CA1196929A - Bis(aminoethyl)ether derivatives and production of polyurethanes - Google Patents

Abstract

BIS(AMINOETHYL)ETHER DERIVATIVES
AND PRODUCTION OF POLYURETHANES

ABSTRACT

A useful balance of catalytic properties in the preparation of polyurethanes by reacting organic polyiso-cyanates with polyester polyols or polyether polyols, is provided by novel compositions having the formula (I) wherein R is hydrogen or alkyl, and R" is methyl or The compositions of formula (I) can be prepared by reacting bis(aminoethyl)ether with an alkylene oxide of the formula

Description

D.75,927-FB

BIS(AMINOETHYL)ETHER DERIVATIVES AND
PRODUCTION OF POLYURETHAN~S

The invention relates to certain novel tertiary amino catalyst which contain ether and hydroxyl moieties, and their use in the production of polyurethanes.
The use of a catalyst in preparing polyurethanes by the reaction of a polyisocyanate, a polyol and perhaps other -ingredients -is -~nown.--- The catalyst is employed to promote at least two, and sometimes three major reactions~ that must proceed simultaneously and compet-itively at balanced rates during the process, in order to provide polyurethanes with the desired physical characteristics. One reaction is a chain extending isocyanate-hydroxyl reaction by which a hydroxy~~containing molecule i~ reacted with an isocyanate-containing molecule to form a urethane. This increases the viscosity of the mixture and provides a polyurethane containing a secondary nitrogen atom in the urethane groups. A seco~d reaction is a crosslinking isocyanate/urethan~ reaction, by which an lsocyanate-containing molecule reacts with a urethane group containing a secondary nitrogen atom.
The thir~ reaction which may be involved i5 an isocyanate-water reaction by whi~h an isocyanate~terminated molecule is extended and by which carbon dioxide is ganerated to blow or a~sist in khe blowing of the foam. The third reaction is not essential i~ an extraneous blowing agent, such as a halogenated, normally liquid hydrocarbon or carbon dioxide, is employed, but is e~sential if all or even a part of the gas for foam generation is to be generated by this in situ reaction (e.g. in th2 preparation of "one-shot" flexible polyurethane foams~.
The reactions must proceed simult~neously at optimum balanced rates relative to each other in ord0r to obtain a good foam structure. If carbon dioxide evolution is too rapid in comparison with chain extension, the . ~,~,, 6~

~oam will collapse. If the chain extension is too rapid in comparison with carbon dioxide evolution, ~oam rise will be restricted, resulting in a high density foam with a high percentage of poorly defined cells. The 5 ~oam will not be stable in the absence of adequate cross-1 inking .
It has long been known that tertiary amines, such as trimethylamine and triethylamine, are effective for catalyzing the second crosslinking reaction. Other typical tertiary amines are set forth in U.S. Paten~s No. 3,925,368; 3,1279436 and 3,243,387, and in German Offenlegungsschrifts No. 2,354,952 and 2,259,980. Some of the tertiary amines are effective for catalyzing the third water-isocyanate reaction for carbon dioxide evolution, but tertiary amines are only partially effective as catalysts for the first chain extension reaction.
To overcome this problem, the so-called "prepolymer"
technique has been developed, wherein a hydroxy-containing polyol component is partially reacted with the isocyanate component in order to obtain a liquid prepolymer containing free isocyanate groups. This prepolymer is then reacted with additio~al polyol in the presence of a tertiary ami~e to provide a foam. This method is still commonly employed in preparing rigid urethane foams, but has proven less satis~actory for the production of flexible urethane foams.
For flexible foams, a one-step or "one-shot" process has been developed, wherein a tertiary amine, such as triethylenediamine, is employed in conjunction with an organic tin compound. Triethylenediamine is particularly active for promoting the water-isocyanate reaction and the tin compound is particularly active in synergistic combination with the triethylenediamine for promoting the chain extension reaction. Even here, ho~ever, the results obtained leave much to be desired. Triethylene-diamine is a solid and must be dissolved be~ore use to avoid processing difEiculties. Also, triethylenediamine and other of the prior art amines can impart a strong - -- 3 ~
amine odour to the polyurethane foam.
In addition to problems of odour and handling due to solid character, other tertiary amines have still further deficiencies. For example, in some instances the compounds are relatively volatile, leading to obvious safety problems. In addition, some catalysts of this type do not provide sufficient delay in foaming. Such a delay is particularly desirable in moulding applications to allow sufficient time to inject a preformed mixture into the mould. Yet other catalysts, while meeting specifications in this area do not yield foams ~ith a desirable tack-free time.
Lastly, while certain tertiary ~mines are somewhat suitable a~ pol~urethane catalysts they nevertheless do not have a suf~iciently high tertiary amine content, in terms of the number of tertiary amine groups compared to overall molecular weight. It is believed that the hi8her the tertiary amine content, the more rapid the catalytic activity.
It would be an advance in the art if a new class of amine catalysts were discovered which would overcome so~e of the aforementioned disadvantages of the prior art. It would also be advantageous if an unused by-product stream from an existing process could be adapted to provide the new amine catalysts.
In the production of morpholine and 2-~2-amino~thoxy) ethanol ~rom ammonia and diethylene glycol, a by-product stre~n that contains methoxyethylmorpholine and bis(amino-ethyl)ether is produced. This by-product stream may be purified by adding ethylene oxide to react with the bis(aminoethyl)ether and then distilling off t~e useful methoxyethylmorpholine according to the teaching of U.S. Patent No. 3,420,828. No use has, however, been made of the ethylene oxide adduct of bis(aminoethyl)ether until the invention of the novel tertiary amine ether urethane catalysts herein.
Other tertiary amine ethers useful as catalysts for isocyanate reactions are the beta-(N,N-dimethyl-6~

_ 4 _ ~
amino)alkyl ethers described in U.S. Patent No. 3,330,782.Other tertiary amines which also have hydroxyl substituents are the hydroxyalkyl tertiary amines of U.S~ Paten~s No. 4,026~840 and 4,101,470.
The present invention provides a composition of rnat ter having the formula ~/ ~/\ N CH3 ( I ) - R" l~ OH
R

where R is hydrogen or alkyl and R" is methyl or R

This invention also provides a method for preparing these components, which proceeds as follows. Bi~(amino-ethyl)ether of the formula is reacted with an alkylene oxide of the formula ~ .
OCH2C~R
This reaction can be carried out in accordance with the method of U.S. Patent No. 3,420,828, to produce a cornpound of the formula R \ ~ ~ N / H

H ~ OH

Where R' is hydrogen or -CH2~HOH

~ y the method of this invention9 compound 11 is reacted with formaldehyde in the presence of hydrogen and a hydrogenation-dehydrogenation catalyst to make compound 1.
This invention also provides a method ~or producing 6~

a polyurethane which comprises reacting an organic polyisocyanate with an organic polyester polyol or polyether polyol in the presence of a catalytic amount of a composition of matter having the formula (I).
The reactions to make the polyurethane catalyst should be conducted at an elevated temperature, generally in -the range from 75 to 250C. The alkoxylation step is preferably conducted at a tempera-ture from 50 to 150C, while the hydrogenation is preferably carried out at a teMperature from 75 to 250C. The hydrogen pressure in the second step is preferably from atmospheric to 210 bars and is especially preferred to be on the order of about 70 bars. The catalyst may be any hydrogenation-dehydrogenation catalyst, though it is preferred that the catalyst contain nickel, copper and chromium oxide, or cobalt, copper and chromium oxide, and it is especially preferred that the catalyst be prepared according to the method described in U.S. Patent No. 3,152,998.
The starting materials are bis(aminoethyl)ether and alkylene oxides. The alkylene oxides are pre~erably ethylene oxide, propylene oxide or butylene oxide, although higher oxides may be used. The formaldehyde reactant of the second step may be employed in another form, such as paraformaldehyde. The preparation of the novel compounds o* this înventlon is further illustrated by the following two Examples.
. .

1~3~j~2~

EXAr~pT.~ _l PREPARATION OF 2-[N-(DIMETHYL-AMINOETHOXYETHYL) N-METHYLAMINO]ETHANOL

A 1500 ml kettle was charged with gOO 8~ of a mixture of methoxyethylmorpholine, bis(aminoethyl)ether, aminoethyl-morpholine and water in the weight proportions 19:61:5:6.
The mixture was heated to 80C and 229.7 g. of ethylene oxide were added. The reaction mixture was then digested at 90C for 1.5 hours. The material was then put through a wiped film evaporator at 90~C and 0.4 rnm Hg vacuum.
There was obtained 876.7 g~ of bottoms material.
500 g. of this material was added to a flask which contained 334.5 g. of paraformaldehyde and 1500 ml of isopropanol.
This mixture was then transferred to an autoclave and reduced using a nickel 9 copper, chromium oxide catalyst at 110C and 70 bars of hydrogen. Following the hydrogen-ation, the reaction mixture was filtered then fractionally distilled. The resulting 2-CN-~dimethylaminoethoxyethyl)-N-methyl~nino~ ethanol had a boiling point of 110-115C
at 0.5 mm Hg.

2~
PREPARATION OF 2-CN-DIMETHYLAM~NO-ETHOXYETHYL)-N-METHYLAMINO~ l-METHYLETHANOL

A 1500 ml kettle was charged with 900 g. of the mi~-ture of bls(aminoethyl)ether and N-methoxyethylmorpholine in the same proportions as in Ex~mple 1. The mixture was heated to 80C and then 15104 g. of propylene oxide was added. After digesting at 90C for 1.5 hours, the reaction mixture was discharged into a 2 litre flask.

3~ ~he unreacted portion was then removed under vacuum, leaving 386.6 g. of material. 300 g. of this material were reductively alkylated using 16Zo3 g. of paraformalde hyde and- a nickel, copper~ chrornium oxide catalyst at 70 bars of hydrogen and 110C. The product was purified using a wiped film evaporator at 120C and 0.25 mm Hg vacuum. The overhead fraction contained mainly the l-propylene oxide adduct, with a little 2-propylene oxide adduct also being present.
The suit~bility of the new bis(aminoethyl)ether derivatives as catalysts for foam formulations is shown in the remaining Examples. The quantities listed in all Examples are parts by weight. The foams are all prepared by conventional means using conventional polyols, isocyanates and additives. For examples of conventional foam preparation, see U.S. Patent No. 4,101,470.
To prepare~polyurethanes using the catalysts according to the present invention9 any aromatic polyisocyanate may be used. Typical aromatic polyisocy~nates include m-phenylene diisocyanate, ~-phenylene diisocyanate, polymethylene polyphenylisocyanate, 2,4-toluene diiso-cyanate, 2,6-toluene diisocyanate, dianisidine diisocyanate, bitolylene diisocyanate, naphthalene-l 7 4~diisocyanate, xylylene-1,4-diisocyanate 9 xylylene-1,3-diisocyanate, bis(4-isocyanatophenyl)methaneg bis(3-methyl-4-isocyanato-phenyl~methane, bis(3-methyl-4-isocyanatophenyl)methane~
and 4,4'~diphenylpropane diisocyanate.
Greatly preferred aromatic polyisocyanates used ln the practic2 of the invention are 2,4- and 2,6-toluene diisocyanates, and methylene-bridged polyphenyl polyiso-cyanate mixtures which have a functionality of Erom 2 to 4. These latter isocyanate compounds are generally produced by the phosgenation of corresponding me-thylene bridged polyphenyl polyamines, which are conventionally produced by the reaction of formaldehyde and primary aromatic amines, such as aniline, in the presence of hydrochloric acid a~d/or other acidic catalysts. Known processes ~or preparing polyamines and corresponding methylene-bridged polyphenyl polyisocyanates therefrom are described in the literature and in many patents, for e~ample 9 U.S. Patents No. 2 7 683 7 730; 2,950,263;
3,012,008; 3,344,162 and 3,362,979.

The most preferred methylene-bridged polyphenyl polyisocyanate mixtures used in accordance with this invention contain 20 to 100 weight per cent of methylene diphenyldiisocyanate isomers? with the remainder being polymethylene polyphenyl polyisocyanates having higher functionalities and higher molecular weights. Typical of these are polyphenyl polyisocyanate mixtures containing 20 to 100 weight per cent of methylene diphenyldiisocyanate isomers, of which 20 to 95 weight per cent thereof is the 4,4' isomer, with the remainder being polymethylene polyphenyl polyisocyanates of higher molecular weight and functionality that have an average functionality of from 2.1 to 3.5. These îsocyanate mixtures are known, commercially available materials and can be prepared by the process described in U.S. Patent No. 3,362,979.
The hydroxyl-containing polyol component which reacts with the isocyanate may suitably be a polyester polyol or a polyether polyol having a hydroxyl number from 700 to 25, or lower. When it is desired to provide a flexible foam, the hydroxyl number is preferably in the range from 25 to 60. For rigid fo~ms, the hydroxyl number ls preferably in the range from 350 to 700.
Semi-rigid foams of a desired flexibility are pro~ided when the hydroxyl number is intermediate to the ranges just given. Also for a fl~xible urethane foam, the polyol should preferably have an average functionality of from 2 to 4 and a molecular weight of from 2,000 .i to about 6,000. For rigid foams, the functionality of the polyol component is preferably from 4 to 8~
When the polyol is a polyester polyol, it is preferably a resin having a relatively high hydroxyl value and a relatively low acid value made from the reaction of a polycarboxylic acid with a polyhydric alcohol. The acid component of the polyester is pre~erably dibasic or polybasic and is usually free of reactive unsaturationS
such as ethylenic groups or acetylenic groups. The unsaturation, such as occurs in the rings of such aromatie acids as phthalic acid9 terephthalic acid, isophthalic acid, is non-ethylenic and non-reactive. Thus, aromatic acods may be employed for the acid component. Aliphatic acids, such as succine acid, adipic,acid, sebacic acid and azelaic acid, may also be employed , and aer preferred.
The alcohol component for the polyester should preferably contain a plurality of hydroxyl groups and is preferably an aliphatic alcohol, such as ethylene glycol, glycerol, pentaerthritol, trimethyloletane, trimethylolpropane, mannitol, sorbitol, or methyl glucside. Mixtures of two or more or the above identified alcohols may be employed also if desired.
When the hydroxyl-containing component is a polyether polool, for use in flexible polyurethane foam, the polyol may be an alkylene oxide of adduct of a polyhydric alcohol with a vuctionally of from 2 to 4. The alkylene oxide may suitably be ethllene oxide, propylene oxide, or 1,2-butylene oxide, or a mixture of some or all of these.
The polyol will suitably have a molecular weight of from 2,000 to 7,000. For flexible polyether polyurethabe foams, the alkylene oxide is preferably propylene oxide, odr a mixture of propylene oxide and etyylene oxide.
For rigid polyether polyurethane foams, the polyol should have a functionally of from 4 to 8 and a molecular weith of from 300 to 1,200. Polyols for rigid polyether polyurthane foams may gbe made in various ways, including the addition of an alkylene oxide as above to a polyhydric alcohol with a functionally of from 4 to 8. These polyols may alos be, for example, Mannich condensation products of a phenol, an alkanolamine, and formaldehyde, which Mannich condensation product is then reacted with an alkylene, oxide (see U.A. Patent No. 3,297,597).
The amount of hydroxyl-cintaining pllyol compound ro vew used relative to the ixocyanate compound in both polyestef and polyethrer foams normally ahould be sucyh thqaat the isocyanate groups are present in a t least an equivalent amount, and Preferably, in slight execss, xompared with the free hydrocyl groups. Preferably, the amounts of the ingredients will be such as to provide from 0.9 to 1.5 mole equivalents of isocyanate groups per mole equivalent of hydroxyl groups. For certain shock absorbing foams, however, we have found that by using the catalyst of our invention the mole equivalents of isocyanate to hydroxyl groups can be as low as 0.4.
When water is used, the amount of water, based on the hydroxyl compound, is suitably from 0.05 to 10.0 moles per mole equivalent of hydroxy compound.
It is within the scope of the pre~ent invention 10 to utilize an extraneously added inert blowing agent, such as a gas or gas-producing material. For example, halogenated low-boiling hydrocarbons, such as -trichloromono-fluoromethane and methylene chloride, carbon dioxide and nitrogen, ~ay be used. The inert blowing agent 15 reduces the amount of excess isocyanate and water that is required in preparing flexible urethane foam. For a rigid foam9 the use of water is often avoided and only the extraneous blowing agent is used. Selection of the proper blowing agent is well within the knowledge 20 of ~hose skilled in the art. See, for example, U.S.
Patent No. 3,072,082.
Th~ catalysts according to this invention, which are use~ul in the preparation of rigid or flexible polyester or polyether polyurethane foams, are employed in an 25 amount from 0.03 to 4.0 weight per cent, based on the combined weight of the hydroxyl-containing compound and polyisocyanate. ~ore often, the amount of catalyst used is 0.06 to 2.0 weight per cent.
The catalysts according to this invention may be ~0 u~ed either alone or in a mix~ure with one or more other catalysts, such as tertiary amines, or with an organic tin compo~nd, or other polyurethane catalysts. The organic tin compound, particularly useful in making flexible foams may suitably be a stannous or stannic 35 compound,- such as a stannous salt of a carboxylic acid, a trialkyltin oxide9 a dialkyltin dihalide, or a dialkyltin oxide, wherein the organic grouFs of the organic portion OI the tin compound are hydrocarbor. groups containing from 1 to 8 carbon atoms. For example, dibutyltin dilaurate, dibutyltin diacetate, diethyltin diacetate, dihexyltin diacetate, di-2-ethylhexyltin oxide, dioctyltin dioxide, stannous octoate, stannous oleate, or a mixture thereof, may be used.
Such tertiary amines include trialkylamines (e.g., trimethylamine or triethylamine), heterocyclic amines, such as N-alkylmorpholines (e.g., N-methylmorpholine or ~-ethylmorpholine), 1,4-dimethylpiperazine or tri-ethylenediamine, and aliphatic polyamines, such as N,N,N'N'-tetramethyl-1,3-butanediamine.
- Conventional formulation ingredients are also employed, for example, foam stabilizers, also known as silicor.e oils or emulsifiers. The ~oam stabilizer may be an organic silane or siloxane. For example, compounds may be used having the formula:
RSiCO-(R2SiO)n-(oxyalkylene)mR]3 wherein R is an alkyl group containing from 1 to 4 carbon atoms; n is 4 to 8; m is 20 to 40 and the oxyalkylene groups are derived from propylene oxide ~nd ethylene oxide. See, for example, U.S. Patent No. ~,194,773.
In preparing a flexible foam, the ingredients may be simultaneously, intimately mixed with each other by the so-called "one-shot" method to provide a foam by a one-step proces. In this instance, water ~hould comprise at least a part (e.g. 10 to 100%) of the blowing agent. The foregoing methods are known to those skilled in the art, as evidenced by the following publication:
duPont Foam Bulletin, "Evaluation of Some Polyols in One-Shot Resilient Foams", March 22, 1960.
When it is desired to prepare rigid foams 9 the "one-shot" method or the so-called "quasi-prepolymer method" can be employed, wherein the hydroxyl-containing component preferably contains from 4 to 8 reactive hydro~yl groups, on the average, per molecule.
Xn accordance with the "quasi-prepolymer method", a portion of the hydroxyl-containing component is reacted in the absence of a catalyst with the polyisocyanate component in proportions so as to provide from 20 per cent to 4Q per cent of free isocyanateo groups in the reaction product~ based on the polyol. To prepare a foam, the remaining portion of the polyol is added and the two components are allowed to react in the presence of cataly-tic systems 9 such as those discussed abo-ve, and other appropr-ate additives, such as blowing agents, foam stabilizing agents, and fire retardants. The blowing agent (e.g., a halogenated lower aliphatic hydrocarbon), the foam-stabilizing agent, and the fire retardant, may be added to either the prepolymer or remaining polyol, or both, before the mixing of the component, whereby at the end of the reaction a rigid polyurethane foam is provided.
Urethane elastomers and coatings may be prepared also by known techniques in accordance with the present invention wherein a tertiary amine of this invention is used as a catalyst. See 7 for example, duPont Bulletin PB-2, by Remington and Lorenz 7 entitled "The Chemistry of Urethane Coatings".
The polyurethane-forming reaction according to this invention will be further illustrated with respect to the following specific Examples.

This Example illustrates the use of these compounds as catalysts for flexible urethane foams.
, ~ A B C D E
~, ~ HANUL F-30161 ~ 100 100100 100 100 Silicone L-62022 1.1 1.11.1 1.1 1.1 Water 2.1 2.12.1 2.1 2.1 50~ Stannous octoate in dioctylphthalate 0.6 0.60.6 0.6 0.6 Catalyst Example 1 0.5 Catalyst Example 11 --- 0.5 --- --~ ---Prior Art Catalyst 13 --- --- 0.5 -~
Prior Art Catalyst 113 ~ -- 0.5 ---Prior Art Catalyst 1113 --- --- --- --- 0.5 Methylene chloride 8.0 8.08.0 8.0 8.0 Toluene diisocyanate 28.928.9 28.9 28.9 28.9 Index 1.05 1.05 1.05 1.05 1.05 Cream time (sec) 6 7 10 11 11 Rise time (sec) 110 134145 136 154 Density, (Kg/m3) 33.32 -_- ___ 32.68 33.00 An ethoxylated-propoxylated glycerine of hydroxyl number 56' sold by Texaco Chemical Co.
2A silicone surfactant sold by Union Carbide Corp.
3Prior art catalyst I is taken from U.S. Patent No.4,026,840 and has the following structure CH
N ~ N''''~`------OH

Prior art catalysts 11 and 111 are taken from U.S.
Patent No. 4,101,470 and have the following structures, respectively CH3\N~ ~ N~ ''~ CH3 3\N--'^~--~'~N~'~ ~CH3 CH3 ~ 3 CH ~ < ~CH3 HO ~ OH

Comparing foams A, C and D from Example lll, one can see that the catalyst of this invention is more efficient than the catalysts in C or D (rise time of 110 seconds vs. 145 a~d 136). The catalysts in C and D also have a lower amine equivalent weight than the catalys~ from Example I (foam C equivalent weight is 73, foam D is 77, while cataLyst of Example I has an equivalent weight of 9530 Thus the catalysts from Example I give a ~aster reaction profile with less equivalents o~ amine being reacted. The same effect can also be obserYed in the propanol amine compounds (foams B and E).

, EXA~PLE 4 This Example illustrates .the use of these amines as catalysts for rigid urethane foams.

THANOL R-4801 ~ 35 35 Silicone L-5420 0.5 0.5 Water 0.3 0.3 Trichlorofluorom2thane 13 13 Catalyst Example 1 0.8 Catalyst Example ll 0~8 MONDUR NR3 ~ 51.2 51.2 Index 1.04 1.04 - Cream time (seconds) 10 12 Gel time (seconds) 55 76 Tack free time (seconds) 70 104 Rise time tse~onds) 90 154 ~n ~ crosc p~lyol, hydroxyl number 5307 sold by Texaco ChemicaL Co.
A silicone sur~actant sold by Union Carbide Corp.
3A polymeric isocyanate sold by Mobay Chemica:L Co.

-~k ~fl D,~ 7J~ J'Z /~

~g6~

This Example illustrates the use of these compounds as catalysts ~or highly resilient ~oams. Again, the unexpec-ted high catalytic activity of these compounds can be observed (for the hydroxyl series ~oams A, C, and D and for the hydroxypropyl series foams B and E~.
In each instance, when used at an equal weight basis, the cataly~ts of this in~ention gave faster rise times than the other amines. Note also that the same weight of catalyst of this invention contains fewer equivalents of amine than the other catalysts.

15 NIAX 34-282 ~ 40 40 40 40 40 Water . ~ 3.5 3.5 3.5 3.5 3.5 silicone L_53Q93~r 2.0 2.0 2.0 2.0 2.0 FOMRE~ UL-14 ~ OoOl O~Ol O~Ol O~Ol O~Ol Catalyst Example I 0. 5 20 Cataly~ Exaanple 11 --- 00 5 --- --- ---Prior Art Catalyst ll -~ 0.5 -~
Prior Art Gat;alyst I --~ 0 .5 ---Prior Art Catalyst lll ~ 0.5 Toluene diisocyanate/PAPI 42 42 42 42 42 25 Cream time (seconds) 7 8 8 8 Rise time tseconds) 125 120 140 140 145 ., _ A propoxylated-ethoxylated glycerine, hydroxyl number 27, sold by Texaco Chemical Co.
2 A polymer-polyol, hydroxyl number 28, sold by Union Carbide Corp.
3 A silicone surfactant sold by Union Carbide Corp.

4 Toluene diisocyanate 80% by weight, PAPI 20% by weight, PAPI is a polymeric isocyanate sold by Upjohn.
Highly resilient polyurethane foams require that an organic polyisocyanate be employed in the formulation.

~R~D~ ,~nf~

Frequently, a blend is used that consists of toluene diisocyanate a~d another polyisocyanate.
A blend of polyols must be used to make foams of high resiliency. One of the blend components is a polyether polyol ~ormed by the addition of a polyhydric alcohol ha~ing a functionality of from 2 to 4 with an alkylene oxide of 2 to 4 carbon atoms. The polyether polyol should have a ~unctionality o~ from 2 to 4 and a hydroxyl number of from 20 to 60. The second blended polyol is preferably a grafted polymer polyol containing from 4 to 25 wei~ht per cent of acrylonitrile and ~rom O
to 10 weight per cent of styrene. The rnolecular weight of the base polyol is preferably from 2,800 to 5,000.
The hydroxyl number of the resulting graft polyol is preferably from 25 to 45. These latter graft po~yols are described in detail in U.S. Patents No. 3,304,273 and 3,383,351.
The mole equivalent ratio of isocyanate groups to hydroxyl groups should be 009 to 1.2, to obtain the highly resilient foams of this invention.

EX~MPLE 6 The compound of Example 1 may be used to prepare a packaging foam as shown below:

Water 20 Trichlorofluoromethane35 Sllicone L-520 1.5 Catalyst Example I 4.0 MO~DUR MR 140.5 Cream time ~seconds) 8 Rise time (seconds) 43 Gel time (seconds) 45 . _ 1 Polyol sold by Texaco Chemical Co., hydroxyl number 220.
2 A silicone surfactant sold by Union Carbide Corp.

Claims (17)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A composition of matter having the formula (I) where R is hydrogen or alkyl and R" is methyl or

2. 2-[N-(dimethylaminoethoxyethyl)-N-methylamino]
ethanol,

3. 2-[N-(dimethylaminoethoxyethyl)-N-methylamino]-l methyl ethanol,

4. A method for the preparation of a composition of matter according to Claim 1 which comprises reacting bis(aminoethyl)ether and an alkylene oxide having the formula wherein R has the meaning given in Claim 1, and reacting the product with formaldehyde in the presence of hydrogen and a hydrogenation-dehydrogenation catalyst,

5. A method for the preparation of a composition of matter according to Claim 2 which comprises reacting bis(aminoethyl)ether and an alkylene oxide having the formula wherein R is hydrogen and reacting the product with formaldehyde in the presence of hydrogen and a hydrogenation-dehydrogenation catalyst,

6. A method for the preparation of a composition of matter according to Claim 3 which comprises reacting bis(aminoethyl)ether and an alkylene oxide having the formula wherein R is methyl and reacting the product with formaldehyde in the presence of hydrogen and a hydrogenation-dehydrogenation catalyst,

7. A method as claimed in Claim 4, 5 or 6 wherein the reactions are conducted at a temperature from 75 to 250°C and a pressure from atmospheric to 210 bars.

8. A method as claimed in Claim 4, 5 or 6 wherein the hydrogenation-dehydrogenation catalyst contains nickel, copper) and chromium oxide, or cobalt, copper and chromium oxide,

9, A method for producing a polyurethane which comprises reacting an organic polyisocyanate with an organic polyester polyol or polyether polyol in the presence of a catalytic amount of a composition of matter according to Claim 1,

10. A method for producing a polyurethane which comprises reacting an organic polyisocyanate with an organic polyester polyol or polyether polyol in the presence of a catalytic amount of a composition of matter according to Claim 2.

11. A method for producing a polyurethane which comprises reacting an organic polyisocyanate with an organic polyester polyol or polyether polyol in the presence of a catalytic amount of a composition of matter according to Claim 3.

12, A method as claimed in Claim 9 where the polyol is reacted with the polyisocyanate in the presence of a blowing agent to form a cellular polyurethane.

13. A method as claimed in Claim 10 where the polyol is reacted with the polyisocyanate in the presence of a blowing agent to form a cellular polyurethane.

14. A method as claimed in Claim 11 where the polyol is reacted with the polyisocyanate in the presence of a blowing agent to form a cellular polyurethane.

15. A method as claimed in Claim 12, 13 or 14 wherein the polyol is a polyether polyol having a molecular weight of 2,000 to 7,000 formed by the addition of a polyhydric alcohol having a functionality of from 2 to 4 with an alkylene oxide of 2 to 4 carbon atoms, and the organic polyisocyanate is employed in an amount sufficient to provide 0.4 to 1.5 mole equivalents of isocyanate groups per mole equivalent of hydroxyl groups thereby forming a flexible polyether polyurethane foam.

16. A method as claimed in Claim 12, 13 or 14 wherein the polyol is a hydroxyl-terminated condensation product having a functionality of from 2 to 4, a molecular weight from 2,000 to 6,000, and a hydroxyl number from 25 to 60, obtained from a polycarboxylic acid and a polyhydric alcohol and the polyisocyanate is toluene diisocyanate employed in an amount sufficient to provide 0.9 to 1.5 mole equivalents of isocyanate groups per mole equivalent of hydroxyl groups thereby forming a flexible polyester polyurethane foam,

17. A method as claimed in Claim 12, 13 or 14 wherein the polyol is a blend comprising a) A polyether polyol having a functionality of from 2 to 4 and a hydroxyl number from 20 to 60, formed by the addition of a polyhydric alcohol having a functionality of from 2 to 4 with an alkylene oxide of 2 to 4 carbon atoms, and b) A grafted polymer polyol containing from 4 to 25 weight per cent of acrylonitrile and from 0 to 10 weight per cent of styrene, the molecular weight of the base polyol being from 2,800 to 5,000, and the hydroxyl number of the grafted polyol being from 25 to 45, the organic polyisocyanate being employed in an amount sufficient to provide 0.9 to 1.2 mole equivalent of isocyanate groups per mole equivalent of hydroxyl groups, whereby a highly resilient polyether polyurethane foam is prepared,