end-use in turn determines whether the product is to be provided as a flexible, semi-flexible, high-resilience or rigid foam. ~ characteristic of the polyol reactant is its hydroxyl number which is determined by and defined as the number of milligrams of potassium hydroxide required for the complete neutralization of the hydrolysis product of the fully acetylated derivative pre-pared from 1 gram of polyol or mixture of polyols. The hydroxyl number is aiso defined by the following equ2tion which reflects its relationship with the functionality and molecular weight of the polyol reactant:

OH r~O. = 56.1 x lOOo x f M. W.
where: OH = hydroxyl number of the polyol;
f = average functionality, that is, average number of hydroxyl groups per molecule of polyol; and M. W. = average molecular weight of the polyol.
The catalyst systems of the present invention are suitably employed as catalytic components of formulations contain-ing polyether polyols having an average hydroxyl num~er f~om about 18 to about 1000. In producing flexible polyether urethane foam, the polyether polyol reactant has a relatively low hydroxyl number such as - from about 20 to about 125. For flexible foam the hydroxyl number is usually no more than about 75. Generally employed for rigid foam formulations are organic polyol reactants comprising polyether polyols having a relatively high hydroxyl number from about 200 up to about 1000 such as, in particular, a hydroxyl number within the range from about '~ 9 S~ 89 9919-C-300 to about 800. In providing semi-flexible foam, the organic polyol reactant may be a polyether polyol having a hydroxyl number within the range from about 100 to about 200. For the manufacture of semi-flexible foam of enhanced load-bearing properties, however, the polyol reactant preferably comprises a polymer/polyol having a hydroxyl number from about 20 to about 65. For high-resilience urethane foam, the organic polyol reactant also preferably comprises a polymer/polyol the hydroxyl number of which may be from about 18 to about 65.
SuitabLe polyether polyols of which the organic polyol reactant may be comprised include linear and branched polyethers having an average functionality from two to eight. For convenience, this class of polyether polyols are referred to herein as Polyol I. These polyols include alkylene oxide adducts of water such as poly-ethylene glycols having average molecular weights from about 200 to about 600, polypropylene glycols having average molecular weights from about 400 to about 2000, and polyoxyalkylene polyols having a combination of different alkylene oxide units. Other.suitable polyols encompassed within the definition of Polyol I are the alkylene oxide adducts of polyhydric organic initiators, the nature of which determines the average hydroxyl functionality of the polyoxyalkylated product. Illus-trative of suitable polyhydric organic initiators are the following which can be employed individually or in combination with one another: (l) diols such as ethylene glycol, diethylene glycol, propylene glycol, 1,5-pentanediol, hexylene glycol, dipropylene glycol, trimethylene glycol, 1~95~89 99l9-c-l 1,2-cyclohexanediol, 3-cyclohexene-1,1-dimethanol and 3,4-dibromocyclohexane-l,l-dimethanol; (2) triols 6uch as glycerol, 1,2,6-hexanetriol, l,l,l-trimethylolethane, l,l,l-trimethylolpropane, 3-(2-hydroxyethoxy)- and 3-(2-hydroxypropoxy)-1,2-propanediols, 2,4-dimethyl-2-(2-hydroxy-ethoxy)methyl-pentanediol-1,5,1,1,1-tris[(2-hydroxyethoxy)-methyl]ethane and l,l,l-tris[(2-hydroxypropoxy)methyl]propane;
(3) tetrols such as pentaerythritol; (4) pentols, hexols, heptanols and octanols such as glucose, sorbitol, bis(2,2,2-trimethylol)ethyl ether, alpha-methyl glucoside, sucrose, mannose and galactose; (5) compounds in which hydroxyl gro.ups are bonded to ar. aromatic nucleus such as resorcinol, pyro-gallol, phloroglucinol, di-, tri- and tetra-phenylol com-pounds such as bis(p-hydroxyphenyl)methane and 2,2-bis(p-hydroxyphenyl)propane; and (6) alkylene oxide adducts of the aforesaid initiators such as propylene or ethylene oxide adducts of glycerol having a rela~ively low average molecular weight up to about 650.
Particularly useful in the preparation of flexible polyether urethane foam are the polyether polyols having an ~verage hydroxyl functionality of from 2 to about 4 and, as`
aforement~ioned, a hydroxyl number from about 20 to about 125.
For rigid foam formulations, the polyol reactant comprise.s a polyether polyol (including nitrogen-containing polyether polyols discussed hereinbelow) having an average hydroxyl functionality from about 3 to about 8, and a hydroxyl number from about 200 up to about 1000. It is to be understood that the organic polyol component of rigid foam formulations may additionally contain, as a second type of polyol reactant, a diol having a hydroxyl number from about 20.0 to-about 800;

1~9s489 9 The above-described polyether polyols are normally liquid materials and, in general, are prepared in accordance with well k~own tech~iques comprising the reaction of one or more polyhydric starters snd an alkylene oxide in the presence of an oxyalkylation catalyst. Usually, the catalyst is an alkali metal hydroxide such as, in par-ticular, potassium hydroxide. The oxyalkylation of the polyhydric initiator is carried out at temperatures ranging from about 90C. to about 150C. and usually at an elevated pressure up to about 200 p.s.i.g., employing a sufficient amount of al~ylene oxide and adequate reaction time to obtain a polyol of desired molecular weight which is con-veniently followed during the course of the reaction by standard hydroxyl number determinations, as defined above.
The alkylene oxides most commonly employed in providing the reactants encompassed by Polyol I, are the lower alkylene oxides, that is, compounds having from 2 to 4 carbon atoms including ethylene oxide, propylene oxide, butylene oxides (1,2- or 2,3-) and combinations thereof. When more than one type of oxyalkylene unit is desired in the polyol product, the alkylene oxide reactants may be fed to the reaction system sequentially to provide polyoxyalkylene chains containing respective blocks of different oxyalkylene units or they may be fed simultaneously to provide sub-stantially random distribution of units. Alternatively, the polyoxyalkylene chains may consist essentially of one t~e of oxyalkylene unit such as oxypropylene capped with oxyethylene units.

24.

i ;t ~L~95'~89 gglg-c-l A second class of organic polyol reactants that are suitable for use in preparing polyurethane foams in accordance with the present invention are polymer/polyols which, for convenience~ are referred to herein as Polyol II.
Such polyols have hydroxyl numbers from about 18 to about 65. They are produced by polymerizing one or more ethylen-ically unsaturated monomers dissolved or dispersed in any of the other types of organic polyol reactants described herein, in the presence of a free radical catalyst. Illus-trative of suitable substrate polyols for producing suchcompositions are those polyether polyols encompassed by the definition of Polyol I which have an average hydroxyl functionality from 2 to about 5. Also effective as the substrate polyol are the polyether polyols defined herein-below as Polyol III. Illustrative of the ethylenically un-saturated monomers are vinyl compounds having the general formula, R
R-C=CH2 wherein: R is hydrogen, methyl or any of the halogens (i.e., fluorine, chlorine, bromine or iodine); and R is R, cyano, phenyl, methyl-substituted phenyl, carboalkoxy, or alkenyl radicals having from 2 to 6 carbon atoms such as vinyl, allyl and isopropenyl groups. Typical examples of such polymerizable monomers are the following which may be employed individually or in combination: ethylene, propylene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, styrene, alpha-methylstyrene, methyl methacrylate, and butadiene. In general, such compositions are prepared by polymerizing the monomers in the substrate polyol at a .
25.

'' ~ `. !
1095~9 9919-C-l temperature between about 40C. ancl about 150C. employing .any free radical-generating initiat:or 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 percent of the vinyl monomer or monomers polymerized in the substrate polyether polyol. Especially effective polymer/polyols are those having the following composition:
(A) from about 10 to about 30 weight percent of a copolymer of (1) acrylonitrile or methacrylonitrile, and (2) styrene or alpha-methylstyrene, the said copolymer con-taining from about 50 to 75 and from about 50 to 25 weight percent of monomeric units of (1) and (2), respectively; and (B) from about 90 to about 70 weight percent of one or more of the aforementioned types of substrate poly-ether polyols.
A third class of polyether polyols of which theorganic polyol reactant may be comprised are polyether polyols having the following combination of characteristics:
(1) an average hydroxyl functionality from 2.1 to about 5;
~2) a hydroxyl number from about 40 to 18; and (3) an average primary hydroxyl content between about 35 and about 35 mole percent, based on the total number of hydroxyl groups contained in the polyol. For convenience, this particular class of polyols are referred to herein as Polyol III. This class of polyols are derived from ethylene oxide and 26.

1~95489 gglg-c-l propylene oxide and one of the aforesaid organic initiators ~a~ing a hydroxyl functionality from about 3 to about 5 (such as, for example, glycerol) including appropriate mixtures of such initiators with one another and/or in combination with dihydric starters. The high primary hydroxyl content is introduced by capping of the polyoxy-alkylene chains with at least a portion of the total ethylene oxide feed. Such highly reactive polyethers (i.e., Polyol III) are also especially useful as the substrate polyol in which the above-described polymer/polyols are formed. r As previously noted, for semi-flexible foam of enhanced load-bearing properties, polymer/polyols (Polyol II) are preferably employed. In general, the organic polyoi reactant of such semi-flexible foam formulations is con-stituted of from about 50 up to 100 percent by weight of such polymer/polyols and correspondingly from about 50 to 0 weight percent of another polyether polyol which may be one or more of the polyether polyols encompassed by the above-described respective classes designated Polyol I and Polyol III. Usually, at least about 80 weight percent of the total polyol contained in such se~i-flexible formu-lations is constituted of the polymer/polyols. When used, the second polyether polyol component is preferably of the type within the scope of Polyol III.
For formation of high-resilience foam, the organic polyol reactant comprises a polyether polyol within the class defined above as Polyol III. They may be used as essentially the sole type of polyether polyol in the formulation or they may be employed in combination with 27.

~ ~ 9 9919-C-l other polyols to control the degree of softness or firm-ness of the foam and to vary the load-bearing properties.
For examplç, when softer grade high-resilience foams are desired, Polyol III may be used in combination with poly-ether diols such as the above-described lower alkylene - oxide adducts of a dihydric initiator such as dipropylene glycol. However, when firm grades of high-resilience foams having enhanced load-bearing properties are desired, the organic polyol reactant of the foam formulation preferably comprises a polymer/polyol. -In such high-resilience formulations, the organic polyol reactant is constituted 5 of from about 20 up to about 60 weight percent of polymer/
polyol and correspondingly from about 80 to about 40 weight percent of those polyether polyols encompassed by the definition of Polyol III. Usually, the high-resilience formulation contains no more than about 50 weight percent of polymer/polyol based on the weight of total polyol reactant contained in the formulation.
Another class of suitable polyether polyols for use in the practice of this invention are nitrogen-contain-ing polyols. Illustrative of this class are-lower alkylene oxide adducts of the following polyfunctional amines which may be employed individually or in combination: primary and secondary polyamines such as ethylenediamine, diethylene-_ triamine and toluenediamine; and aminoalkanols such as - ethanolamine, diethanolamine, triethanolamine and triiso-propanolamine. Also suitable are mixed starters containing one or more of the aforesaid polyfunctional amines, aniline, and/or one or more of the polyhydric initiators employed to produce Polyol I such as dipropylene glycol, glycerol, 28.

- l~9S~9 9919 -C-l sucrose and sorbitol. Preferably, the alkylene oxide is ethylene oxide, propylene oxide or a combination thereof.
Such nitrogen-containing polyether polyols are usually employed in rigid foam formulations either as the sole type of organic polyol reactant or in combination with one or more polyether polyols encompassed by Polyol I.
For application in forming rigid foam, such nitrogen-containing polyols, that is, polyols derived at least in part from a polyfunctional amine star~er, also have hydroxyl numbers which are within the range from about 200 to about 1000, and are more usually from about 300 rto about 800. Other types of nitrogen-containing polyols are aniline/formaldehyde and aniline/phenol/formaldehyde condensation products which are also useful in rigid foam formulations.
The polyisocyanates used in the manufacture of cellular polyurethanes are known to the art and any such reactants are suitably employed in the practice of the present invention. Among such suitable polyisocyanates are those represented by the general formula:
Q(NCO)i wherein: i has an average value of at least two and is usually no more than six, and Q represents an aliphatic, cycloaliphatic or aromatic radical which can be an unsub-stituted hydrocarbyl group or a hydrocarbyl group substituted, for example, with halogen or alkoxy. For example, Q can be an alkylene, cycloalkylene, arylene, alkyl-substituted cycloalkylene, alkarylene or aralkylene radical including corresponding halogen- and alkoxy-substituted radicals. Typical examples of such polyiso-29.

`

1~9~89 9919 -C-l cyanates for use in preparing the polyurethanes of this invention are any of the following including mixtures thereof: 1,6-hexamethylenediisocyanate; 1,4-tetramethylene-diisocyanate; bis(2-isocyanatoethyl~fumarate; 1-methyl-2,4-diisocyanatocyclohexane; methylene-4,4'-diphenyldiiso-cyanate, commonly referred to as "MDI"; phenylene diiso-cyanates such as 4-methoxy-1,4-phenylenediisocyanate,

4-chloro-1,3-phenylenediisocyanate, 4-bromo-1,3-phenylene-diisocyanate~, 5,6-dimethyl-1,3-phenylenediisocyanate and 6-isopropyl-1,3-phenylenediisocyanate; 2,4-tolylene diiso-cyanate and 2,6-tolylene diisocyanate including mixtures .
of these two isomers as well as crude tolylene diisocyanate;
isophoronediisocyanate; methylene-4,4'-dicyclohexyl-diiso-cyanate; durylene diisocyanate; triphenylmethane-4,4',4"-triisocyanate; and other organic polyisocyanates known to the polyurethane art. Of the aforesaid types of polyiso-cyanates, those containing aromatic nuclei are generally preferred.
Also useful as the polyisocyanate reactant are ~0 polymeric isocyanates having units of the formula: . -NCO
~CH

., . ' .- _ _ i ..

30.

1~95~89 9919 -C-l wherein R' is hydrogen and/or lower alkyl and J has an average value of at least 2.1. Usually, the lower alkyl radical is methyl and ; has an average value no higher than sbout 4. Particularly useful polymeric aryl iso-cyanates of this type are the polyphenylmethylene poly-isocyanates produced by phosgenation of the polyamine obtained by acid-catalyzed condensation of aniline with formaldehyde. They 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 fro~ about 25 to about 35 weight percent depending upon the specific aniline-to-formaldehyde molar ratio used in the polyamine preparation. Suitable polymeric isocyanates of this type for use in the practice of this invention are those available commercially as PAPI 901 (The Upjohn Company) and NIAX Isocyanate AFPI (Union Carbide Corporation).
Also useful as polyisocyanate reactants are tolylene diisocyanate residues obtained from the manu-facture of the 2,4- and 2,6- isomers of tolylene diiso- -cyanates, and having a free -NC0 content of from about 30 to abput 50 weight percent. For example, as is known, tolylene diisocyanate is commercially made by reacting toluene and nitric acid to form the 2,4- and 2,6-dinitro-toluene isomers, hydrogenating and then phosgenating, typically in a solvent such as dichlorobenzene, to provide the conventional mixture of 80 per cent 2,4-tolylene di-isocyanate and 20 percent 2,6-tolylene diisocyanate. After removal of the solvent, the crude product undergoes a further evaporation in a still, with the refined or pure 31.

` 1~95~89 ;`i 9919 -C-l tolylene diisocyanate coming over. The evaporator tails remaining are blac'~. in color and extremely viscous, even often solid, materials. It is the evaporator tail material which is commonly referred to as tolylene diiso-cyanate residue.
Other useful polyisocyanate reactants are "lîquid MDI," and combinations of diisocyanates with polymeric isocyanates having an average of more than two isocyanate groups per molecule. Illustrative of such combinations are: a mixture of 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate and the aforesaid polyphenyl-methylene polyisocyanates and/or the aforementioned tolylene diisocyanate residue product.
The aforesaid types of polyisocyanate reactants are generally useful in forming cellular urethane polymers of the flexible, semi-flexible, high-resilience and rigid variety. For example, in regard to semi-flexible foam formulations, tolylene diisocyanates, tolylene diiso-cyanate residue and polymeric isocyanates are suitable.
More usually, however, semi-flexible formulations contain the polymeric isocyanates such as PAPI, AFPI and the like.
The more commonly employed polyisocyanates for rigid foam formulations are tolylene diisocyanate residue and polymeric isocyanates. For rigids, tolylene diisocyanates are also useful although they are usually employed for this purpose as quasi-prepolymers having a free -NCO
content from about 25 to about 35 percent. In regard to high-resilience formulations, polyisocyanates used with particular advantage are mixtures containing from about 60 to about 90 weight percent of the isomeric tolylene 32.

- ~95~89 ~;' 9sl~c-1 diisocyanates and from about 40 to about 10 weight percent of the polyphenylmethylene polyisocyanates, in order to enhance the average -NCO functionality and thus the reactivity of the reaction mixture. When the high-resilience formulations contain the isomeric diisocyanates - as essentially the sole source of reactive -NCO" it is often desirable to include minor amounts of cross-linking agents, such as up to about 1.5 parts by weight per one hundred parts of polyol reactant.
10On a combined basis, the polyol reactant and organic polyisocyanate usually constitute the major pro-portion by weight of the polyurethane-forming reaction mixture. In general, the polyisocyanate and polyol reactants are employed in relative amounts such that the ratio of total -NC0 equivalents to total active hydrogen -equivalent tof the polyol and any water, when used) is from 0.8 to 1.5, usually from 0.9 to 1.35, equivalents of -NCO per equivalent of active hydrogen. This ratio is known as the Isocyanate Index and is often also expressed as a percent of the stoichiometric amount of polyisocyanate required to react with total active hydrogen. When expressed as a percent, the Isocyanate Index may be from 80 to 150, and is usually within the range from about 90 to about 135. More usually, in ._flexible, semi-flexible and high resilience formulations the Isocyanate Index is no more than about 115.

1~9 ~i~89 991~C-l The catalyst systems of the present invention are comprised of the dimethylamino ether mono-ols either individually, in combir.ation with one another or as distillable residue products formed in their manufacture such as the above-described "DMEEE-R". The catalyst systems of the invention may additionally contain another tertiary-amine component and/or an organic compound of tin. Thus, the catalyst systems employed in the practice of the invention may contain the dimethylamino ether mono-ol as essentially the sole type of catalytic component.
'l'he catalvst systems may al~so be bir,ary systems in the sense of containing the dimethylzmino ether mono-ol in com-bination with either at least one other tertiary-amine com-ponent or at least one organic compound of tin. Further, the catalyst systems may also be ternary in the sense of containing at least one other tertiary-amine component and, additionally, at least one organic compound of tin.
In their use as components of cellular urethane formulations as described herein, the catalyst systems are present in the foam formulation in a catalytically effective amount.
Ihus, the total concentration thereof may vary over a relatively wide range such as from about 0.01 to about 12 or more parts by weight (exclusive of any carrier solvent or other non catalytic additive) per one hundred parts by weight of the total polyol reactant (p.p.h.p.) contained in the'reaction mixture. The more usual concentration is from about 0.05 to about lO p.p.h.p. The particular con-centration employed in any given formulation depends upon the nature of the intended foam product. For example, in flexible polyether and high-resilience foam formulations, .:
34.

~ ~9 S~8 ~ 9919 -C-l the catalyst systems of the invention are usually employed in an amount from about 0.05 to about 4 p.p.h.p. In rigid and semi-flexible formulations, the catalyst systems may be used in amounts from about 0.1 up to about 12 p.p.h.p., although usually no more than about 10 p.p.h.p. is used.
Among the suitable classes of other tertiary-amines of which the catalyst ~ystems of the invention may be comprised a e tertiary-amines consisting of carbon, hydrogen and amino nitrogen. Such hydrocarbyl amines may contai.n one or more tertiary-amino groups such as up to about five, and from three to 24 and usually no mo;e than 12 carbon atoms. Illustrative of suitable hydrocarbyl mono- and polyamines which may be employed as catalyst components cf the dimethylamino ether mono-ol-containing catalyst systems of the invention are one or more of the following: trimethylamine; triethylamine; tributylamine;
N,N-dimethylcyclohexylamine; N,N-dimethylbenzylamine;
triethylenediamine; N,N,N',N'-tetramethylethylenediamine;
N,N,N',N'-tetraethylethylenediamine; N,N,N',N'-tetramethyl-1,3-butanediam;ne; and 1,1,4,7,7-pentamethyldiethylene-triamine.
~ Another class of suitable tertiary-amines which may be present in the catalyst systems of the present invention are the beta-amino carbonyl compounds described _ in U.S. Patent No. 3,821,131 such as, in particular, the 3-dialkylamino-N,N-dimethylpropionamides. Of this class, 3-dimethylamino-N,N-dimethylpropionamide is a particularly useful component of the catalyst systems described herein.

. .
35.

9919 - 'C - 1 A third cla66 of terti~lry-amines for use as a catalytic component of the catal~st sy6tem6 of this invention are bis[2-cN~N-dimethylamino)alkyl~ethers such as, in particular, bisl2-CN,N-dimethylamino~ethyl~ether ("BDMEE").
Also useful as an amine catalyst for use in combination with the dimethylamino ether alcohols as des-cribed herein is distilled residue product formed in the manufacture of the aforementioned bis[2-(N,N-dimethyl-amino)ethyl~ether ("BDMEE") by the method of aforementioned United States Patent No. 3,957,875.
The said method comprises reacting trimethyl~m;ne and 2-(2-dimethylaminoethoxy)ethanol C"DM$E") in the presence of a nickel catalyst such as ~aney nickel, at a temperature within the range from about 50C. to about 300C. employ-ing at least one mole up to about 10 moles of trimethyl-amine per mole of DMEE, A generally preferred combination of reaction conditions for continuous production of BDMEE
includes operating at a temperature from about 140 to about 200C. under autogenous pressures from about 500 to about 2000 p,s.i.g. employing a mole ratio from about 2 to about 5 moles of trimethylamine per mole of DMEE. The reaction mixture is filtered to re ve catalyst and is then fractionally distilled, first under pressure to remove unreacted trimethylamine (e.g., overhead boiling up to 80C. at 30 to 40 p.s.i.g.), then at atmospheric pressure up to 105C. to remove a water/~-methylmorpholine azeotrope, then at reduced pressure to recover overhead containing ~DMEE as the major component Cboiling range 36.

l~g 5~ 89 9919-C-l of 100-120C. at 50 millimeters of mercury pressure) and a fuxther overhead fraction containing unreacted DMEE Cboiling range from about 120 to about 130C. at 55 m~. mercury pressure). The product remaining in the still after separation of the latter fraction is then combined with residual product remaining after further distillation (105C. at 50 mm.) of the afore-mentioned BDMEE-containing cut. The combined material is then subjected to distillation to separate overhead boil-ing from about 65C. to abcut 85C. at 1-2 mm. mercury pressure, and finally a heavier fraction is recovered having a boiling range fro~. about 85C. to about 1~0C.
at 1-2 mm. of mercury pressure. The latter distillate con-stitutes from about 50 to about 70 percent by weight of the combined residues from which it is recovered. For convenience, this particular distilled residue including narrower cuts thereof, derived from the aforementioned method for producing bis~2-(N,N-dimethylamino)ethyl]ether is referred to herein as "BDMEE-R." This material is catalytically active for cellular urethane formation and is particularly suited for use in combination with the dimethylamino ether alcohols described herein. The said distilled residue product, BDMEE-R, is a complex mixture of components which have not been identified. Without wishing to be bound by any theory, it is believed that the ma~or components (60 to 75 percent by weight) are polymers of BD~E such as those having the formula, [(CH3)2N-CH2CH2O-CH2CH2 ~ (N~

..
37.

~5~89 9919- c-l where m h~ a value of two upward~ of about five. For cx~mple, whcn m i~ two, the pol~m~.r woult be trlamine, (CH3)2N-cH2cH2o-cH2cH2-N-cH2~H2-o-cH2cH2N(cH3)2 and when m is three, the polymer would be a tetramine, and 80 forth. Other possible components of BDMEE-R are, (cH3)2~-cH2cH2-o-cH2cH2-N-cH2cH2-o-cH2cH2-oH ant ~CH2CH2~
(CH3)2~-~H2CH2-O-cH2cH2-N~ /

Other classes of tertiary-amines which may be used in combination with the dimethylamino ether mono-ols as described herein are: N,N-dialkylalkanolamines such as, in particular, N,N-dimethylethanolamine; the beta-aminopro-pionitriles described in the aforementioned United States Patent No. 3,925,268, such as, in particular, 3-dimethylaminopropionitrile; and saturated heterocyclic tertiary-amines such as N-methyl-rpholine; N-ethylmorpholine, 1,4-dimethylpiperazine and N-(2-hydroxyethyl)piperazine.
Suitable organic tin compounds which may be contained in the catalyst systems of the invention are any of the fol'ow$ng: stannous salts of carboxylic acids such as stannou6 octoate, stannous oleate, stannous acetate and staDnous laurate; dialkyltin dicarbo~ylates ~uch as dibutyltir, dilauraee, dibutyltin diacetate, dilauryltin diacetate, dibutyltin di(2-ethylhexanoate) and other such stannous and stannic salts as well as dialkyltin oxides, 38.

~95'~89 gglg-c-l trialkyltin oxides, tin mercaptides such as, for example, di-n-octyl tin mercaptide, and the like.
When the dimethylamino ether mono-ol is used in combination with other catalysts, the components of the catalyst system may be added to the foam formulation as individual streams or in preblended form.
In accordance with a more specific embodiment of the present invention, the catalyst systems of the above-described binary or ternary type are provided and introduced to the foam formulation in preblended form.
In general, such blends contain: (1) a total of from about 5 to about 98 weight percent of the dimethylamino ether mono-ol component including DMEEE-~ which is described above with specific reference to equation 2a, (2) a total of from about 2 to about 95 weight percent of one or more of the above-described other types of tertiary-amine components including BDMEE-~, and (3) zero or up to about 15 weight percent of an organic compound of tin, the said weight percentages being expressed on the basis of the combined total weight of components (1), (2) and (3) contained in the blend (that is, exclusive of any carrier solvent or other non catalytic additive). When present, the total concentration of tin compound in the blend is at least about 0.1 and is usually at least about 0.5 and no more than about 10 weight percent.
The blended catalyst systems of the invention usually contain: (1) a total of from about 10 to about 95 weight percent of the dimethylamino ether mono-ol compo-nent; (2) a total of from about 5 to about 90 weight percent of one or more of the above-described other types 39.

1~ ~ 5'~ 9 9919-C-l of tertiary-amine components; and (3~ from zero up to about 10 weight percent of the organic compound of tin. When component (2) comprises dimethylethanolamine, the latter is generally present in the blend in an amount of no more than about 60, and usually no more than about 50, weight percent.
Illustrative of generally preferred blended catalyst systems of the invention are those containing:
(1) a total of from about 10 to about 90 weight percent of the dimethylamino ether mono-ol component such as, in particular, 2-(2-dimethylaminoethoxy)ethanol (D~E), 2-[2-(2-dimethylaminoethoxy)ethoxy]ethanol (D~EEE) or the above-described distillable by-product (DMEEE-R) formed in the manufacture of D~, including any combination of such dimethylamino ether mono-ol components;
(2) a total of.from about 10 to about 90 weight percet of bis[2-(N,N-dimethylamino~ethyl]ether (BDMEE), the above-described distillable by-product (BDMEE-R) formed during the manufacture of BDMEE, 3-dimethylamino-N,N-dimethylpropionamide, N,N-dimethylcyclohexylamine, or a hydrocarbyl polyamine (such as, in particular, triethylene-- diamine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethyl-1,3-butanediamine, and 1,1,4,7,7-pentamethyl-diethylenetriamine) including any combination thereof;
(3) zero or up to about 60 weight percent of dimethylethanolamine; and (4) zero or up to about 10 weight percent of an organic compound of tin such as, in particular, dibutyltin dilaurate or stannous octoate.

40.

``` ~L~95489 `~-9919-C-l When used as a component of such blends, dimethylethanol-amine is usually present in an amount of at least about 2 and no more than about 50 weight percent.
Especially suitable catalyst systems of the invention for flexible polyether and high-resilience formu-lations are blends containing:
(1) a total of from about 10 to about 80 weight percent of DMEE, DMEEE or DMEEE-R including any combina~ion thereof;
(2) a total of from about 20 to about 90 weight percent of bis[2-(N,N-dimethylamino)e~hyl]ether, B~.~E-R,.
3-dimethylamino-N,N-dimethylpropionamide or a hydrocarbyl polyamine (as above-illustrated) including any combination thereof;
(3) from zero up to about 50 weight percent of dimethylethanolamine; and (4) from zero up to about 10 weight percent of an organic compound of tin.
Illustrative of this group of blended catalysts of the invention are those containing: (1) a total of from about 10 to about 60 weight percent of at least one of D~E, DMEEE or DMEEE-R; (2) a ~otal of from about 40 to about 90 weight percent of bis[2-(N,N-dimethylamino)ethyl]ether or BDMEE-R including any combination thereof; (3) zero or up to about 45 weight percent of dimethylethanolamine; and (4) zero or up to about 10 weight percent of stannous octoate or dibutyltin dilaurate.
Especially suitable catalyst systems of the invention for rigid foam formulations are blends containing:

41.

1~9~a~89 9919-C-l (1) a total of from about 40 to about 90 weight percent of DMEE, DMEEE or DMEEE-R including any combination thereof;
(2) a total of from about 10 to about 60 weight percent of another tertiary-amine component such as, in particular, bis[2-(N,N-dimethylamino)ethyl]ether, BDMEE-R, 3-dimethylamino-N,N-dimethylpropionamide, N,N-dimethyl-cyclohexylamine or a hydrocarbyl polyamine (as above-illustrated) including any combination thereof;
(3) from zero up to about 40 weight percent of dimethylethanolamine; and A
(4) from zero up to about 10 weight percent of an organic compound of tin such as, in particular, dibutyl-tin dilaurate.
For rigid foam formulations, particular advantage is realized in the employment of blends in which the organic compound of tin, especially dibutyltin dilaurate, is present. In such ternary catalyst systems of the invention, the tin compound may be present in an amount from about 0.1 to about 15 weight percent, the more usual concentration being from about 0.5 to about 10 weight percent. In addition to exhibiting good performance latitude in rigid foam formulations, such ternary blends are also effective catalyst systems for other types of formulations such as, for example, those designed for flexible polyether foam formation.
It is to be understood that the dimethylamino ether mono-ols, as well as the above-discussed blends based thereon, may be introduced to the foam formulations in undiluted form or as solutions in suitable carrier .
42.

1~95~S9 99l9-C-l sol~ents or diluents. Commonly employed for this purpose are diethylene glycol, dipropylene glycol and hexylene glycol. Another type of suitable carrier medium for the catalyst systems described herein are organic sur-factants which, when used, are usually of the non ionic variety. Such non ionics include: the polyoxyethylene ethers of higher alcohols having from lO to 18 carbon atoms including mixtures thereof; and polyoxyethylene ethers of alkyl-substituted phenols. Typical of such non ionic organic surfactants for use as the carrier medium for the catalyst systems described herein are the ethylene oxide adducts of nonylphenol having the average composition, CgHlg-C6H4-(OC2H4)h-OH, wherein h has an average value from about 4 to about 20, inclusive of whole and fractional numbers, such as 6, 9, 10.5 a~d 15.
When used, the glycol and/or non ionic organic surfactant type of carrier may be present in the catalyst systems including the above-described blends, in a total amount from about 5 to about 90, and usually in a total amount no more than about 80, weight percent, based on the combined weight of the catalytic components, glycol andtor organic surfactant diluent. The extent of dilution depends primarily on the activity specifications _ of any given foam formulation.
The foam formulations employed in the practice of the present invention may also contain a minor amount of any of the organic compounds of tin described herein-above with specific reference to their presence in blended catalyst systems of the invention. Of such org`anic com-43.

l~9S4~9 gglg-c-l pounds of tin, stannous octoate and dibutyltin dilaurate are especially effective. It is to be understood that, when used, he tin co-catalyst may be added to the formulation directly as a separate stream, as a component of the above-described catalyst systems of the invention, or by a combination of these two modes of addition. When used, such tin co-catalysts may be present in the formu-lation in a total amount from about 0.001 to about 3 parts by weight per 100 parts by weight of total polyol reactant.
In flexible polyether foam formulations and, when used in semi-flexible foam systems, the organic compound of tin is usually present in a total amount from about 0.01 to about one p.p.h.p., and most preferably in an amount no more than about 0.6 p.p.h.p. For high-resilience formu-lations, the tin compound is generally used in an amount from about 0.001 up to about 2 p.p.h.p. When used in rigid foam formulations, the tin compound is generally present in the formulation in an amount of at least about 0.01. Although in some r gid systems up to about 3 p.p.h.p.
may be used, as a general rule no more than about 2 p.p.h.p.
of tin compound is present.
~ Foaming is accomplished by the presence in the foam formulation of varying amounts of a polyurethane blowing agent such as water which, upon reaction with iso-_ cyanate, generates carbon dioxide in situ, or through the use of blowing 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. Thus, in addition to or in place of water, other blowing agents which can be employed in the process of this invention 1~95~9 9919-C-l include methylene chloride, liquefied gases which have boiling points below 80F. and above -60F., or other inert gases such as nitrogen, carbon dioxide added as such, methane, helium and argon. Suitable liquefied gases include aliphatic and cycloaliphatic fluorocarbons which vaporize at or below the tcmperature of the foaming mass. Such gases are at least p~rtially fluorinated and may also be otherwise halogenated. Fluorocarbon agents suitable for .
use in foaming formulations of this invention include:
trichloromonofluoromethane; dichlorodifluoromethane; 1,1-dichloro-l-fluoroethane; i,2,2-trifluoro-1,1,2-trichloro-ethane; l,l,l-trifluoro-2-fluoro-3,3-difluoro-4,4,4-trifluorobutane; hexafluorocyclobutene; and octafluoro-cyclobutane.
In general, the blowing agent is e~ployed in an amount from about l to abGut 100 parts by weight per lO0 parts by weight of total polyol reactant, the particular blowing agent and amount thereof depending upon the type of foam product desired. When water is used as the sole or as a partial source of blowing action, generaily no more than about 10 p.p.h.p. of water is introduced ~to the foam system. Flexible polyether foam and high-resilience foam are blown with water either as the sole source of blowing action or in combination with up to about 40 p.p.h.p. .
of fluorocarbon such as trichlorofluoromethane. Flexible foam formulations usually contain from about one to about 6 p.p.h.p. of water. The more usual water concentration for high-resilience foam systems is from about one to about 4 p.p.h.p. In semi-flexible foam systems, the more 45.

( I ~ ;
~L~gs~89 g9l9-c-l commonly employed blowing agent is water (usually from about one to about three p.p.h.p.~, although up to about lO p.p.h.p. of fluorocarbon may also be used. For rigid foam formulations, blowing action is supplied employing a fluorocarbon in a relatively high proportion such as fronl about 10 to about lOO (usually no more than 80) p.p.h.p~ either as the sole type of agent or in combi-nation with up to about 10 p.p.h.p. of water. When -present in rigid foam syste~s, water is usually used 10 in an amount no more than about 5 p.p.h.p. The selection and amount of blowing agent in any particular fo2~ fol~.u-lation is well within the sl;ill of the cellular poly-urethane art.
In producing cellular polyurethanes in accordance with the method of this invention, a minor amount of an organosilicone surfactant may also be present as an additional component of the polyurethane-forming reaction mixture. When used, such surfactants are present in the formulation in a foam-stabilizing amount, that is, in an 20 amount sufficient to prevent collapse of the foam until the foamed product has developed sufficient strength to be self-s~upporting. Usually, foam-stabilizing amounts do not exceed about 5 parts by weight per 100 parts by ~eight of total polyol reactant. One class of especially useful _ stabilizers for flexible polyether-based polyurethane foam are the polysiloxane-poly(oxyethylene-oxypropylene) co-polymers described in United States Reissue Patent No.
27,541. Also suitable are the branched copolymers des-cribed in United States Patent No. 2,834,748. Particularly .

46.

1~95489 9919-C-l useful as foam-stabilizing components of flexible polyether urethane formulations containing a flame-retardant, are the cyanoalkyl-substituted polysiloxane-poly(oxyalkylene) copolymers described in United States Patent No. 3,846,462.
Illustrative of effective foam stabilizing components for high-resilience and semi-flexible foam systems are the relatively low molecular weight particular class of organo-silicones described in United States Patent No. 3,741,917.
When used in high-resilience and semi-flexible foam systems, the organosilicone component is usually present in an amount between about 0.025 and about 3 p.p.h.p. Illustr2tive 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.
The catalyst systems described herein are also effective catalytic components of foam formulations con-taining a flame-retardant. The flame-retardants can be chemically combined in one or more of the other materials used (e.g., in the polyol or polyisocyanate), or they can be used as discrete chemical compounds added as such to the foam.formulation. The flame-retardant may also be reactive with polyisocyanate and constitute a portion of the total organic polyol reactant contained in the formu-_ lation. In the use of flame-retardants of the chemically reactive variety, due regard should be given to the possible effect of the functionality of the compound on other prop-erties (e.g., degree of flexibility) of the resulting foam.
The organic flame-retardants preferably contain phosphorus or halogen, or both phosphorus and halogen. Usually, the .
47.

~ 9 9919- C-1 halogen, ~hcn present, 1B chlorine ~nd/or bromine.
Illustrative of ~uitable flame-retartant6 of the dis-crete chemical compound variety are those disclosed in United States ~atent No. 3,846,462 (column 34, beginning with line 39, through column 35, line 12). Other suit-able flame-retardants comprise halogen-containing poly-meric resins such as polyvinylchloride re6ins in combi-nation with antimony trioxide and/or other inorganic metal oxides such as zinc oxide, as described in ~nited States Patents 3,075,927; 3,075,928; 3,222,305; and 3,574,149. It i6 to be understood that other flame-retardant6 known to the art may be ~sed and that the aforesaid types may be employed individually or in combi-nation with one another.
When used, the flame-retarding agent can be pre~ent in the foam formulation6 described herein in an amolmt from about 1 to about 45 parts by weight per 100 parts by weight of the polyol reactant, the particular amount employed depending largely on the efficiency of any given agent in reducing the burning extent of the foam product.
If desired, other additional ingredients can be employed in minor amounts in producing the polyurethane foams in accordance with the process of this invention.
Illustrative of such additives that can be employed are:
cross-linking agents such as glycerol, diethanolamine, triethanolamine and their oxyalkylene adducts; atditives to enhance load-bearing properties; fillers (e.g., calcium carbonate and barium sulfate which are often used in semi-48.

1~95~89 9919-C-l flexible foam formulations); as ~ell as dyes, pigments, anti-yellowing agents and the like.
In general, final or post-curing of the foam products produced in accordance with the method of this invention is achieved by allowing the foam to stand at ambient temperatures until a tack-free product is obtained, or by subjecting the foam to elevated temperatures up to about 500F. in order to achieve more rapid curing. In those systems based on the more highly reactive polyol reactants such as those employed in producing high-resilience foams, a sufficiently high degree of curing is achieved during foam formation without the necessity of subjecting the foam to conventional high temperature (e.g., 300-500F.) post-curing procedures which are otherwise applied in the commercial manufacture of flexible foams from less highly reactive flexible foam formulations.
The polyurethane foams produced in accordance with the present invention are useful as cushioning material, mattresses, automotive interior p~dding, carpet underlay, packaging, gaskets, sealers, thermal irsulators and other such well-known end-use applications.
~ The following examples are offered as further illustrative of the present invention and are not to be construed as unduly limiting on the scope thereof.
_ The 2-(2-dimethylaminoethoxy)ethanol ("DMEE") employed in the examples is plant-produced material (purity, 95+ percent) and has a typical boiling range of about 90 to 110C. at 25 millimeters of mercury pressure.

49.

-1~ 9 S4 89 9919-C-l The 2-l2-(2-dimethylaminoethoxy)ethoxylethanol (DMEEE) e~ployed in the examples was prepared as follows:
A flask equipped with a magnetic stirrer and a cold-finger type condenser was charged with 2-(2-dimethylaminoethoxy)-ethanol (665 grams, 5.0 moles). The contents were heated to 125C. and addition of ethylene oxide (44 grams, 1.0 mole) was begun. Ethylene oxide was added in small portions via a chilled syringe and required about one hour to com-plete. After addition, the mixture was subjected to a cook-out period of two hours at 150-170~. Following this, the ~.ixture was fractionated at reduced pressure. An amount of lower boiling materials were removed followed by unreacted 2-(2-dimethylaminoethoxy)ethanol (D~E), recovered at 95C./
15 mm. Hg, and product 2-[2-(2-dimethylaminoethoxy)ethoxy]-ethanol (DMEEE). The latter was recovered at 128-135~C./
10-15 mm. Hg. [Literature: boiling point = 130-134C./12 mm.
Hg. Chemical Abstracts, 63, 6899d (1965);C. van der Stelt et al., Arzneimittel-Forsch., 14, 1053 (1964)]. Yield was 66 grams or 37 percent of theory based on ethylene oxide added. The material was redistilled and the heart cut collected and employed. Analysis by nuclear magnetic resonance spectroscopy indicated a purity of greater than 90 percent; a gas-liquid chromatographic analysis indicated a purity of greater than 95 percent.
_ Various terms, foam procedures and abbreviations repeatedly used or referred to in the examples are explained below:
The abbreviation "p.p.h.p." means parts by weight of a given component per 100 parts by weight of total polyol reactant contained in the foam formulation.

50.

. .

1l~9 S~ ~9 9919-C-l Breathability or Porosit~ is roughly proportional to the number of open cells in a foam, and was measured in accordance with the NOPCO breathability test procedure described by R. E. Jones and G. Fesman, "Journal of Cellular Plastics" (January 1965~. It is a measure of air flow through a 2" x 2" x 1" foam sample and is expressed as standard cubic feet per minute (SCFM).

Foamin~ Procedure I-A (Free-Rise Flexible Polyether Fozm) In accordance with this procedure, the polyether polyol reactant, silicone surfactant, amine catalyst and water are dispensed in predetermined relative proportions into a one-quart capacity container. A stainless steel baffle is inserted into the resulting polyol-containing mixture which is then mixed by means of a turbine blade operated at 2000 revolutions per minute. Mixing is interrupted after 15 seconds and stannous,octoate co-catalyst is added from a syringe. ~Iixing is then con-tinued for an additional 15 seconds, adding the polyiso-cyanate reactant after the first 8 seconds of this second mixing period. After the mixing cycle, the mixture is poured into a sup?orted container (12" x 12" x 12"). The foam is àllowed to rise and both the "cream time" and "rise time" are recorded. The latter terms denote the interval of time from the formation of the complete fo~m -. formulation to: (1) the appearance of a creamy color in ~ the formulation, and (2~ the attainment of the apparent maximum height of the foam, respectively. The fo2ms are oven cured at 120-150C. for 12-15 minutes after the rise is complete. A post-curing period of at least one day is allowed at room temperature before foam porosity is measured.
51 .

~_ ' ` J
1~95~89 gglg-c-l Foaming Procedure I-B (Free-Rise Flexible Polyether Foam~
In accordance with this procedure, the polyether polyol reactant, silicone surfactant, amine catalyst and water are dispensed in predetermined relative proportions into a 1/2-gallon capacity container. A stainless steel ~affle is inserted and a timer is set for a total of 90 seconds. The polyol-containing material is mixed for 60 seconds by means of a turbine blade operated at 2700 revolutions per minute. The mixer is stopped manually for a 15-second degassing period during which stannous octoate co-catalyst is added. The mixer is res~arted and continued for the remaining 15 seconds, adding the poly-isocyanate after 9 seconds of this final m~xing period.
The mixture is then poured into a supported container (14" x 14" x 6") and the cream and rise times are recorded.
I~hen the rise is complete, gel time may also be measured as that interval of time from formation of the complete foam formulation to the attainment of a foam which has developed sufficient strength to be self-supporting.

Foaming Procedure I-C (Free-Rise Flexible Polyether Foam) The manipulative steps involved in this procedure are essentially as described under Foaming Procedure I-A
except that mixing is done in a l/2-gallon capacity cylin-drical cup at 2700 revolutions per minute, and the mixture ~ is poured into and allowed to rise in a 14" x 14" x 6" con-~ tainer.

52.

1~95~1~39 gglg-C-l Foaming Procedure II (Free-Rise Rigid Foam) The polyol, blowing agent: ~fluorocarbon and, when used, water) and catalyst or catalysts are weighed into a one-quart, circular cardboard cup. The container is stirred by hand to adjust the blowing agent to the proper level. The materials are then mixed for 10 seconds at 2000 revolutions per minute. The polyisocyanate reactant containing the surfactant, is poured into the cup for 5 seconds. The total mixture is then mixed for an additional

5 seconds and then poured into an 8" x 8~" x ~" cardboard box ar.d allowed to rise. The cream, gel, tack-free and rise ~imes are recorded and the foams are allowed to cure overnight before cutting and determination of physical proper~ies such as density and closed cell content. In those instances where cold age shrinkage was determined, the foam samples (after the aforementioned overnight aging) were cut into cubes (2" x 2" x 2") which were then cold aged at minus 30C. for ~ period of 16 to 24 hours. Volume contraction was measured by water displacement after cold aging.
In the first series of free-rise flexible poly-ether urethane foam preparations described under Examples 1 to 12, respective foam systems, designated herein as Foam Formulations A and B, were employed. The composition of these reaction mixtures is given in Table I which follows.

. , 53.

9919-C-l TABLE I - FOAM FORMULATIONS A AND B

Components Parts By Weight A B
Polyol A: A polyether triol having 100 100 a Hydroxyl No. of 46, produced from glycerol, propylene oxide and ethylene oxide.
Polyisocyanate A- A mixture of 48 38 .

the 2,4- and 2,6- isomers of tolylene diisocyanate present in a weight ratio of 80:20, respectively. (Index = 105) Water 4 0 3 0 Stannous octoate 0.3 0.3 Surfactant A /1/ 1.0 1.0 Amine catalyst /2/ -Varied--/1/ A polysiloxane-polyoxyalkylene block copolymer having the average composition.
Me3SiO(Me2SiO)72[MeO(C3H60)2g(C2H4O)20c3H6siMeo]5-lsiMe3 where Me is methyl, employed as a 55 weight per cent active solution.
/2/ The specific amine catalysts and the concentration _ thereof are as given in Tables II and III, respectively.
.

- - ~ 54.
.

9919-C-l 1~95~89 In accordance with these examples, two series of water-blown urethane foams were prepared employing in one series, 2-(2-dimethylaminoethoxy)ethanol (DMEE), and in the second series, 2-[2-(2-dimethylaminoethoxy)-ethoxy~ethanol (DMEEE), as the respective sole amine catalyst component of Foam Formulation A (Table I). In each series, the amine catalyst was evaluated at three different concentrations, namely, 0.15, 0.30 and 0.45 p.p.h.p. For the purpose of comparison, another series of foams was prepared as Run Nos. C-l to C-3 employing dim2thylethanolamine (DMEA) at corresponding concen-trations as the sole amine catalyst component of Foam Formulation A. In each of these foam preparations, Foam Procedure I-A was followed. The results are given in Table II which follows.

.

55.

l~9S489 9919-c-l .

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56 .

1~95'~89 9919-C-l The results of Table II demonstrate that, relative to dimethylethanolamine (DMEA), the amino ether alcohols, DMEE and DMEEE, exhibit greater act-ivity as catalysts for forming water-blown polyether urethane foam when compared on either a parts by weight basis or a contained amino nitrogen basis.
Thus in Examples 1 and 2 the rise times achieved with DMEE and DMEEE were 84 and 89 seconds, respectively, whereas, in Run C-l with DMEA, the rise time was sig-nificantly longer (102 seconds) even though each cata-lyst was employed at 0.15 p.p.h.p. and even though the amino ni~rogen contents provided by DMEE and D~IEEE
(0.016 and 0.012, respectively) were substantially lower than that provided by DMEA (0.024 p.p.h.p.).
Also noteworthy is that at 0.45 p.p.h.p. of each catalyst a rise time of 71 was realized wiLh DMEA
(corresponding amino nitrogen content = 0.072 p.p.h.p.) whereas rise times of 62 and 67 seconds were achieved with DMEE and DMEEE even though the latter catalysts provided much lower amino nitrogen contents (0.047 and 0.036 p.p.h.p., respectively). Further, when compared at about the same level of contained amino nitrogen such as at 0.047 and 0.048 p.p.h.p., a rise time of 83 seconds was obtained with DMEA (Run No. C-2) whereas with DMEE the rise time was 62 seconds (Example 5).
Similarly, at a contained amino nitrogen content of 0.024 p.p.h.p., DMEA provided a rise time of 102 seconds (Run C-l) whereas a rise time of 74-s~conds was achieved with D~EE (Example 4). This enhancement in catalytic activity relative to that of DMEA is un-- ' 1~95489 ~. 3 ssl~c-expected from the standpoint that DMEE and DMEEE have a higher molecular weight group bonded to the tertiary amino nitrogen atom, that is, -CH2CH2O-CH2CH2-OH and -CH2CH2(0CH2CH2~2-OH, versus -CH2CH2-OH in DMEA. If anything, DMEE and DMEEE would have been expected to be slower catalysts than DMEA inasmu~ch as the longer nitrogen-bonded chains have, in effect, diluted the dimethylamino group.

In accordance with these examples, two further series of water-blown urethane foams were prepared em-ploying in one series, DMEE, and in the second series, DMF.EE,.as the sole amine catalyst component of 3 parts H20 Foam Formulation B (Table I). Each series included foam preparations at different levels of amine catalyst, namely, 0.4, 0.6 and 0.8 p.p.h.p. For comparison, another series of foams was prepared as Run Nos. C-4 to C-6 em-ploying dimethylethanolamine (DMEA) as the sole amine catalyst component of Foam Formulation B. Each foam was prepared following above Foaming Procedure I-A. The results are given in Table III which follows.

30. . ~ .
.. ...

58.

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59 .

la 9 5~ 89 gglg-C-l The results of Table III further demonstrate the unexpectedly higher catalytic activity of DMEE and DMEEE in providing water-blown po].yether foam relative to dimethylethanolamine when compared on either a parts by weight or contained amino nitrogen basis. Further, and as recognized in its use, 3 parts water Foam Formu-lation B is a more difficult reaction mixture to foam to a high porosity product than a corresponding 4 parts H20 system such as Foam Formulation A of Table I. It is note-worthy, therefore, that although the respective foams pro-duced with D~EA in comparative runs C-4 to C-6 were of acceptable porosity, in each instance corresponding foams provided with D~IEE and DMEEE had significantly higher porosities.

The purpose of these examples is to illustrate the efficacy of "DMEEE-R" as 8 catalyst for cellular urethane formation. As previously described herein, DMEEE-R is a normally liquid fraction obtained by distill-ation of residual product formed in the production of DMEEby the oxyethylation of dimethylethanolamine (DMEA). The particular DMEEE-R employed in this example was taken as the fraction which distilled at 96 to 140C. and 5 milli-meters of mercury pressure. Analysis of this distillate by vapor phase chromatography indicated that it contained about 70 to 75 weight percent of DMEEE, about 13 weight percent of D~IEE and about 10 to 15 weight percent of other components which have not been identified. In these examples, the said DMEEE-R was employed as the amine cata-lyst component of a water-blown polyether polyol-contain-.

60.

' ~ ~
~95~89 9919-C-l ing reaction mixture, referred to herein as Foam Formu-lation C, the other components of which are as identified in the following Table IV.

TABLE IV - FOAM FORMULATION C
Component Parts B~ Wei~ht -Polyol A /1/ 100 Polyisocyanate A /1/ 49.0 (Index 107) Water 4.0 Stannous octoate 0.225 Surfactant A /1/ 1.0 Amine catalyst Varied /1/ As defined in Table I.

For the purpose of comparison, another series of foams was prepared as Run Nos. C-7 through C-10 in which dimethylethanolamine (DMEA) was employed as the amine catalyst of Foam Formulation C. The foams were prepared following above-described Foaming Procedure I-B. The results of these examples and comparative runs are given in Table V which follows.

61.

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62 .

~L~95'~39 99l~c-l The results of Table V demonstrate the efficacy of DMEEE-R as a catalyst for the formation of water-blown flexible foam, the activity thereof being at least as good and, overall, somewhat faster than that of neat DMEA.

In accordance with these examples a further series of water-blown flexible foams was prepared employ-ing a blended amine catalyst system of the present invention as the amine catalyst of Foam Formulation C of Table IV.
The particular blend employed is referred to herein as Blend I and was constituted of: (1) 40 weight percent of the same DMEEE-containing distilled residue product employed in Examples 13-16, that is, DMEEE-R; and (2) 60 weight per-cent of the further distilled residue product referred to herein as "BDMEE-R". As previously described, the lat~er material is distillate ~boiling range, 85-180C. at 1-~mm. mercury pressure) obtained by distillation of heavier - residual products formed in the manufacture of bist2-(~,N-dimethylamino)ethyllether by the nickel-cataly~ed reaction of trimethylamine and DMEE at, for example, a mole ratio of about 3:1 and a temperature of about 180C. For the purpose of comparison, two further series of foams were prepared as Run Nos. C-ll to C-18. In one series (Run Nos.
C-12, -14, -16 and -18), an amine catalyst blend containi~g 40 weight percent of M~EA and 60 weight percent of BDMEE-R
was employed as the amine catalyst component of Foam Formu-lation C; this particular binary blend is referred to as Blend A and as such is not of the present invention. In the second series of comparative runs, a 70 weight percent solution of bis~2-(N,N-dimethylamino)ethyl]ether was em-63.

~95~189 99l9-c-l ployed as the amine catalyst of the same formulation.
The foams of the examples and comparative runs were prepared following Foaming Procedure I-B. The results are given in Table VI which follows.

..

64.

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~9~48C~ 9919 C-l The reactivity data of T~ble Vl further temon-strate that in blended 6ystems compri6ing BDMEE-R, the replacement of DMEA with DMEEE-R allows for the utilization of combination of two residual products without ~acrifice in reactivity. Also noteworthy is that, at the low con-centration t0.05 p.p.h.p.) employed in Example 17, B;end I
of ~he invention exhibited reactivity which compared favor-ably with that of the 70 weight percent solution of the bis-ether which, as is well known,$s one of the more highly reactive amine catalyst~ employed in flexible polyether foam manufacture.

These examples illustrate the catalytic effect-iveness of ternary amine catalyst systems of the present invention comprising 2-(2-dimethylaminoethoxy)ethanol (DMEE). The blends used in Examples 21-28 contained DMEE, BDMEE-R (which is as described under Examples 17-20) and, as the third amine component, either bis[2-(N,N-dimethyl-amino)ethyllether (BDMEE) or dimethylethanolamine (DMEA).
These particular blends are referred to herein as Blends II
and III, respectively. Examples 34-38 illustrate the per-formance of the ternary amine blends of the invention when used as ~olutions in dipropylene glycol ("DPG"). For this purpose, blends were prepared by forming respective 53 and 55 weight percent solutions of Blend II in dipropylene glycol; these particular solutions are designated herein as Blends IV and V, respectively. The composition of these var~ous blends i~ given ~n the following Table VII
wherein the weight percentages are based on the combined total weight of the components contained ~n the blend.

66.
A

1~9S4~9 99l9-c-l TABLE VII
Compon~ent Wei~ht %
Blend II: BDMEE-R 72.5 DMEE . 15.0 BDMEE 12.5 Blend III: BDMEE-R 60 Blend IV: BDMEE-R 38.4 BDMEE 6.6 Blend V: BDMEE-R 40 D~$EE 8 The blends described in Table VII were employed as the amine catalyst component of a 3.0 parts water-blown flexible polyether urethane foam-producing reaction mixture,`referred to as Foam Formulation D. The other components of the formulation are gi~en in Table VIII
which follows.

67. -l~9S'189 g919 c-l TABLE VIII - FOAM ~ORMULATION D
ComPonent Parts By Weight Polyol A /1/ 100 Polyisocyanate /1/ 38.1 ~Index 105) Water 3,0 Stannous octoate 0.225 Surfactant B /2/ 1.0 Amine catalyst Varied /1/ As defined in Table I.
/2/ UNION CARBIDE Silicone Surfactant L-6202 ("UNION
CARBIDE" is a Registered Trade Mark.) The foams of these examples were prepared following Foam-ing Procedure I-C. The results obtained employing Blends II and III are given ln Table IX. The latter table also includes foam data as Run Nos. C-l9 through C-22 based on the use of a 33 weight percent solution of triethylene-diamine ("TEDA" or DABCO~ in dipropylene glycol as the amine component of Foam Formulation D. As is well known, the said triethylenediamine solution employed as a standard in Run Nos. C-l9 through C-22, is one of the more highly active catalysts used for commercial manu-facture of water-blown polyether urethane foam. The foams of the C-runs were prepared with the foam series of Examples 21-24 only, also following Foaming Procedure I-C. The results obtained with Blends IV and V which contained dipropylene glycol, are given in Table X.
The latter table also includes another series of foam preparations based on Blend II which did not contain di-propylene glycol. Tables IX and X follow.

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~9S489 9919-C-l As demonstrated by the data of Table IX, DMEE-containing Blends II and III exhïbited good overall per-formance. These illustrative blends of the invention offer the advantages of being comprised of low odor, normally liquid components and allow for utilization of - by-product ~BDMEE-R) formed in the manufacture of bis~2-CN,N-dimethylamino)ethyl]ether which latter catalyst is also a highly active but relatively expensive urethane blowing catalyst. The data of Table X demonstrate that the ternary amine blends of the invention as illustrated by Blend II, for example, may also be employed in dilu.e form without sacrifice of overall performance. Thus in Example 35, Blend IV was employed at 0.20 p.p.h.p. corres-ponding to about 0.11 p.p.h.p. of total amine content, and provided a rise time of 122 seconds, a height of rise of

6.3 inches and a breathability value of ~.50. This com-pares favorably with the results of Example 30 in which 0.10 p.p.h.p. of corresponding undiluted Blend II pro-~ided a rise time of 129 seconds, a height of rise of 6.3 inches and a breathability value of 4.75. Similarly, in Example 36, Blend IV was employed at 0.25 p.p.h.p. corres-ponding to about 0.13 p.p.h.p. of total amine content and provided results which compare favorably with those of Example 31 in which Blend II was used at 0.14 p.p.h.p.

These examples illustrate the catalytic.effect-iveness of blends within the scope of the-i~vention con-taining 2-(2-dimethylaminoethoxy)ethanol (DMEE) in combi-nation with hydrocarbyl polyamines referred to for brevity as "PMDETA" and "TMBDA" where:

1O95L~89 9919 --C--l PMDETA ~ 1,1,4,7,7-pentamethyldiethylenetriamine which has the formula, C,H3 (CH3)2N-CH2CH2-N-CH2CH2-N(CH3)2 - TMBDA ~ N,N,N',N'-tetramethyl,1,3-butanediamine which has the formula, (CH3)2N-CH2CH2-cH-N(cH3)2 The blended catalysts of the invention are referred to herein as Blends VI and VII. For the purpose of compariso~.t, the standard chosen for these foam preparations was a blend, designated Blend B, of BDMEE and D~A where:

BDMEE = bis~2-(N,N-dimethylamino)ethyl]ether.
D~A = N,N-dimethylethanolamine Blend B was employed in Run Nos. C-23 to C-28. The compo-sition of comparative Blend B, and of Blends VI and VII of the invention, are given in the following Table XI.

TABLE XI
Component Wei~ht %
Blend B: BDMEE 33.3 DMEA 66.7 Blend VI: PMDETA 55 .~ Blend VII: TMBDA 55 DMEE __ 45 1~95~89 gglg-c-l In one series of foam preparations, that is, in Examples 39-44 and Run Nos. C-23 to C-25, the respective blends were used as the amine catalyst component of 4 parts water Foam Formulation A of Table I. In the second series, that is, in Examples 45-50 and Run Nos. C-26 to C-28, the respective blends were used as the amine cata-lyst component of 3 parts water Foam Formulation B which is also defined in Table I. In both series, Foam Pro-cedure I-A was followed. The results are given in Tables XII and XIII which follow.

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1~ 9 ~4 8 9 9919-C-l 5he d tc of S blc~ nd ~ lllu~erate the util~ty ~f bl nd~ of DMEE ~th tbe ~ner-lly ~ore odor-~ferou6 hydroc~rbyl poly mine6 ~uch 6 TMBDA nd PMDETA
to produc- well cured "one-~hot" flexible polyether poly-urcthane foam with ~n cceptable pr~ce~ing tlmP The u~e of the relatively non volatile DMEE ~ blend compo-nent llows re volatile or odorouc mine cataly6ts ~uch 6 TMBDA and PMDETA to be employed for their catalytic ctivity wh$1e ~eeping cataly6t vapors reduced The tata of Table6 XII and XIII 1BO lllu6trate that the use of DMEE ln combination with PMDETA as ln 81end VI, provides n amine catalyst ~y6tem for water-blown polyether urethane foam formation hs~ing n e~peci ll~ ~ood combination of catalytic activity and ability to provide open foam EXAMPL~ 50A, 51 and 52 In the6e example6, free-rise rigid foams blown with a combination of fluorocarbon and wster were pre-pared employing DMEE as the mine cataly6t component of the foam-producing resction mixture The other compo-nent6 of the reaction mixture are ~6 ldentified in Table XIV

~ 9 5~9 9919 -C-l TABLE XIV - FOAM FORMULATION E
Component Parts By ~eight Pol~ol B: ~ polyol having a Hydroxyl100 No. of about 400, derived from ethylene oxide and propylene oxide and a mixed starter containing sucrose, diethylene-triamine and aniline.
Polyisocyanate B: Ccntains (1) isocyanate 99.9 having a free -NCO content of about 38.5 weight percent, produced as a residue product in the manufacture of the 2,4-and 2,6- isomers of tolylene diisocyanate, and (2) a silicone surfactant; the weight ratio of (1):(2~ is 98:2. /1/
Blowing Agent:
Water 1.5 Trichlorofluoromethane 45.0 Catalyst system Varied /1/ Surfactant component (2) is UNION CARBIDE Silicone Surfactant L-5340.

-In these examples, the DMEE was employed as the solecatalyst of Foam Formulation E at 1.0, 2.0 and 3.0 p.p.h.p. Foams were also prepared based on the use of dimethylethanolamine CRun Nos. C-29, -31 and -33) and tri-ethylamine CRun Nos. C-30, -32 and -34) as the respective catalyst components of Foam Formulation E at corresponding concentrations of 1.0, 2.0 and 3.0 p.p.h.p. Each foam preparation followed Foaming Procedure II. The results are given in Table XV w~ich follows.

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5~ 3 9919 C-l ~ s ~n the c~e of it~ emp:Loym~nt ln the form-~tion of ~ter-bl~wn gl~ible polyelcher fo~ e dAt~ of ~able XV lndicate that, relat~ve to DMEA (a6 well as tri-ethyl~mine), DMEE al60 e~hibit~ an overall ~nhanced re-~cti~ity as a c~taly~t ~n forming riigid foam partlally blown with water. Thi~ improvement iæ realized ~hen com-pared on either a parts by weight or contalned ~mino nitro-~en basis. ~or example, on a part6 by weight basi6, the ri6e times achieved with DMEE in E~smple6 50A, 51 and 52 at a concentration vf 1.0, 2.0 and 3.0 p.p.h.p. were 216, lB3 and 155 Reconds, respectively, whereas with DMEA em-ployed in Runs C-29, -31 and -33, the ri6e times at corres-ponding concentrations were nbout 300, 203 and 173, respectively. Similarly, in Example 52, DMEE provided an amino nitrogen content of 0.32 p.p.h.p. and a rise time of 155 6econds whereas in Run C-31, DMEA provided a ri6e time of 203 seconds at aboue the 6ame amino nitrogen content of 0.31 p.p.h.p. It i6 al~o noted that DMEE pro-vided a 6eti6factory cure and acceptable clo6ed cell con-tent which are 6ignificant features of rigid urethane foam.

In accordance with these examples, 2-(2-dimethyl-sminoethoxy)ethanol ~DMEE) was employed as the 601e amine cataly~t of sn sll fluorocarbon-blown rigid foam formulation.
The particular reaction mixture employed is designated as Foam Formulation ~ snd contained the component6 given in Table XVI.

79.

8~ ggl9-c-l TABLE XVI - FOAM FOR~lATION F
Component Parts By Weight -Polyol B /1/ 100 Polyisocyanate B /1/ 99.9 Blowing Agent:
Water o.o Trichlorofluoromethane 56.4 Catalyst system Varied _ /1/ Same as in Foam Formulation E of Table XIV.

The rigid foams of these examples were prepared following free-rise Foaming Procedure II, employing DMEE at a con-centration of 1.0, 2.0 and 3.0 p.p.h.p., respectively.
Another series of all fluorocarbon blown rigid foams were provided following Foaming Procedure II employing dimethyl-ethanolamine (D~A) as the sole amine catalyst componenL of Foam Formulation F, also at 1.0, 2.0 and 3.0 p.p.h.p.
(Run Nos. C-35 to C-37, respectively). The results are given in Table XVII which follows.

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~ 8~ 9gl9-C-l The results of Table XVII illustrate the utility of 2-(2-dimethylaminoethoxy~ethanol (DMEE) as a catalyst in forming all fluorocarbon-blown rigid foam having an acceptable closed cell content. As discussed with specific reference to the rigid foam data of Table XV, when compared with DMEA on either a parts by weight or contained amino nitrogen basis, DMEE exhibits enhanced reactivity as a catalyst for forming rigid foam blown with fluorocarbon and water.
On the other hand and as indicated by the data of Table X-~II, when the blo~ing agent does nct comprise r water, D~E appears less active than DMEA when the comparison is made on a parts by weight basis. Further, when compared at about the same amino nitrogen content as in the case of Example 55 (0.32 p.p.h.p. as DMEE) and Run C-36 (0.31 p.p.h.p. as D~A), the respectivc rise times are 189 and 196 which for all fluorocarbon-blown rigid foam preparations may be considered about the same.

The purpose of these examples is to illustrate the use of "D~EE-R" as a catalyst for forming rigid urethane foam. As previously described herein, DM~EE-P~
is a normally liquid fraction obtained by distillation of residual product formed in the production of 2-(2-dimethylaminoethoxy)ethanol (D~E~ by the oxyethylation of d~methyle,hanolamine at, for example, a mole ratio of DMEA:ethylene oxide of between about 7:1 and about 9:1, a ~eaction temperature from about 140 to about 160C.
and autogenous pressure. The particular DMEEE-R employed 82.

~ ~ 5~ 9 9919 -C-l i.n the foam preparations of these examples is distillate ha~ir~ a typical boiling range from about 120 to about 140C. at 10 mm. of mercury pressure, and, for convenience, is referred to herein as D~EE-R-l. Analysis by nuclear magnetic resonance, appears to indicate that this material .ontains approximatelv 65 weight percent of 2-[2-(2-dimethylaminoethoxy)ethoxy]ethanol Although the remainder has not been identified, it is belie~Ted that the most likely principal components are various linear ethoxylated derivatives of dimethyl and monomethyl amines. In these examples, the said D'.~E~-P~-l was employed as the catalyst component o Foam Formulation F (Table XVI) at a concen-tration of 1.0, 2.0 and 3.0 p.p.h.p., and the foams were prepared in accordance with Foaming Procedure II. The results are given in Table X~III which follows.

TABLE XVIII
Example No. 56 57 58 Foam No. 84 85 86 Foam Formulation Amine catalyst:
DMEEE-R-12, p.p.h.p. 1.0 2.0 3.0 Cream time, seconds 25 18 lS
Gel time,~seconds 277 184 134 Tack-free time, secor.ds 290 192 144 Rise time, seconds ~400 ~ 335 250 Foam density, lbs./cu.ft. 1.57 1.44 1.42 Closed cells, percent 81.8 86.1 87.5 -lThe other ccmponents are as defined in Table XVI.
2Distilled residue containing approximately 65 weight percent of 2-[2-(2-dimethylaminoethoxy)ethoxy]ethanol;
boiling range = 120~-140DC./10 ~m.

~ L~ 9 919 C-l The results of Table XVIII show that the normally liquid residual produc~ containing 2-~2-(2-dimethylaminoethoxy)ethoxy]ethan.ol (that is, distillate containing a major proportion by weight of DMEEE) is also catalytically effective in forming all fluorocarbon blown rigid polyurethane foam of acceptable closed cell - content.

These examples illustrate the use of 2-(2-dime~hylaminoethoxy)ethanol (DMEE) in preblended form with an organic compound of tin for the formation of rigid foam blo~n with fluorocarbon alone or in comhi-nation with water. The particular blend employed in these examples is referred to as Blend VIII and con-tained 95 parts by weight of DlEE and 5 parts by weight of dibutyltin dilaurate. In Example 59, Blend VIII was employed as the catalyst system of all fluorocarbon blo~l Foam Formulation F (Table XVI) at a concentration of 1.5 r.P .h.p. In E~amples 60 and 61, Blend VIII was used as the catalyst system of water/fluorocarbon blown Foam Formulation E (Table XIV) at a concentration of 1.0 and 1.5 p.p.h.p., respectively. As a standard, a 3~ weight percent solution of triethylenediamine ("TEDA") in dipropylene glycol was also used at corresponding concentrations as the catalyst component of Foam Formu-lation F (Run No. C-38) and Foam Formulation E (Run Nos.
- C-39 and C-40). Each foam was prepared following free-rise rigid Foaming Procedure II. The results are given in Table XIX which follows.

. B/~.

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85 .

~5~g ~919-C-l Preliminary to the discussion of the data of Table XIX, it is noted that the triethylenediamine sol-ution used as a standard in Run Nos. C-38 to C-40 is a widely used amine catalyst in the commercial manufacture of both partially water blown and all fluorocarbon blown rigid foam. The objective, therefore, is to provide catalysts the performance of which, in all fluorocarbon-blown systems, at least app,oaches that of commercially employed catalysts such as the aforementioned solution of triethylenediamine and which, at the same time, are not too active when used to catalyze rigid foam formu-lations partially blown with water. In other words, a catalyst which may exhibit good performance in forming rigid foam partially blown with water may not exhibit the same relative performance in all fluorocarbon blown systems and, conversely, a catalyst which may show excellent reactivity in all fluorocarbon blown systems may be too active a catalyst when used to form partially water blown rigid foam. With specific reference to the results of Table XIX, it is seen that the perfol~ance of Blend VIII of the invention in forming all fluorocarbon blown rigid Foam No. 88 approached that of the triethylene-diamine solution employed in the formation of Foam No. 87 and, although performance surpassed that of the standard in forming partially water-blown Foams 91 and 92, Blend VIII was not too active in this respect. It is also noted that the use of Blend ~III at 1.0 p.p.h.p., as in Example 60, introduced a low level (0.05 p.p.h.p.)-of dibutyltin dilaurate to the foam-producing reaction mixture, and provided a foam having an acceptable cold age shrinkage 86.

1~95~9 99l9-c-l (16.3 percent) relative to that of Foam 89 (11.2 percent) produced with the standard. It is evident, therefore, that catalyst systems of the invention comprising DMEE
and an organotin compound such asl.in particular, di-butyltin dilaurate, have good performance latitude in rigid foam formulations.

In accordance with these examples, further illustrative blended catalyst systems of the invention were evaluated for their performance in forming rigid foams blo~n with fluorocarbon only and fluoroearbon in combination with water. The particular catalysts of these examples comprised D~E and N,N,N',N'-tetramethyl-ethylenediamine ("T~l~DA") as binary blends or in further combination with dibutyltin dilaurate ("DBTDL"); their composition is given in Table XX which follows.

TABLE XX
Component Wei~ht /
D
Blend lX: DMEEl 75 Blend X: DMEE 74 Blend XI: DMEE 72 -. TMEDA 25 2-(2-dimethylaminoethoxy?ethanol.
2N,N,N',N'-tetramethylethylenediamine.
3Dibutyltin dilaurate.

87.

991~C-l S4~

In Examples 62-70, Blends IX, X and YI were employed as the catalyst syste~. of all fluorocarbon-blown rigid Foam Formulation F at 1.0, 2.0 and 3.0 p.p.h.p. The results are given in Table Y~I below. The latter table also in-cludes data as Run Nos. C-41 to C-43 based on the employ-ment of the 33 weight percent active solution of tri-ethylenediamine as the catalyst of the same formulation, this standard solution also being used at 1.0, 2.0 and 3.0 p.p.h.p. In Examples 71-74, Blends IX and XI were evaluated as the catalyst system of partially water-blo~n rigid Foam Formulation E. The results are given in Table XXII which also includes corr~sponding data as Run ~os. C-44 to C-47 based on the 33 weight percent solution of triethylenediamine. The foams of the examples and C runs were prepared following Foaming Procedure II.
Tables Y~I and XXII follow.

.

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90 .

~95,~9 9919 Overall, the results of Tables XXI and XXII
~how that D~EE-containing Blends IX, X and XI of the invention are effective catalyst systems for forming rigid foam. More specifically, the results further show that, whereas the reactivity of binary Blend IX
approached that of the standard in forming partially water-blown rigid foam, there was a greater differential in reactivity in the all fluorocarbon-blown system. (To facilitate discussion, reference is made in the following analysis of the data to the average of the rise times ob-served in the respective series of foam preparations.) For example, with specific reference to the data of Table XXII, in forming fluorocarbon/water blown Foams 108 to 110 with binary Blend IX and corresponding Foams 105 to 107 with the standard catalyst, the respective average rise times were about the same (175 and 178 seconds). In contrast, in forming all fluorocarbon-blown Foams 96 to 98 with binary Blend IX and corresponding Foams 93 to 95 with the standard catalyst, the average rise times are about 206 and 153, respectively. As discussed with specific reference to the data of Examples 59-61 of Table XIX, it has been found that this differential in the all fluorocarbon systems is not only substantially reduced by the addition to the D~IEE-containing blend of dibutyltin dilaurate, as in Blends X and XI, but the enhancement in reactivity is achieved without sacrifice of the good processing characteristics of binary ~lend IX for partially water-blown formulations. Thus, in the all fluorocarbon blo~n foam preparations of Table XXI, ternary Blend XI provided an average rise time (Examples 91 .

1~9 S~ ~ 9919-C-68-7n~ of about 171 seconds which value approaches the average rise time of 153 seconds provided by the standard catalyst in Run Nos. C-41 to C-43. Notwithstanding this desirable enhancement of reactivity for all fluorocarbon-blown formulations, Blend XI is also an excellent catalyst for forming rigid foams blown ~ith fluorocarbon in combi-nation with water as shown by the results of Example 74 (Table XXII).
EX~LES 75-84 In accordance with these examples, further illustrative catalyst systems of the invention were evaluated for their performance in forming rigid foams blo~. with fluorocarbon only as well as fluorocarbon in c~mbination with water. The particular catalysts of these examples comprise D~lEE and 3-dimethylamino-N,N-dimethyl-propionamide ("DDPA") as a binary blend (Blend XII) or in further con~bination with dibutyltin dilaurate (Blends XIIT and XIV). The respective compositions of these cata;yst systems are givcn in Table XXIII which follows.

92.

.

9919-C-l ~1~9S'~
TABLE XXIII
ComponentWeight %
Blend XII: DMEEl 75 -Blend XIII: DM~E 74 Blend XIV: DMEE 72 2-t2-Dimethylaminoethoxy)ethanol.
23-Dimethylamino-N,N-dimethylpropionamide which has the formula, (C~3)2~-CH2C~l2C(0)-l~(CH3)2 3Dibutyltin dilaurate.

In the series of foam preparatisns of Examples 75 to 80, Blends XII, XIII and XIV were employed as the catalyst system of all fluorocarbon-blown Foam Formulation F of Table XVI. Also provided were foams catalyzed with the commercially employed 33 weight percent solution of tri-ethylenediamine (Run Nos. C-48 and -49), and N,N-dimethyl-cyclohexylamine (Run Nos. C-50 and -51). The latter catalyst is also employed in the commercial manufacture of rigid foa~. In the series of foam preparations of E~amples 81 to 84, Blends XIII and XIV were_used as the catalyst system of partially water-blown Foam Formulation E of Table XIV. Corresponding foams were also prepared 93.

.

~Run Nos. C-52 to C-55~ employing the aforementioned respective amines used in commercia:L practice. The foams of the examples and comparative runs were formed following Foaming Procedure II. The results are given in Tables ~XIV and XXV which follow.

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96 .

lV95~39 991 9 -c - 1 The results of Tables XX][V and XXV illustrate the utility for rigid foam formation of catalyst systems of the invention comprising 2-(2-d:imethylaminoethoxy)-ethanol (DMEE) in combination with 3-dimethylamino-N,N-dimethylpropionamide tDDPA). More particularly the data show that the performance latitude of DMEE in combination with DDPA is significantly improved by the presence in the blend of an organic compound of tin such as dibutyltin dilaurate, as in Blends XIII and XIV. For example, as reflected by rise time, the reactivity of Blend XIV in the all fluorocarbon-blown rigid formulation (Examples 79 and 80 of Table XXlV) approached that of the tri-ethylenediamine solution and surpassed the reactivity of N,N-dimethylcyclohexylamine. The overall performance of Blend XIV, as well as Blend XIII, in the fluorocarbon/H20-blown formulation (Examples 81 to 84 of Table XXV) was also excellent being comparable ~o or better than t~e commercially employed catalysts. Blends XIII and XIV (~s well as Blend XII) offer the further advantage of being composed of low odor components.

These examples illustrate the catalytic effect-iveness for rigid foam formation of catalyst systems of the invention comprising D~IEE in combination with BDMEE-R
as a binary system or in further combination with an organic compound of tin. As described in greater detail under Examples 17-20 hereinabove, BDMEE-R is a distilled ~esidue product derived from the manufacture of bis[2-(N,N-dimethyl-amino~ethyl]ether. The particular catalyst systems employed in these examples had the respective compositio~s given in the following Table XXVI.

g7.

~9s4~39 99l9-c-l TABLE XXVI
Component Weight ~/O
Blend XV: DMEEl 75 -BD~IEE-R2 25 Blend XVI: DMEE 72 -Dibutyltin 3 dilaurate 12-(2-Dimethylaminoethoxy)ethanol.
2As described under E~am?les 17-20.

Rigid fo~ms wcre prepa~ed following Foaming Procedure II
employing Blends XV and XVI as the catalyst components of fluorocarbon-blown Foam Formulation F, and Blend XVI as the catalyst component of fluorocarbon/water-blown Foam Formulation E. The results are given in the following Table XXVII which, for convenience, repeats comparative Runs C-51 (from Table XXIV) and C-55 (from Table XXV).

_ 98.

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99 .

l~9S489 9919 -C-l The results of Table XXV.II indicate that Blends and XVI of the invention are al~so effective catalyst components of rigid foam formulations. The data further show that ternary Blend XVI which was tested in both the fluoroca-bon and water/fluorocarbon blown formulations, also exhibited excellent performance latitude relative to N,N-dimethylcyclohexylamine (DMCHA). Thus, the reactivity of Blend XVI in the fluorocarbon system was about the same as that of Di~GHA as sho~n by comparing the results of Example 88 and Run C-51, and, in the fluorocarbon/water system, Blend XVI was a faster (bu~ not too highly active) catalyst than D~CHA as shown by comparing the results of Example 90 and Run C-55.
EX~LES 91 and 92 In these examples, the reactivity of catalysts of the invention was evaluated in a rigid foam formulation containing a higher concentration of water and a lower level of fluorocarbon than in Foam Formulation E of Table XIV. This particular reaction mixture is referred to herein as Foam Formulation G and has the composition given in the following Table XXVIII.
TABLE XXVIII - FOA~ FOR~IL~TIO~I G
Component Parts By Wei~ht Polyol B /1l 100 Polyisocyanzte B /1/ 110.9 ~lowing Agent:
Water 2.4 Trichlorofluoromethane -~6.0 Catalyst system /2/
ll/ As defined in Table XIV.
2l As given i~ Table XXIX.

100 .

In Example 91, the catalyst system 1was Blend XIV which, as defined in Table XXIII, contains 72 weight percent of 2-(2-dimethylaminoethoxy)ethanol (D~), 25 weight percent of 3-dimethylamino-N,N-dimethylpropionamide (DDPA) and 3 weight percent of dibutyltin dilaurate.
In Example 92, a further ternary catalyst system of the invention, designated herein as Blend X~'II,was em-ployed. The latter blend contains: (l) 72 weight per-cent of D~EE-R-l which is a distilled residue com-prising a major proportion of 2-[2-(2-dimethylamino-ethoxy)ethoxy]ethanol (D~EE) and is as described in greater detail under Examples 56-58; (2) 25 w2ight per-cent of DDPA; and (3) 3 weight percent of dibutyltin dilaurate. Each of Blen~s XIV and XVII was employed as the catalyst system of Foam Formulation G at a concen-tration of 2.5 p.p.h.p. Comparative reactivity data were also obtained (Run C-56) employing, as the catalyst system of Foam Formulation G, 1.2 p.p.h.p. of the standard 33 weight percent solution of triethylenediamine in di-propylene glycol and 2.4 p.p.h.p. of dimethylethanolamine(D~A~. The said catalyst system used in ~un C-56 is also employed in commercial practice for rigid foam manufacture.
Each foam preparation followed the same procedure which was substantially as described under Foaming Procedure II.
The results are given in the following Table XXIX.
_ 101 .

l~D95~1~39 9919 -c-l TABLE XXIX
Example No. -- 91 92 Run No. C-56 -- --Foam No. 137 138 139 Foam Formulati G
Catalyst system:
TEDA2, p.p.h.p. 1.2 -- --DME~3, p-p-h-p- 2.4 __ __ Blend XIV4, p.p.h.p. -- 2.5 --Blend XVII5, p.p.h.p. -- -- 2.5 Cream time, seconds 7-8 7-8 10 Gel time, seconds 45 40 45 Tack-free time, seconds 55 55 55 Rise time, seconds 100 85 88 The other components are as defined in Table XXVIII.
2Triethylenediamine employed as a 33 weight percent solution in dipropylene glycol.
3Dimethylethanolamine.
4DMEE (72), DDPA (25) and dibutyltin dilaur2te (3), as defined in Table XXIII.
5DMEEE-R-1 (72), DDPA (25) and dibutyltin dilaurate (3).

The reactivity data of Table XXIX indicate that Blends XIV and XVII of the invention are faster catalysts _ for promoting rigid Foam Formulation G than the combination - ~f triethylenediamine and dimeLhylethanolamine.
EXA~LES 93 and 94 _ _ In accordance with these examples, Blend XIV of the invention was emplGyed as the catalyst component of 3 parts water, flexible polyether Foam Formulation D of 102.

1~954~9 9919-C-l Table VIII. As defined in Table XXIII, Blend XIV is constituted of (weight percent): Di~EE (72), 3-dimethyl-amino-N,N-dimethylpropionamide (25) and dibutyltin dilaurate (3). The foams of these examples were pre-pared following Foaming Procedure I-C. The results are given in the following Table XXX.

TABLE XXX
-Example No. 93 94 Foam No. 140 141 Foam Formulation Catalyst:
Blend XIV2, p.p.h.p. 0.20 0.30 Cream time, seconds 11 11 Rise time, seconds 106 100 Brea.hability, SCFM 4.5 4.25 Density, lbs./cu.ft. 1.94 1.99 lThe other components are as defined in Table VIII.
2As defined in Table XXIII.

As previously demonstrated herein such as, for example, by the data of Tables XXIV and XXV, Blend XIV of the invention exhibits excellent performance latitude in its ability to catalyze water/fluorocarbon-blown rigid -- formulations as well as those which are blown with fluoro-- carbon only, at acceptable processing times. The versat-ility of such catalyst systems of the present invention is further indicated by the data of above Table XXX, which shows that Blend XIV is also a suitable catalyst for form-ing all water-blown flexible polyether urethane foam of good breathability and density.
103.

9919-C-l 1~95~

The purpose of these examples is to demonstrate the efficacy of illustrative catalyst systems of the present invention in forming molded rigid foam under simulated flow characteristics encountered in actual manufacture of refrigeration foam. For this purpose, a standard test, known as the "L-panel" test, was followed.
In this test, the foam formulation is placed in a heated mold after mixing and is allowed to rise. The mold is comprised of a lower section (10" x 16.7" x 1") and an upper section (24" x 10" x l") positioned at a right angle to the first; hence the term "L-p~nel." The foam formulation is poured into the lower mold section and is allowed to rise up into the upper part. In so doing, the foaming mass must accomplish a right angle turn and enter the back panel. Critical to the production of good foam is the balance of reactivity to allow the mass to enter the upper part of the mold before complete gelation.
Gelation too soon creates stress lines at the angular construction and results in separation and other structural deficiencies. Once the foam has entered the back cavity, the height of the foam rise therein is a measure of the final activity. If maximum rise is reached too early, high overall density will be obtained and more charge will be required to fill any given cavity.
Another measure of reaction balance is the angular deform-ation on cold aging. In this test, a cured L-pancl foam (allowed to cure overnight at room temperature) is cut so as to provide an L-shaped section about 6" wide with each leg about 6" long. These samples are placed in a freezer 104.

~9S4~3~ gglg-c-l at minus 30C. and allowed to remain overnight. After this time, the angular deformation is measured. The smaller angular deformation indicates a better cold age stability.
The particular catalyst systems employed in forming the L-panels of these examples contained D~E
and N,N,N',N'-tetramethylethylenediamine ("TMEDA") as a binary catalyst system (Blend X~'III) or as the amine components of a ternary catalyst system containing dibutyltin dilaurate (Blend XIX and above-described Blend XI). The resp2ctive compositions of these catalyst systems is given in the following Table XXXI which, for convenience, also includes the composition of Blend XI.
TABLE XXXI
ComPonent Wei~ht C/o Blend XVIII: DMEEl 65 Blend XIX: DMEE 69 DBTDL

. Blend XI: DMEE 72 ~ 12-(2-Dimethylaminoethoxy)ethanol.
2N,~,N',N'-Tetramethylethylenediamine.
3Dibutyltin dilaurate. _ 105.

~ S ~ ~ ~ 9919-C-l In ~xamples 95 and 96, B:Lends XVIII and XIX
were employed as t~e respective catalyst systems of Foam ~ormulation E (Table XIV~ at a concentration of 1.5 p.p.h.p.
and, in Examples 97-99, Blend XI was employed as the catalyst system of the same formulation at 1.0, 1.5 and 2.0 p.p.h.p. Thus, in Example 95, the formulation con-tained no dibutyltin dilaurate. In Example 96, Blend XIX
provided the foam system with 0.015 p.p.h.p. of tin com-pound and, in Examples 97-99, Blend XI provided a tin con-centration of 0.03, 0.045 and 0.06 p.p.h.p. As standards for tl.e performance of the cat.~lyst systems of the inventiol~, L-panels were also prepared employing a 33 weight percent solution cf triethylenediamine (Run l~os. C-57 to C-59) and N,N-dimethylcyclohexylamine (Run Nos. C-60 to C-62), as the respective catalysts of Foam Formulation E at 1Ø
1,5 and 2.0 p.p.h.p. In each fo2m preparation, the above-described L-panel mold ~as used and the s~me manipulative steps were followed. Thus, in the examples and C runs, the L-panel mold was waxed lightly with mold release agent and placed ir~ an oven at about 150C. When the mold temper-ature w~s about 150DC., it was removed and allowed to cool to about.120C. The foam components were mixed following the mixing procedure described under Foaming Procedure II.
The mix was then poured into the L-panel mold at a mold tem~erature of 120C. Clamps were placed and the mold kept at ambient temperature until foam rise was complete (less than 5 minu~es). The mold was then placed in the oven for about S minutes, then removed and allowed to~cool. Foams were demolded after a 10 minute cooling period. ~oam characteristics such as cream, gel, tack-free and rise times 106.

~'9~ ~ 9 9919 -C-l were determincd on the foam residue remaining in the cup in which the components were mixed. ~l~ese measurements are given in Table XXXII which also includes the height of rise (in millimeters) and the overall density of the molded L-panel shaped foams as well as their angular deformation on cold aging at minus 30~C. Flowability `
in all of the molded samples was good and no separations or pockets were observed. Table XXXII follows.

'-;~

107.

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08 .

~ ~9 9919_C-1 The data of Table XX~II indicate the good performance of the catalyst systems of the invention in providing mclded refrigeration foam. It is noted that in Example 96, the use of ternary ~lend XIX at 1.5 p.p.h.p.
provided 0.015 p.p.h.p. of dibutyltin dilaurate to the formulation. Relative to binary Blend XVIII (no tin com-pound) employed in Example 95, also at 1.5 p.p.h.p., ~lend XIX provided molded foam of substantially increased angular deformation on cold aging (14 in Example 95 versus 25 in Example 96). However, relative to N,N-dimethyl-cyclohexylamine (D~ICHA) which is employed co~mercially for the manufacture of refrigeration foam, Blend XIX
provided molded foam having about the same cold aging stability, that is, an angular deformation of 29 in Example 96 versus 31 in Run C-61. Further, although in the series of foam preparations of Examples 97, 98 and 99, the use of ternary Blend XI (3 weight percent of tin compound) provided higher concentrations of tin compound (0.03, 0.045 and 0.060 p.p.h.p.) to the res-pective foam systems than in Example 96, cold agestability also remained at acceptable levels relative to the commercially employed DMCHA. Thus, in Examples 97, 98 and 99 and Runs C-60, -61 and -62 in which the respective catalysts were used at 1.0, l.c and 2.0 p.p.h.p.
(the gel time advancing with increasing catalyst concen-tration~, the angular deformations of the foams obtained with Blend XI were 19, 34 and 30, the values obtained with D~CHA being 11, 31 and 30. It is eviaent that the catalyst systems of the present invention exhibit good performance for molded refrigeration foam relative to the 109.

~915~39 99l9-c-l more highly odorous catalyst, DMC~A, employed in commer-cial practice.

In these examples, an evaluation was made in accordance with the L-panel test described under Examples 95-99, of other illustrative catalyst systems of the inventior. as compon~nts of an all fluorocarbon-blown rigid foam system containing a flame-retardant. The particular system employed, Foam Formulation H, had the composition given in the following Table XXXIII.
YABLE ~XIII - rl~l F~`~L~I~CN :l Component Parts By Weight Polyol B /1/ 70.0 Flame-re~ardan~ diol /2/ 30,0 Polyisocyanate C: A polyphenylmethylene 101.4 polyisocyanate having an average -NCO
functionality of 2.7 and a free -NCO
content of 30.5-32.3 weight percent.
Blowing agent:
Water 0.0 Trichlorofluoromethane 50 0 Surfactant C /3/ 0.2 Catalyst system Varied /1/ As defined in Table XIV.
/2/ 0,0-diethyl-N,N-bis(2-hydroxyethyl)amino-methyl phosphonate.
/4/ Silicone Surfactant Y-6760 (Union Carbide Corporation).

-.

110 .

~L~39~ 99l9-c-l In Examples 100 and 101, the respective catalyst systems were above-described Blends XIII ~md XIV. In Example 102, the catalyst system contained D.~IEE, N,N,Nt,N'-tetramethyl-1,3-butanediamine and dibutyltin clilaurate. The compo-~ition of Blend XX is given in the following Table XXXIV
which, for convenience, also includes the composition of Blends XIII and XIV.
_BLE Y~XIV
ComponentWeight %
Blend XIII: DMEEl 74 DD~A2 25 Blend XIV: DMEE 72 .

Blend XX: DMEE 73 12-(2-Dimethylaminoethoxy)ethanol.
23-Dimethylamino-N,N-dimethylpropionamide.
3Dibutyltin dilaurate.
4N,N,N',N'-tetramethyl-1,3-butanediamine.

111 .

1095~39 gglg-c-l In each of Examples 100-102, the above-identified blends were used at 0.75 p.p.h.p. Comparative data were also obtained in the L-panel test based on the use of N,N-dimethylcyclohexylamine (DMCHA) at l.5 p.p.h.p. (Run C-63) and N,N,N',N'-tetramethyl-1,3-butanediamine (TMBDA) at 0.75 p.p.h.p. (Run C-64~, as the respective catalyst components of Foam Formulation H. The L-panels of the examples and Runs C-63 and C-64 were prepared in accordance with the procedure described under above Examples 55-99.
The results are given in Table XXXV which follows.

112.

1~9'~ 9 gglg-c-l U)o ~ J o ~ O~ h r--L ~ oo o . Lr~ ., In O ~) ~ ~ OC`
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E~ ~ ~ a) ~3 0 ~ o a a ~ _ ¢~ a 113 .

~ ~c~ 9919 -C-l The results of Table XXXV further demonstrate the excellent performance latitude of catalyst systems of the invention comprising DMEE, a second tertiary-amine compo-nent and a tin compound, in their ability to provide all fluorocarbon-bl~wn molded rigid foam of good quality and cold age stability. It is also evident that the catalyst systems of the invention allow for either the replacement or reduction in concentration of amines such as N,N-dimethyl-cyclohexylamine (DMCHA) and ~,~,N',N'-tetramethyl-1,3-butanediamine (T~IBDA) which, although relatively potent catalysts for rigid foam formulations, are relatively high in volatility and objectionable odor. Thus, Blend XX
employed in Example 102 at 0.75 p.p.h.p. contained only 25 weight percent of TMBDA, corresponding to the intro-duction of only about 0.19 p.p.h.p. of TMBDA to the formulation, whereas in Xun C-64, the formulation con-tained 0.75 p.p.h.p. of I~IBDA. Blends XIII and XIV are especially attractive catalyst systems in that they are based on low odor components, the results obtained there-with (Examples 100 ar.d 101) indicating their suitability as replacements for DMCHA. A further advantage of the blended catalyst systems of the invention for rigid foam formation is that they allow for the facile, controlled addition of ~ery low concentrations of tin compound to rigid foam ormulations to obtain a proper balance of catalyst reactivities required to achieve refrigeratiGn foam of satisfactory cold aging properties and overall density.

114.

~ 9919 -C-l EXA~LES 103-104 The purpose of these examples was to determine the efficacy of DMEE in providing molded semi-flexible foam which is free of voids. For this purpose, DMEE was employed as the sole catalyst of a semi-flexible foam system, designated Foam Formulation I, the organic polyol component of which was comprised of a polymer/polyether polyol. The composition of this formulation is given in Table XXXVI which follows.

115.

~ ~ S ~ ~ ~ 9919 -C-l TABLE XXXVI - FO~ FOR~ULATION I
Component Parts By Weight Polyol C: An ethylene oxide- 5 capped, glycerol started poly-(oxypropylene) triol having a Hydroxyl No. of about 34, a molecular weigh~ of about 5000, and a primary hyd,oxyl content of 70-75 mole percent.
Polyol D: A polymer/polyether 95 polyol havir,g a Hy~roxyl No.
of about 28 and based on (parts by weight): styrene (10), acrylo-nitrile (10) and Polyol C (80), produced by polymerizing said mono-mers in Polyol C.
Polyisocyanate D: A polyphenyl- Index 100 methylene polyisocyanate having an average -NCO functionality of 2.6 and a free -NCO content of 31.2 weight percent.
Water 1.5 Surfactant D /1/ 1.5 Filler o Amine catal~st ~aried ,.
/1/ A polysiloxane oil having the average composition, Me3SiO(~e2SiO)4[MeO(C2H4O~3C2~14SiMeO~2 gSiMe3 where ~le is methyl, employed as a lO weight per cent solution in Polyol C.

116.

l~C~S'1~9 9919-C-l In addition to DMEE, other catalysts evaluated as the respective catalyst components of Foam Formulation I
were triethylenediamine as a 33 weight percent active solution and dimethylethanolamine. The same procedure was applied in each foam p-eparation and entailed the following manipulative steps.
Foam Procedure For Molded Semi-Flexible Foam The polyol is weighed into a one quart cup and, except for the blowing agent and polyisocyanate, the other ingredients are added to the polyol while mixing at 1000 revclutions per minute. After the last ingredient is added, mixing is continued fo- 5 minutes, also at 1000 r.p.m. The polyol master is conditioned to 80F.~2.
Blowing agent is added followed by the addition of the polyisocyanate reactant which is also preconditioned to 80~F.+2. Mixing is then started immediately at 2500 to 3000 r.p.m. and is continued for 10 seconds with vigorous ci.rcular motions of the cup. The system is then poured immediately into a standard baffled test mold. Systems which perform well in this test, flow enough to fill the mold and cure in a manner which produces a foam pad free from voids. In addition, acceptable systems should not yield molded parts which show excessive shrinkage after demolding or which cream so fast as to be impractical.
Following the above procedure, in addition to DMEE (at a concentration from 0.75 to 2.0 p.p.h.p.), dimethylethanolamine (0.2 to 2.0 p.p.h.p.) and tri-ethylenediamine (0.5 to 2.0 p.p.h.p. as a 33~weight percent solution) were also employed as the respective amine compo-nents of Foam Formulation I. In each series, the resul~s 117.

:~09~ 3,9 99l9-c-l obtained at the lower and upper concentrations of the indicated respective ranges were dleficient and, except for DMEE, the results obtained with the other two catalysts at intermediate concentrations were also deficient. The results are summarized in Table XXXVII
which follows.

118.

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-~19 .

lO g~ 9919-C-l As indicated in Table ~ CVII (footnote 5), at a concentration of 0.75 p.p.h.p., ])~E did not cure the 8ystem and, at 2.0 p.p.h.p., the system was creaming rapidly and voids were formed. However, at 1.25 and 1.5 p.p.h.p. (~xamples 103 and 104, respectively), DMEE
produced excellent cure and rise time. The surface of these pads was excellent ~ith a good demoldable skin, and did not shrink upon demolding. As also summarized in Table XXXVII, D~A provided voids and a slightly under-cured foam at low ccncentra~ion (Run C-69) and, although increasing the conccntration provided a satisfactory cu~e and reduced voids considerably (Run C-70), the foam pad was not void free and slight shrinkage of the demolded foam occurred. As further recorded in Table XXXVII, the t~iethylenediamine solution employed in Runs C-65 to C-6~, provided a foam pad at 0.5 p.p.h.p. which was undercured and showed large voids and, at 2.0 p.p.h.p., the system creamed so fast under the standard test conditions, that it required cooling to allow pouring into the mold. At 1.5 and 1.75 p.p.h.p. (Runs C-66 and -67~, even though cure was improved, the molded foam pad still had large voids and, due to the high blowing efficiency of tri-ethylenediamine, the surface of the pads was torn apart.

In accordance with these examples, DMEE was employed as the amine component of a semi-flexible foam system containing a relatively high content of calcium carbonate as a filler. The composition cf the foam system, designated Foam Formulation J, is given in the following Table XXXVIII.

120.

~093~89 9919-C-l TABLE XXXVIII - FOA~I FOR~ULATION J
Component Parts By Weight Polyol C tl/ 40 Polyol D /1/ 60 Poiyisocyanate D /1/ Index 100 ~ater 1.5 Surfactant D /1/ 1.5 Filler (calciurl~ carbonate) 20 Amine catalyst Varied -/1/ Same as in Formulation I of T~ble X~'~VI.

Foams were also prepared employing dimethylethanolamine (Runs C-71 and -72) as the amine component of Foam Formu-lation J. Each foam preparation followed the procedure described under Examples 103 and 104, employing the same baffled test mold. The catalyst concentration and results are given in Table XXXIX which follows.

121.

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~9~ 991~-C-l The results of Table XXXIX further demonstrate that, relative to dimethylethanolamine, DMEE exhibits unique properties in its ability to provide molded semi-flexible filled foam which is free of voids and does not shrink upon demolding.
EY~LES 107-110 These examples illustrate the utility of DMEE-containing catalyst systems of the invention as components of a high-resilience foam formulation comprising a polymer/
polyether polyol. The cGmposition of the high-resilience foam sys.em employed is glven in Table YL which follows.

_ 123.

TABLE XL - FOAM FORM~LATION K
ComPonents Parts By Weight Polyol C /1/ 60 Polyol D /1/ 40 Polyisocyanate E: A mixture of: ~0 ~eight Index 107 percent of the 2,4- and 2,6- isomer6 of tolylene diisocyanate, the weight ratio of said isomers being 80:20, respectively;
and (2) 20 weight percent of a polyphenyl-methylene polyisocyanate having an average -NCO functionality of 2.7 and a free -NCO
content of 30.5-32.3 weight percent.
Water 2.6 Dibutyltin dilaurate 0.015 Surfactant D /1/ 1.65 ; Amine CatalYst SYstem:
Amine CatalYst A: A 33 weight percent 0.30 solution of 3-dimethylamino-N,N-dimethylpropionamide in TERGITOL TP-9*.
Amine Catalyst B: A 33 weight percent Varied solution of triethylenediamine in dipropylene glycol.
Amine Catalyst C: A 70 weight percent Varied solution of bis[2-(N,N-dimethylamino)-ethyl]ether in dipropylene glycol.
Other Amine CatalYsts:
PMDETA /2/ Varied TMBDA /3/ Varried /1/ As defined in Table XXXVI.
/2/ 1,1,4,7,7-Pentamethyldiethylenetriamine.
/3/ N,N,N',N'-Tetramethyl-1,3-butanediamine.
/4/ 2-C2-Dimethylaminoethoxy)ethanol.
* "TERGITOL" is a Registered Trade MarkO

124.

~ ~ S 4~9 9~19 -C-l In Examples 107 and 108, DMEE was employed at 0.4 p.p.h.p.
as the other amine catalyst component of Foam Formulation K.
In Example 109, DMEE was added to lhe system preblended with 1,1,4,7,7-pentamethyldiethylenetri~mine (PMDETA). In Example 110, DMEE was added preblended with ~,N,N',N'-tetra-methyl-1,3-butanediamine (TMBDA). The said blends were Blends VI and VII defined in Table XI hereinabove and, as indicated, each contained 45 weigh~ percent of DI~E. In Examples 109 and 110, Blends VI and VII were added to the Eormulation in a concentration of 0.2 p.p.h.p., thereby providing 0.11 p.p.h.p. of PMDETA ar.d TMBDA to the res-pective reaction mixtures and 0.09 p.p.h.p. of D~
For comparison, foams were also prepared with catalyst systems containing no D~E (Runs C-73 to C-75); P~ETA
and TMBDA were present in the formulations of Runs C-74 and C-75, respectively. The same procedure was applied in each foam preparation and entailed the follo~Jing manipulative steps.
Foam Procedure For Molded Hi h-Resilience Foam g An sluminum mold (4.5" x 15" x 15") is 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 mold to 175-200F. Excess mold-release agent is wiped off and the mold is allowed to cool to 120F. before foaming. The initial mixing of the components of the foam formulation is started when the mold is cooled to about 130~F. All components of the seac~ion mixture, except the polyisocyanate reactant, are measured or weighed into a one-half gallon, five inch diameter, cylindrical, cardboard carton and mixed 60 seconds with 125.

~ gS ~ 9~ 9919 -C-l a 2-l/2 inch, 6-blade turbine at 4C)00 revolutions per minute.
The polyisocyanate reactant is then weighed into the mixture of other components; s~ainless-steel baffles designed for the l/2-gallon carton are inserted, and mixing is continued for 5 seconds. The carton is then lowered to allow the mixer to drain, and the contents are quickly poured into the mold. The mold lid is closed and clamps are placed around the mold to permit flashout. "Exit time" is observed and defined as the time when all four top holes of the mold are full, that is, when the foam begins to exude from all four holes of the mold. The mold is demolded after standir.
at room temperature for 10 minutes. After trimming around the edges with scissors, the foam sample is weighed. The foam is then allowed to cure for at least one day at room temperature before being submitted for porosity measurements.
In those instances where, at the time of demolding, the surface of the foam was slightly tacky (Run C-74 and Exa~ple 107) or tacky (Examples 108-110), the surface became fully cured and tack-free within about an hour.
The results including the porosity measurements are given in Table XLI which follows.

126.

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?
9919-C-l ~5~89 The results of Table XLI indicate that Foams 173 to 176 of Examples 107 to 110, in which DMEE was present, were of higher porosity (1.1, 1.5, 2.6 ,Rnd 2.3~ than the porosity of Foam 170 of Run C-73 (0.74). Further, although Foam 171 of Kun C-74 in which PMDETA (0.15 p.p.h.p.~ but no DMEE was present, provided a foam of enhanced porosity (1.6) relative to Foam 170 (0.74~, the presence of DMEE (0.~9 p.p.h.p.) in combination with PMDETA (0.11 p.p.h.p.) as in Example 109, provided a foam porosity of 2.6. Enhancement in porosity was also observed when DMEE was used in combination with TMBDA. Thus, in Exam?le 110, 0.09 p.p.h.p. of D~E and 0.11 p.p.h.p. of TMBDA provided a foam porosity of 2.3 whereas in Run C-75 in which TMBDA was present at 0.15 p.p.h.p., foam porosity was only 0.8.
It is evident from the data presented herein that the catalyst systems of the invention have excellent performance latitude in providing cellular urethane pro-ducts derived from organic polyol reactants comprising a polyether polyol, such products ranging from all water-blown flexible polyether foam to all fluorocarbon-blown rigid foam (both free-rise and molded) including semi-flexible and high-resilience foam. As demonstrated and discussed with particular reference to Examples 1 to 12, D~E as well as D~5EEE exhibit unexpected catalytic reactivity relative to DMEA in water-blown flexible poly-~. ether foam systems. A corresponding enhancement in ~ catalytic activity relative to DMEA was not observed, how-ever, when DMEE was used as a replacement for D~IEA in an all water-blown flexible polyester foam formulation.
Table XLII presents data (Runs C-76 and C-77) based on 128.

the use of DMEA and DMEE as respective components of a water-blown flexible polyester foam formulation designed to provide free-rise, diecutable foam. ~oth foams were prepared in accordance with the same procedure which entailed the following manipulative steps: The surfactant, amine catalysts and water are premixed in a 50 milliliter beaker. The polyester polyol reactant is weighed into a tared 32-ounce capacity container. The tolylene diiso-cyanate reactant is also weighed into the container and mixed with a spatula until homogeneous. Further mixing s done on a drill press equipped with a double three-bladed marine-type propeller about three inches in diameter.
The mixing in the drill press is accomplished at 1000 revolutions per minute for eight seconds. Then the activator solution of surfactant, catalyst and water is added and mixing is continued for seven additional seconds.
The reaction mixture is poured into a 12 in. x 12 in. x 12 in. cardboard box, is allowed to rise and is then cured for about 30 minutes at 130C. The components of the foam formulation and the results are given in Table XLII which follows.

129.

1~ 9 s4r~ 9919 ~-1 TABLE XlII
Run No. C-76 C-77 Formulation, parts by weight Polyester polyol /1/ 100 100 Polyisocyanate A /2/ 47.2 47.2 N-Cocomorpholine 1.4 1.4 Hexadecyldimethylamine 0;25 0.25 DMEA 0.4 __ DMEE -- 0.4 Water 3.3 3-3 Silicone surfactant l3/ 1.0 1.0 Activator solubility Clear Cloudy Cream time, seconds 13 14 Rise time, seconds 78 76 Height of rise, inches 5.7 5.8 Breathability, SCFM 0.9 1.15 Density, lbs./cu.ft. 1.8S 1.78 Elongation, % 262 377 Diecutability /4/
Recovery, %
After 5-10 seconds 100 --After 15 seconds -- 70 After 30 seconds -- 90 After 60 seconds -- 98+

/1/ A polyester polyol having a Hydroxyl No. of 49-55, a typical viscosity at 25C. CBrookfield LVF) of 19,000-23,000 centipoise and an acid number not greater than 2Ø This particular polyester polyol was that marketed as "Wilmar Polyester 180" (Wilson-Martin Division of Wilson Pharmaceutical & Chemical Corporation).
/2/ As defined in Table I.
/3/ ~ION CARBIDE Silicone Surfactant Y-6769.
/4/ Sample thickness was 0.5 inch.

The results of Table XLII indicate that, in con-trast to the marked improvement in catalytic activity of DMEE relative to dimethylethanolamine ~IEA) in providing water-blown flexible polyether urethane foam, DMEE and DMEA
showed about the same activity on a parts by weight basis in the water-blown flexible polyester foam system.

130.

Claims (7)

WHAT IS CLAIMED IS:

1. A catalyst combination for cellular urethane formation which comprises:
(1) a total of from about 10 to about 95 weight percent of at least one dimethylamino ether mono-ol having the formula, wherein n has an average value of at least one and no more than five, and each of R1, R2, R3 and R4 represents hydrogen methyl or ethyl with the proviso that, R1 and R2 cumulatively, and R3 and R4 cumulatively, have no more than two carbon atoms;
(2) a total of from about 5 to about 90 weight percent of at least one other tertiary-amine component selected from the group consisting of bis[2-(N,N-dimethylamino)ethyl]ether, 3-dimethylamino-N,N-dimethylpropionamide, 3-dimethylaminopropionitrile, triethylenediamine, N,N,N',N'-tetramethyl-1,3-butanediamine and N,N-dimethylethanolamine; and (3) zero or up to 15 weight percent of an organic compound of tin selected from the group consisting of a stannous salt of a carboxylic acid, a dialkyltin dicarboxylate, a dialkyltin oxide, a trialkyltin oxide and a tin mercaptide;
said weight percentages being based on the combined total weight of components (1), (2) and (3).

131.

9919-C-l

2. A catalyst combination as defined in claim 1 wherein component (1) comprises 2-(2-dimethylamino-ethoxy)ethanol.

3. A catalyst combination as defined in claim 1 wherein component (2) comprises bis[2-(N,N-dimethylamino)ethyl]ether.

4. A catalyst combination as defined in claim 1 wherein component (2) comprises 3-dimethylamino-N,N-dimethylpropionamide.

5. A catalyst combination as defined in claim 1 wherein component (2) comprises triethylenediamine.

6. A catalyst combination for cellular urethane formation which comprises:
(1) a total of from 10 to about 95 weight percent of 2-(2-dimethylaminoethoxy)ethanol; and (2) a total of from about 5 to about 90 weight percent of bis[2-(N,N-dimethylamino)ethyl]ether.

7. A catalyst combination for cellular urethane formation which comprises:
(1) a total of from about 40 to about 90 weight percent of 2-(-dimethylaminoethoxy)ethanol:
(2) a total of from about 10 to about 60 weight percent of 3-dimethylamino-N,N-dimethylpropionamide;
and (3) from about 0.5 to about 10 weight percent of an organic compound of tin selected from the group consisting of a stannous salt of a carboxylic acid, a dialkyltin dicarboxylate, a dialkyltin oxide, a 132.

trialkyltin oxide and a tin mercaptide;
said weight percentages being based on the combined total weight of components (1), (2) and (3).

133.