CA1264767A - Polyoxyalkylene polyether amino alcohols containing a tertiary hydroxyl group and flexible polyurethanes made therefrom - Google Patents

Abstract

POLYOXYALKYLENE POLYETHER AMINO ALCOHOLS
CONTAINING A TERTIARY HYDROXYL GROUP AND
FLEXIBLE POLYURETHANES MADE THEREFROM
(Docket #80,410-F) ABSTRACT OF THE DISCLOSURE

Polyoxyalkylene polyether amino alcohols are pre-pared which have the following formula:

(IV) Wherein, R represents hydrogen or a methyl or an ethyl group, x represents a number having an average value of about 1 to about 4 and n represents a number having an average value of about 1 to about 40.
The polyoxyalkylene polyether amino alcohol is prepared by alkoxylating a glycol that contains one tertiary hydroxyl group and also a primary or secondary hydroxyl group in order to form an alkoxylated interme-diate and by then reductively aminating the alkoxylated intermediate.

Description

~Z~i~7~7 CONTAINING A TERTIARY HYDROXYL GROUP AND
FLEXI_LE POLYURETHANES MADE_THEREFROM
(Docket #80,4l0--F) BACKGROUND OF THE INVENTION

Field of the Invention , _ ___ _ _ _ __ _ _ __.
This invention relates ~enerally to the preparation of polyoxyalkylene polyether amino alcohols containin~ a tertiary hydroxyl group and their use as chain extenders in the preparation of flexible polyurethane elastomers and flexible polyurethane foam.
The amino alcohols of the present invention, which may also be characterized as alpha, tertiary hydroxy-polyoxyalkylene polyether-omega-amines are prepared from a polyalkylene ylycol containing a tertiary hydroxyl group and a secondary hydroxyl group which is a:Lkoxylated with ethylene oxide, propylene oxide or butylene oxide or a mlxture t:hereof to form a pol.yether intermediate which is then reductiveLy aminatetl to provide the desired amino al.cohol. The thu.s prepared materials are useful as chain extenders in the preparation of flexible polyurethanes, such c15 flexi.ble polyurethane elastomers and flexlble polyurethane oams, coatings, adhesives, sealants, etc.
~Prtor_Art Prescott et a:l.. U.';. Patent No. 3,:L-79,606 i.c.l cll.rf~cted l~o G~11U1~Ir-~I~O~Y~ rIf~ In~ 3 1 I 0111 ~

C

polyoxyalkylene polyether polyol and a polyethylene polyamine.
Edwards et al. U. S. Patent No. 3,297,597 is di-rected to Mannich condensates of a phenol, formaldehyde and an alkanolamine and to their use in the manufacture of polyurethanes.
Lee et al. U. S. Patent No. 3,236,895 discloses diamines prepared from polyoxypropylene glycol starting materials.
Yeakey U. S. Patent No. 3,654,370 is directed to polyoxyalkylene polyamines prepared from the correspond-ing polyoxyalkylene polyols.
Moss et aL. U. S. Patent No. 3,838,076 is directed to polyurethane foams prepared from partially amin.ated polyoxyalkylene polyether polyols wherein the amine groups are introduced by reductive amination of the poly-oxyalkylene resin in the presence of a hydrogenation-dehydrogenation catalyst, hydrogen and ammonia.
Cuscurida et al. U. S. Patent No. 4,296,213 is directed to polyurea polymcr polyols Im~ e hy re.l~t-il-lq a hyd.roxyJ.-contai.nin~ ilmll~ c.~ly- l.h~r t~ I yo.l .ill'lt organic polyiso~yan.lte. 'l'l1e hydroxy containlng amin~
is an alkanolamine or a heterocyclic compound such as hydroxyethyl piperazine, otc. ~rhe use of 2-hydroxy-ethylethylenediamine is d:isclosed as a suitablehydroxyl-containing amine.

7~603-~SUMMARY OE THE INVENTION
The present invention is directed to the preparation of polyoxyalkylene polyether amino alcohols having the following fo.rmula:

~IV) HO-C-[CH21X-C IOCH2-C]n-NH2 Wherein, R represents hydrogen or a methyl or an ethyl group, x represents a number haviny an average value of about 1 to about 4 and n represents a number having an average value of about 1 to about 40.
The polyoxyalkylene polyether amino alcohols of the present invention are prepared by the reductive amination of an alkylene oxide adduct of a glycol contalning either a secondary or a prlmary hydroxyl L~
~, group and a tertiary hydroxyl ~roup. The polyoxyalkyl-ene polyether amino alcohols of the present invention are useful as chain extenders in the manufacture of flexible polyurethanes such as flexible polyurethane elastomers and flexible polyurethane foam.

DETAILED DESCRIPTION
The Polyoxyalkvlene PolYether ~mino Alcohol The starting materials for the preparation of the polyoxyalkylene polyether amino alcohols of the present invention are a glycol and an epoxide.
The glycol to be used is a glycol that contains one tertiary hydroxyl ~roup. The other hydroxyl group may be primary or secondary, as illustrated by the following formula:

CH3 Cll3 HO IC [CH2]X IC OH

2~

Wherein, x hrl~a ll v.~lU~ oL zll)ouE l lo CIL~out 4.
}~cpresenta~ive ~lycol~ th~t rrl~y t)~ usad ;nclucle, ~or example, 2-methyl-2,4-pentane diol ~comrllonly known a~

hexylene glycol), 2-e~hyl-2,4-hexancdiol, 2-methyl 2,5 ~5 hexaned~ol, 2-ethyl-4-methyl-3,5-heptlnediol, etc.

The epoxide starting mate~ial to be used is suita-bly ethylene oxide, propylene oxide or butylene oxide or a mixture ~hereof. Such epoxides have the formula:

R
(II) l Wherein, R represents hydrogen, a methyl group or 10 an ethyl group.
The glycol feedstock is alkoxylated with the epox-ide under basic alkoxylation conditions. Thus, the glycol may be reactecl in a suitable reaction vessel, such as a jacketed kettle containing temperature con-trol means and an agitator together with appropriate feed lines and a draw off line. The glycol is reacted with from about 1 to about 40 moles of the alkylene oxide to form a polyoxyalkylene polyether glycol inter-mediate. The reaction is suitably conducted at a tem-perature of about flO to about l5n~C un~er a mod~stly t~31t~v~tt3cl pr@~l~u~t~ 'x~ lr~J~ k~l~lnl~ln~ r~
Illcly l)e USl.`d 'ill ~lle rl`~ i.OIl il`~CI.utlo '::O~`hi~llll lly(lt'OX.i(l(~!~
potassium hydroxicle and the corresponc3in~3 hydride~3 an<l alkoxides.
The polyoxyalkylene polyether intermediatt-~ charac~
teristically will have the Eollowing formula:
-12~ 7 HO-C-[CH21x-C-[OCH2-C]n--OH

Wherein, R has the meaning given above and wherein x represents a number having an avera~e value of about 1 to about 4, and n has a value of 1 to 40.
The thus prepared polyoxvalkylene polyether i~ter-mediate is then reductively aminated in the presence of hydrogen and ammonia using a nickel, copper, chromia catalyst of the type disclosed by Yeakey U. S. Patent No. 3,654,370. Such catalysts are described, for exam-~ , i.n U. .s. Pntc~n~ No. ~,152,~3. Tlle c.lt.lyst. i~
prepared by the reduction of a mixture of the oxides of nickel, copper and chromium in the presence of hydrogen at a temperature within the range of about 250 to 400C. Calculated on an oxide-free b~si.s, t.he c.at~lyst contains about 60-85 mole percent nickel, 14-37 mole percent copper and 1-5 mole percent chromium. A
particularly preferred ca~.llyst composi.tion is one ct~nt.l~Lrlirl~ 7()~ ol- p~r(~ i~k(~ 2'~ )t~l~r~
k ~.`t~pt~r ~ r~ t~ r~ . cl~lre~
The process is con~ucted i.~t a ~mpera~ure withln the range of from about 1.5() to 275"C wit.h a pre~erred range be-~in~ trom 20t) to 250C. The pressure may be v,~ried from 500-5000 psig with the pre~ferrecl r.an~e beinq 2000-40()0 psi~.- 'rhe process may be conducted . ~ ~

7~7 with or without a solvent. Solvents that may be em-ployed include water and inert hydrocarbons such as heptane and cyclohexane. A preferred solvent is liquid a~ onia whi~h can bc;)resent in a 10-40 mo3e e~xcess with a 20-30 mole excess being preferred. It is con-venient to use ammonia as a solvent since ammonia is necessary to the reaction.
The process may be conducted batchwise, as is done with prior art processes using Raney nickel catalyst, or it may be conducted continuously. Continuous opera-tion is preferred, since, in general, batch processes are slow and require filtration to remove the catalyst.
The resu]tant reductive amination product will be comprised primarily of a polyoxyalkylene polyether amino alcohol having the following formula:

(IV) l l l HO-C-[cfl2]x-c~[oc~l2-l]n Nll2 Whc~r~iTl, ~, [~ éln~ n ~ v~ rn~ i rl~1fl ~I i.v-~n ~ c~ve~.

Manufclcture of Flexible Po1yurethanes The components utiLized ~or the mLtnuEacturc of ct ]~xible polyurethane~ include the po]yoxyalky1etle poly-ether amino alcohol of the present invention, a polyol, ~X6~L767 an organic polyisocyanate, a catalyst, and other desired additives such as fire retardants, dyes, fillers, etc.
The polyol componen~ in ~he present invention comprises a polyoxypropyloxyethylene polyether polyol haviny a hydroxyl numher between 20 and 60, a functionality of 2 ~o 8 and a molecular weight in the range of about 2,000 to abou~ 8,000.
Normally, propylene oxide will constitute from about 80 to ahout 100 wt.'o of the total polyol composition. Up to about 20 ~t.~, of ethylene oxide may be utilized if desired, based on the weight of the propylene oxide.
A wide variety of initiators may be alkoxylated to form useful polyoxypropylene polyols. Thus, for example, polyfunc-tional amines and alcohols of the following types may be alkoxy-lateds monoethanolamine, diethanolamine, triethanolamine, ethylene glycol, polyethylene glycols, propylene glycols, polypropylene glyco:Ls, glycerine, trimethylolpropane, penta-erythritol, sorbito:L, sucrose, and mixtures thereof.
Such above amines or alcohols may be reacted with an alkylene oxide component consisting of 100 to about 80 wt.% of propylene oxide and 0 to about 20 wt.% of ethylene oxide usiny tecllni~ues known t,o t.ho.se sk:lLI.ed i.n 1 h~l ar l,. 'I'hlls, fl)r ~x..unl?1~3, t:he relction ol. al.kyl~.~t~ oxlde?; wlt,ll :I.nll,l.~ rs (.~1: I,h:l?l tyl)~ .L?3 set fort,ll :ln IJnl~ecl ~,t.ates Palerlt Nos. 2,9~3, 1'~1 arlcl 3,00(),~63.
E,ssentlally such alkoxylations are carried out in the presence of a ~2~7~' _9_ basic catalyst at a temperature sufficient to sustain the reaction. The hydroxyl number which is desired for the finished polyol will determine the amount of alkylene oxide used to react with the initiator. The polyoxy-propylene polyether polyol may be prepared by reacting the initiator with propylene oxide or by reacting the initiator first with propylene oxide followed by ethyl~
ene oxide or vice versa in one orrnore sequences to give a so-called block polymer chain or by reactin~ the initiator with a mixture of propylene oxide and ethylene oxide to achieve a random distribution of such alkylene oxides. As noted above, the polyoxypropylene polyether polyols useful here have a hydroxyl number ranging from about 20 to about 60. The reaction mixture is then neutralized and water and excess reactants are stripped from the polyol.
Typical aromatic polyisocyanates that may be used in the practice of the present invention include m-phenyl-ene diisocyanate, p-phenylene diisocyanate, polymethyl-ene polyphenylisocyanate, 2,4-toluene diisocyanate, 2,6-tolylene diisocyanate, dianisidine diisocyanate, bitolylene diisocyanate, naphthalene-1,4-diisocyanate, diphenylene-4,4'-diisocyanate, aliphatic-aromatic diiso-cyanates, such as xylylene-1,4-diisocyanate, xylylene-1,2-diisocyanate, xylylene-1,3-diisocyanate, b1s(4-iso-cyanatophenyl) methane, bis(3-methyl-4-isocyanatophenyl) methane, and 4,4'-diphenylpropane diisocyanate.

~, , '':' ' "` '' , . , ' . '' ' ' ~;2647~i'7 Methylene-bridged polyphenyl polyisocyanate mix-tures which have a functionality of from about 2 to about 4 may also be used. These latter isocyanate compounds are generall.y produced by the phosgenation of corresponding methylene bridged polyphenyl polyamines, which are conventionally produced by the reaction of formaldehyde with a primary aromatic amine, such as aniline, in the presence of hydrochloric acid and/or other aci.dic catalysts. Known processes for preparing the methylene-bridged polyphenyl polyamines and corres-ponding methylene-bridged polyphenyl polyisocyanates thcrefrom are descr:i.bed in the literature and in many patents, for example, V. S. Patent Nos. 2,683,730;

2,950,263; 3,0:L2,008; 3,344,162; and 3,362,979.
The methy:Lene-brid~ed polyphenyl polyisocyanate mixtures used here may contain from about 20 to about 100 wt.% of met:hylene diphenyl dii.socyanate isomers wi.th the remainder being polymethylene polyphenyl diisocyanates havin~ higher functional..i.ti~s an~l hi.~h~r molecular weic3ht.~;. Typic~ll. ol~ kh~r)-t /lrQ polypherlyl.

~ I.yi~-;o~y~ Illixl-~lr,..~ tf~ i.llL~ ul ~ t(~ ) wt.'h methyl.ene dipllenyl. ~li.isocy.lnnt:e :i sotners~ o:t' whi.ch 20 to about 95 wt.~ ther~o~ is the ~ isomet^ with thc remainder he.i.nq polym~thylene po:lyphenyl poly.isacyanates ~5 o higll~r moleculrlr wei~ht arl~l lunctionality that htve `. an average functionalit.y o~ from about 2.1 to about

3.5. The isocyanate mi.xtures are known materials.

~2~4767 The catalysts which may be used to make the foams are well known. ~ertiary amines and organo-metallic compounds are normally preferred. They are used in effective amounts.
Examples of suitable tertiary amines, used either individually or in admixture, are the N-alkylmorpho-lines,N-alkylalkanolamines,N,N-dialkylcyclohexylamines and alkylamines where the alkyl groups are methyl, ethyl, propyl, butyl, etc. Examples sf specific terti-ary amine catalysts useful in my invention are triethyl-enediamine, tetramethylethylenediamine, triethylamine, tripropylamine, tributylamine, triamylamine, pyridine, quinoline, dimethylpiperazine, dimethylhexahydroaniline, diethylpiperazine, N-ethylmorpholine, dimethylaniline, nicotine, dimethylaminoethanol, tetramethylpropanedi-amine, and mel:hyltriethylenediamine.
Organo-metallic compounds useful as catalysts include those of bismuth, leatl, tin, titanium, iron, antimony, uranium, cadmium, cobalt, thorium, aluminum, mercury, zinc, nickel, cerium, molyhclenum, vanatlium, cc)~per, mant3allosa, z.i rcc~n iUfll, t-~t C. C~OIII~.' oxarllF~ 3~l ol~
tl~ 3~.~lllt~ 3 t~ ly~ u(l~ t)i~ , lt3tl~l 2-etllyL}ltxoate, lead benzoate, Lead oleate, dibutyl.ti dilaurate, tributyltin, butyltin tric~lloride, st~lnnic 2~ loriclo, st-;lnnou~3 octoat:e, stannous o1e~te, diblJtyltin di(2-ethy]hexoate), ~erric chloride, antimony trichlo-ride, antirmony qlycolate, tin glycolates, etc.

~ZIEi~L~6~

Selection of the individual catalysts and the effective amounts to use in the polyurethane reaction are well within the knowledge of those skilled in the art, and an amine and organo-metallic compound are often used together in the polyurethane reaction.
Another conventional ingredient that is usually employed is a so-called foam stabllizer. The foam stabilizers are frequently used even when the desired product is a urethane elastomer in order to minimize the formation of large void spaces in the elastomer.
Foam stabilizers are also known as silicone oils or emulsifiers. The foam stabilizer may be an organic silane or siloxane. For example, compounds may be used having the forrnula:

(V) RSi[O-(R SiO)n-(oxyalkylene)mR]3 wherein R is an alkyl group containing from 1 to 4 carbon atoms; n is an integer of from 4 to 8; m is an 2n integer of 20 t:o 40; and the oxyalkylene groups are derived from pror)yl~ e ~x-ide .lrlll ~hyl(!nQ ~xi~lf~

r~,~ (!X~ , U. ~ nl Nt). ~ ,/7~.
'l'h~ fl.lme r~tar~ cy ol the pc~lyllrcthi~ne compo~

t:lon can be enhanc~cl ~y usin~l known ire retarclLInt:s.
~1; Uxalllr?les o( -;uit.l~lc rlal~ rctardants are: tris(l,3 (li-chLoropropyl)phosphate, tr:is(2,3-dibromopropyl)phosph~lte, ~2~4~

2,2-bis(chloromethyl)-1,3 propylene bis[-di(2-chloro-ethyl)phosphatel, tris(2-chloroethyl)phosphate, tris(2-chloropropyl)phosphate, bis(dichloropropyl)tri-bromopentyl phosphate, tetrakis-(2-chloroethyl)ethylene diphosphate (sold by Olin Chemicals ar~ THERMOLINR101), FY~OLR EFF (oligomeric chloroalkyl phosphate, sold by Stauffer Chemical Co.), tricresyl phosphate, cresyl diphenyl phosphate, chlorinated paraffins, and bromi-nated paraffins. Although a single flame retardant is preferred from the standpoint of simplicity of formula-tion, mixtures of two or more of the same type or ofdifferent types may be found to give improved perform-ance in some c:ases, and such mixtures are included in the scope of this invention. The amount of flame retardant can be varied over a wide range of from about 10 to about 50 parts by weight per 100 parts by weight of polyol in the reaction mixture. It is preferred to use from about 10 to about 20 parts by weight.
The polyurethane foams are preferably made in one step by re~aet.illc~l all the :i ntlre~llt~nt a toyet;llQr ( I 1~ on shok procc~qf3)~ kl~rnately~ Iho so-ta.l 1.@~1 "prepolylllt!r"
mtlthodlmay be ust!tlw~lertin olll.y a portl.on o~ th~ pol.yo1 is init.i.ally reaoted with ~.he polyisocy~nate to form a so-calletl prepc.)lylller havin~l an excess Oe free, or unre-acted isocyanate groups. I'ht rest of the polyol and other ingredients may then be added to the prepolymerto co~plete the reaction.

~2~7~7 When it is desired to form a flexible polyurethane foam, an effective amount of a so-called blowing agent should also be employed.
Water is normally the preferred blowing agent for flexible foam. All or part of the water may be re-placed with an inert blowinq agent such as trichloro-monofluoromethane, dichlorodifluoromethane, dichloro-monofluoromethane, l,l-dichloro-l-fluoromethane, 1,1-difluoro-1~2,2-trichloroethane, chloropentafluoro-ethane, and the like. Other useful blowing agents including low-boiling hydrocarbons such as l~utane, ~ntlne, hexnne, oyc]oh~xan~, ~nd th~ like. ,See IJ. ~.
Patent No. 3,072,582, for example.
~n accor(Jance with the present invention ~rom about 0.5 to about S wt.% of the polyol component is replaced with the chain extender polyoxyalkylene poly-ether amino alcohol of the present invention. Since the chain extender contains a primary or secondary amine group, it is self-catalyzing. Moreover, the amine group wi.ll react rapidly with the other ingre-dients in the ormulntion.
I~n ~ICIVn~ aq~3 Or ~h~ prc3~lent lnv~ull.:ic3rl .is, l~ t ( llet~rminLIl t:ert.iary hydrcxyl tlroup 19 signiEit.3ntly le5~;
reactive than the amine ~roup an(l therc~Eore reclcts only ;5 s,lowly wit:h t:he other colnponerlts of ~:he ~ormulatlon.

~s a consequence, the chain extender of the present 7~;7 invention is more uniformly incorporated into the poly-urethane resulting in a product having improved tensile strength properties. When the polyurethane product is a flexible polyurethane foam, flexibility will not he impaired but at the same time a firmer foam will be formed.

SPECIFIC EXAMPLES
~xample l This example will illus~rate the preparation of the hexylene glycol-~ased diol. This diol served as the startinq material for the amino alcohols of this invention.
Hexy]ene ~lycol* (~.0 lb) and 72g 45% aqueous -5 potassium hydroxide were charged into a five-gallon kettle. Maintaining a nitrogen purge the mixture was heated to 100C and stripped to a water content of 0.032 wt.%. Propylene oxide (9.6 lb) was then reacted at lOS-115C at S0 psig. Approximately 2.5 hours was required for addition of the propylene oxide. ~he reaction mixturc was then di~3este-l ~.5 hours t-o nrl ~!ql,l'i.~ r.i,l.llrl r~ C`~ lr~ k~ ? ~3r~3~ t~ W~l!; t.~
lleUtra i.i.'~.cd ~y st' i rr:in(l two hc~llrs at. ~5UC with ~O()~l magne~sium silicate which was a(lclc~d aci nn llq-lcous slllrry.
~5 Di-t~butyl p-crcsol (13.2q) rlrl(l llyllo ~Sup~r(el~(',0~) were also ndde~d at thlC, timc~. 'l'he nelltrali%ecl l)roduct was vacuum stripp~d to a minimulrl pressure, nitrogen ~r~ hla~k ~ 167 ~

stripped, and filtered. The finished product had the following properties:

TABI,E I
Sample No. 5748-32 l'rol~ertic~:i Acid no., m~ KO~/~ n.no3 Hydroxyl no., mg KOli/g 163 Water, wt.% 0.02 pH in 10:6 isopropanol-water 7.8 Color, Pt-Co 25 Sodium, ppm 0.5 Potassium, ppm 1.4 *2-methyl-2,4-pentanediol; Ashland Chemical Co.
The NMR spectra of the product indicated that the propylene oxide~ addition had taken place at the second-ls ary hydroxyl with less than 10% addition taXing place at the tertiary carbon.

Exarnple 2 This example will illustrate the reductive amina-tion of the hexylene glycol-initiated diol of thi.s invention. The diol of ~xamplt? 1 wa5 retluctively an)i-n~t~d at 21()C in a on~?-liter con~L~ us retltt)t c~v~r copp~r, ch~onliulZl~ nick~.l clltalyst (Ni 2717). I~eaction conditions were as follows:

.

~26~6~

TABLE II

Polyol space velocity, g/ml/hr 0.28 Polyol ~ced r~te, lh/ilr 0.75 ~mmonia fced r~)tc, lh/hr n.~n Hy~ro~en feed rate, l/hr 50 The amino alcohol had the followinq properties:

TABLE III
SamPle No. 5663-83 Properties Total acetylatables, meq/g 2.96 Total amine, meq/g 2.77 Primary amine, meq/g 2.72 Water, wt.% 0.04 Color, Pt-Co 25-30 pH 1 2 . 2 Peroxide, ppm 0.25 Viscosity, F, cs The data show the tertiary hydroxyl group to be unreactive in the total acetylatable test. The NMR
spectra showed that no amination had occurred on the tertiary alcohol group.

F.xam ~
Thi.s exumple wLl.l i.L.Ius~rllt~ thQ ~ .enlpte~-l rQtluc-tive aminati.on o~ hexylen~ glyco:l. It ~urther shows the necessity of alkoxylating these type materialsbeEore they can be reducti.vely aminatcd.

~L2~4~

The hexylene gl~col was reductively aminated at 200-23nc in a 12nO ml continuous reactor over a nickel, copper, chromium catalyst (Ni 2717). Reaction condi-tions were as follows:

TABLE IV

Polyol space~ vt~locity, g/ml/hr ].. 36 Polyol feed rate, lb/hr 1.5 Ammonia feed rate, lb/hr 2.2 Hydrogen feed rate, l/hr 25 n An analysis of the product showed that little, if any of the desired reaction had taken place.

Example 4 This example will show the use of the aminopolyols of this invention in the preparation of flex.ible ure-thane foam~ It will further show that higher levels of the products of this invention can b~ incorporated into the ~ormulation as compared to a 400 molecular weight polyoxypropylenediamine. (JEFFAMINE D-400; Texaco Chemical Co.) This rc~1ccts tho l~c~t'luct.~d rc~,lct..J.v:lty ol~
t:hc nmino a'lcollol~lt~ In~l3ll1 ion~ tt l~~lrt~lt-n~r ~ilOW~;
I.hat-. the te:r.~t:i.lry hy~lro:~yl. ol the nmi.llo ;~l.coho:l.s clot3s rcact with the isocyanatc ~t.oup.
~5 Formulat:ions, det~:i.l.s of reacti.oll, and results ~nre shown in ~he fol1owi.ng tahlc:
~ rr~de l~ark ~L2~,~7~ ~

TABIE V

5~395- 5895- 5895- 5895-Foam No. 48B 48C 48D 48E
l~onnul tion, ~,l~f /\Nf~ n1~ nn 1nn lon 1nn ~ l.f~ ~I.f f~llf~l f~~ L,~ - fJ --Polyoxypropylenediamineb - 2 - 5 (40n m.w.) Wat~r 4.0 4.0 4.0 4.0 L-711 SiliconeC 1.0 I.0 1.0 1.0 All~rD-33d o.3 n . 3 o . 3 0 . 3 50% st,~nnous oct~ate 0.5 0.5 0.5 0.5 in dioctyl phtllalate'~
Toluene diisocyanate 5().2 50.6 50.9 52.0 Is~yanate index 1.05 1.05 l.05 1.05 Details Cr~m time, sec. 11 10 9 9 Rise time, sec. 82 82 80 75 Density, pcf 1.46 1.43 1.41 Appearance ~x~3 C~x3 Good Shrunk open slightly slightly badly, foam tight tight discarded '~300() m.w. pr~py]en~? oxide/~t:tlyl~!ne oxicle a~ u~ ol ~llyot~r.irl;
q'~ x,~f~, Cll~
~ rNl~ If--~o,n; I~x~ilt~ n~ f.1~
C,~ pr~xl~lt~t ~ lJrlit~lf~ r~ t~ 'c~.
33~ trit-~tl-yll~ntY~ in(l in prol)yl(lle ~jlycol; f~'exflco ~hemi~ l Co.
'Cataly3t T-lO; MhT ChwTu.cals ~ Tl~e /~

. ..

~L2~;47~
-~,o -It will be noted from Table V that examples 5895-48B and 5895-48D demonstrate the improved results obtainable with the present invention. Thus, when the use of the amino alcohol of Example 1 is compared with a 400 molecular weight polyoxypropylene diamine, it is observed that at an equivalent weight level, a better quality foam is obtained with the product of the pres-ent invention. This demonstrates that higher than normal amounts of the chain extender of the present ln invention may be used with good results in the manufac-ture of polyurethane foam in (lccordance with the present invention.
Ilaving thus dl-scribe~d our invention, what is claimed is:

~5 .

Claims (10)

The embodiments of the invention which an exclusive property or privilege is claimed are defined as follows:

1. A method for preparing a polyoxyalkylene polyether amino alcohol containing a tertiary hydroxyl group which comprises the steps of:
(a) alkoxylating a glycol feedstock under basic alkoxylation conditions with an epoxide to pro-vide a polyoxyalkylene polyether glycol intermediate, and (b) reductively aminating said polyoxyalkyl-ene polyether glycol under reductive amination condi-tions in the presence of a nickel, copper, chromia reductive amination catalyst, ammonia and hydrogen to thereby provide said polyoxyalkylene polyether amino alcohol containing said tertiary hydroxyl group.
(c) said glycol feedstock having the formula:

(d) said epoxide having the formula:

II

(e) said polyoxyalkylene polyether interme-diate having the formula:

III
(f) said polyoxyalkylene polyether amino alcohol having the formula:

IV
(g) wherein, in said formulae, R represents hydrogen or a methyl or an ethyl group, x represents a number having an average value of about 1 to about 4 and n represents a number having an average value of about 1 to about 40.

2. A method as in claim 1 wherein R is methyl, x has a value of about 1 and n has a value of about 6.

3, A method for preparing a flexible polyurethane where-in a hydroxy compound is reacted with an excess of an organic polyisocyanate in the presence of an effective amount of a catalyst, the improvement wherein the hydroxy compound is composed of from about 99.5 to about 95 wt.% of a polyoxypropylene poly-ether polyol and from about 0.5 to about 5 wt.% of a chain extender hav-ing the formula:

IV

wherein R represents hydrogen or a methyl or an ethyl group, x is a number having an average value between about 1 and 4 and n represents a number having an average value between about 1 and about 40.

4. A method as in claim 3 wherein R is methyl, x has a value of about 1 and n has a value of about 6.

5. A method as in claim 3 wherein effective amounts of a blowing agent and a foam stabilizer are included in the formula-tion to thereby provide a flexible polyurethane foam.

6. A method as in claim 5 wherein R is methyl, x has a value of about 1 and n has a value of about 6.

7. A flexible polyurethane foam prepared by reacting a hydroxy compound with an excess of an organic polyisocyanate in the presence of an effective amount of a catalyst, the improvement wherein the hydroxy compound is composed of (a) from about 99.5 to about 95 wt.% of a polyoxy-propylene polyether polyol having a hydroxyl number between about 20 and 60, a functionality of from about 2 to 8 and a molecular weight within the range of about 2,000 to about 8,000, said poly-oxypropylene polyether polyol having been prepared by reacting an initiator having a functionality of about 2 to about 8 with an alkylene oxide component consisting essentially of from about 100 to about 80 wt.% of propylene oxide and, correspondingly, from about 20 to about 0 wt.% of ethylene oxide, and (b) from about 0.5 to about 5 wt.% of said polyoxy-propylene polyether polyol is replaced with a chain extender having the formula:

IV
wherein R represents hydrogen or a methyl or an ethyl group, x is a number having an average value between about 1 and 4 and n represents a number having an average value between about 1 and about 40.

8. A polyurethane as in claim 7 wherein R is methyl, x has a value of 1 and n has a value of about 6.

9. A polyurethane as in claim 7 wherein the formulation also includes effective amounts of a blow-ing agent and a foam stabilizer to thereby provide a flexible polyurethane foam.

10. A polyurethane foam as in claim 9 wherein R
is methyl, x has a value of 1 and n has a value of about 6.