CA1043682A - Polyurethane foam composition and method of making same - Google Patents

Abstract

POLYURETHANE FOAM COMPOSITION
AND METHOD OF MAKING SAME
ABSTRACT OF THE DISCLOSURE
One-shot, flexible polyurethane foams capable of being thermally bonded to various substrates are pro-duced by adding low molecular weight alkylene glycols, glycol ethers, triols, alkanolamine, or polyhydric phenols as modifiers to conventional polyisocyanate foaming mixtures.
S P E C I F I C A T I O N

Description

~0~ Z
BACKGROUND OF THE INVENTION

This invention pertains to flexible poly-urethane foams which can be thermally bonded to sub-strates and more particularly to polyurethane foams formulated from polyisocyanates and polyether polyols.
It i8 known in the art that the urethane link-ages of polyurethane foams are formed by the exothermic reaction of a polyfunctional isocyanate ant a poly-functional active hydrogen-containing compound in the presence of a catalyst and a blow$ng agent. In accord-ance with the "one-shot process" which is the most widely uset industrial technique, direct reaction i8 effected between the polyisocyanate, and the active hydrogen-containing compound or compounds and is regu-lated by the cataly~t system and surfactant.
; It is also well known that ~uitable active hydrogen-containing compounts include polyether polyols and polyester polyols. However, it i8 equally well known that while flexible polyurethane foams formulated from polyester polyols have excellent flame lamination properties, those flexible polyurethane foams formu-lated from polyether polyol~ are unacceptable for flame lamination. Unortunately the polyesters u6ed in this application sre much more expensive than the polyether polyols. This means that fabricators wishing to bond polyurethane foams de~rived from polyether ~ 2.

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polyols must re~ort to the use of an additional com~
ponent, namely, an adhesive in order to bond flexible polyurethane foams derived from polyether polyols The inconvenience and added expense of this procedure is obvious Two previous solutions to this problems have been provided but each introduces proSlems of its own which has left much room for Improvement in this art First of all J C Flanders in ~ S Patent No 3,205,120 10 issued on September 7, 1965 describes the preparation of ~ ;
polyether polyol-based polyurethane foams suitable for f-brication of laminates by a heat sealing technique wherein the conventlonal commercial polyether polyol flexible polyurethane foam reaction mixture contained a minor~amount of a polyol having a lecular weight of 200~to 15~00~ The pr-ferred low lecular weight polyol ~ -~
; ~ ~ was tris(dipropylene~glycol);pho~phite Other low mol-cul-r welght~polyoIs dlsclo~-d by Flander~ include -~
lene oxide~-dduct- of~polyhydroxy alkanes,~phos- ;~
20 ~ phorua-containing acids, and the~like It wàs later Pound that there are proce~ing difficulties encounter-;ed~in~thé~productlon~of the~FIanders polyether poly-urethane~foams that~stem from the high réactivity of~ th-~po:lyè;ther ~
.

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~ 04au~ Z 9S85 polyol mixture. These difficulties at least csncel the cost advan~age of the polyether polyol based foam over polye~ter polyol based foam with the result that there has been no great incentive for laminate manufacturer~
to switch from polyeeter to polyether.
The second improvement described by F. E.
Critchfield and R. D. Whitman in U.S. Patent No.
3,497,416 issued on February 24, 1970 comprises the use, in the production of heat-sealed polyurethane foam laminates, of polyurethane foam which ic produced by reacting, in ~he presence of a foaming agent, a poly-ether polyol with the reaction protuct of an aromatic polyisocyanate and diprcpylene glycol or dibutylene glycol. This reaction product, a qus~i-prepolymer, is pre~ared by u~ing an excess of an aromatic polyisocyanate over the amount of dipropylene glycol and/or dibutylene glycol used. While this disclo8ure con3titutes a further adv~nce in the art, it is ~till not completely satlsfactory for commercisl u~e by laminate manufactu-rers because in order to obtain an open foam one mustincorporate a powerful cell opening agent, such ~s, dimethylform~mide. The use of a cell opener i~ normally not u~ed in polyurethane foam processing. In addition these polyurethane foam~ h~ve very high compression sets which are unacceptable for most end use appli-cation~ ;

10436~Z gs8s SUMMARY OF THE INV~NTION

It ha~ now been found possible to thermally ,' bond a flexlble polyether polyurethane to a substrate without the disadvantag-s of the prior art by a method *hich compri~es (A) Reacting and foamlng compo~itlon con-sisting essentially of `~
(a) polyisocyanate reactant containlng '~ ~ -at l-ast two isocy nato g~oup- per molecul-; -~ -,, ~ (b) at l-a~t oné polyol rea,ctant having ', a molecul-r w ight of t l J~t -bout 2000 and contain- ' ~ , : -ing an~average of at lea~t 2 hydro~yl groups per ', ~ol-cule;~
(o) a~blowlng~Jgent;

M~ e) ~a~ur'facèant;~ an~d -bout one to ,m,',`~ evon~percont,~b ~ d on',the ~ Lg ~ of'pol~ ~her , ~' polyol,~of;-e loast one polyo1~ ~ lfier sel-c~ed~from W ~ t~`,~c ~ ~ con~ of~
g ol~ h~ in 2 to ~ t 8 ;"~"~ bo~ ~ "

2~) ~gl ~ ~-~h-r ` b ~ I ~ t e irlcal ~ ~ .
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lO~UB~ ~ 9585 wherein n i5 an integer having values of 2 to 4 and m is an integer having values 2 to 4 when n is 2, 2 to 3 when n i8 3 ant 2 when n ~9 4;

(3) tr~ 018 having the emplrical formula CxH2x-1(H)3 whereln x i~ an integer having value~ of 3 to about 10;

(4) alkanolamines having the emplrica formula CyH2yNz(OH)p wherein y i9 an integer having values of 2 about 10, and z is an lnteger havlng values of 1 to 2 and p i8 an integer h~vlng 2 to 4; and (S) polyhydric mononuclear phenols;
~ B) Heating the surface of the oamed compo-sitlon of (A) above it~ melting or fu~ion temperature;
(C) Contacting the melted or fused surface o~ the foamed composltion of (A) with a aubstrate, where-by a flexible polyurethane oam/substrate laminate 18 formed; and (D) Cooling the flexlble polyurethane foam/
substrate laminate below the melting or usion point of the flexible polyurethane foam.

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1 ~ 3U~ 2 9585 DESCRIPTION OF THE INVENTION

Although about one to about seven per cent of polyol modifier can be u~ed ln this inventlon, $t 19 preferred to use about t~o to about 8iX per cent bssed on the weight of polyether polyol employed in the foaming composltion Illustrative of the alkylene glycols having 2 to sbout 8 atoms used in this invention are ethylene glycol, 1,2-propylene glycolJ 1,3^propylene glycol, 1,2-butylene glycolj 1,3-butylene glycol~ 1,4-butylene glycol, 1, 2-pentylene glycol~ l,S-pentylene glycol~
1,2-hexylene glycol, 1,4-hexylene glycol, 1, 2-heptylene glycol, l,7-heptylene glycol, 1,2-octylene glycol, and 1,8-octylene glycol and the like Exemplary glycol ethers useful in this in-v ntion include dietbylene glycol, di(l,2-pr~opylene) g~lycolJ d$(1,3-propylene) glycol, triethylene glycol~
:
tetr-ethyl-ne glycol, tri(l,2-propylene) glycol~
trl(l,3-propylene) glycol, and dibutylene glycol Repre~entativ- example5f triols useful in .

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1 0~U58 ~ 9585 this invention include glycerine, 2-methyl-2 hydroxy methyl-1,3-propane diol, 2-ethyl-2-hydroxymethyl 1-1,3-propane diol and the like.
AlkanolamineP whlch can be used include:
diethanolamine, di-n-propanolamine, di-isopropanolamine, tri-n-propanolamine, tri-i~opropanolamine, di-n-buta-anolamine, diisobutanolamine, tri-n-ethanolamine, di-n-pentanolamine, di-isopentanolamine, N,N'-dihydroxy-ethyl ethylene diamine, and the like.
Representative polyhydric mononuclear phenols include catechol, resorcinol, hydroquinone, pyrogallol, hydroxyhydroquinone and phloroglucinol.
The polyisocysnate reactants used in making the flexible polyurethane foams of this invention are known in the art snd any such reActants can be suitably employed in producing the flexible polyurethane foams.
Among such suitable polyisocyanates are those repre-sented by the general formula:
Q -~NC0) wherein i has an average value of at least 2 and is usually no more than 6, and Q represents an aliphatic, cycloaliphatic or aromatic radical which can be an un-substituted hydrocarbyl group or a hydrocarbyl group substituted, for exampl~, with halogen or alkoxy. For ex~ple, Q can be an alkylene, cycloalkylene, arylene, . . .
- - - - -.. - . : . . - - . . .

958s 10436~Z
alkyl-substituted cycloalkylene, alkarylene, or aralky-lene radical incluting corre~ponting halogen-~nd alkoxy-substitutet radical8. Typlcal examples of polyisocysnates which can be uset in prepsring the polyurethanes of thls invention are any of the following incluting mix-tures thereof 1,6-hexamethylene tlisocyanate, 1,4-tetra-methylene dllsocyanate, l-methyl-2,4-dilsocysnatocyclo hexane, bis(4-isocyanato phenyl)methane, phenylene dilsocyanates such as 4-methoxy-1,4-phenylene diiso-cyanate, 4-chloro-1,3-phenylene dllsocyanAte, 4-bromo-1,3-phenylene d$isocyanate, 5,6-timethyl-1,3-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocysnate, crude tolylene dii~ocyanates, 6-iso-propyl-1,3-phenylene diisocyanate, durylene diisocy-an te, triphenylmethane-4,4',4"-triisocyanate, and other organic polyisocyanates known to th~ polyurethane art. Of the aforessid type~ of l~ocyanates. those con-t-ining aromatic nuclel are generally preferred.
Also useful as the polyisocyanate reactants are polymeric lsocyanates having units of the formula:
~CU23~

wherein R i~ hydrogen and/or lower alkyl and 3 has an average value of at lea~t 2.1. Preferably the lower alkyl radical is methyl and 3 has an av-rage value of 8.

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from 2.1 to about 3Ø Psrtlcularly useful polyiso-cyanates of this type are the polyphenylmethylene poly-i~ocysnstes produced by phosgenatlon of the polgamine obt~lned by cit catslyzed condensaelon of aniline with formaldehyde. Polyphenylmethylene l~ocy~nates of this type are available co~,~ercially.
These product6 are low vl~cosity (50-500 centipoi~es at 25C~ liquids having verage isocyanato funct~on-al$ties in the range of ~bout 2.25 to about 3.2 or , higher, depending upon the specific aniline-to-formalde-hyde molar ratio u6et in the polyamine prepsration.
Other useful polyisocyanates ~re combinations .
of diisocyanates with polymeric isocyanates containing more than 2 isocyanate groups per molecule. Illustra-tive of such combin tions re: B mixture of 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate and the afore-said polyphenylmethylene polyisocyanate and/or poly-meric tolylene dii~ocyanates obtained as residues from the manufacture of the diisocyanates.
On a combined basis, the polyether polyol snd organic polyisocyanate usually constitute the ma~or proportlon by weight of the polyurethsne-forming re-~ctlon mixture. In geneiral, the polyisocyanate and polyether polyol r Actant~ are employed ~n rel-tive ~, ' ' .' ' . . ' ' '~
. ~:
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1C~ 2 amounts such that the ratio of total-NC0 equivalents to total ac~ive hydrogen equivalent9(of the polyether polyol and any w~ter, wh2n u~ed~ is from 0.8 to 1.5, preferably from 1 0 to 1.15 e~uivalen~s of -NC0 per equivalent of active hydrogen~ Thls ratio is known as the Isocyanate Index and i~ often al~o expressed as percent of the stotchio~etric a unt of polyi~ocyanate required to react with total active hydrogen. When expres~ed as a percent, the Igocyanate Index may be from 80 to 150, and i~ preferably within the ran8e from ~bout 100 to about 115.
In protucing the flexible polyurethane foams of the present invention, one or more polyether poly-yols is employed for reaction with the polyi~ocyanate reactant to provite the urethane linkage. Such polyols have an average of at least 2 ant usually not more than 6 hydroxyl groups per molecule and include compounds which consist of carbon, hydrogen, and oxygen and com-pounds which also contain phosphorus, halogen and/or nitrogen. Such polyol~ al~o have an average molecular weight of at lea~t about 2000.
Among the suitable polyether polyols that can be employed are ~he poly~oxyalkylene) polyol~, that i9 alkylene oxide adducts o water or a polyhytric organic compound uset as the initiator or starter. Suitable 10.

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~)5~5 polyhydric organic initi~tors include the following ind~vidually or in comblnation Ethylene glycol; di~
ethylene glycol; propylene glycol; 1,5-pentanetiol;
hexylene glycol; dipropylene glycol; trimethylene glycol; 1,2-cyclohexanediol; 3-cyclohexane-1, l-di- ' ~ -methanol; glycerine; l,2,6-hexane trio~; l,l,l-trl-methyolethane; l,l,l-trimethyolpropane; 3-(2-hydroxy ethoxy)-and 3-(2-hydroxypropça~-1,2-propane diols;
2,4-dimethyl-2-(2-hytroxyethoxy) methylpentanediol-l

5; 1 l-trl~ [(2-hydroxyethoxy) methy~ ethane; 1,1,1-tri- C2-hydroxy propoxy) methy ~ propane; pentaory-thrltol; sorbitol; sucro~e; slph~-methyl glucoslde;
. .
and'the llke.
The above-tescribed polyether polyols are preparet in accordance with well known techniques com-prislng the reaction of the polyhydrlc starter ant an alk~ lene oxide in the pre~ence of an oxyslkylation cat-lyst which is ususlly an alkaline metal hydroxlte The oxyalkylatlon of the polyhytric initiator is carri-d out at tempe N ture~ ran8lng rom about 90C
to about 150C ant u~ually at an elevated pressure to about 200 psig, employi~g~a ~ufficient amount of alkylene oxite ant adequate reaction tlme to obtain a polyol of tesired lecolar weight whicb 1~ convenient-- ly followet during tbe cour~o of~the reaction, by ~tantard hytroxyl nu~ber teterminations A~ i~ well ~-., .
known in the art the hytroxyl numbers are tetermined ~ .
11. . , 9s85 10436t~Z

by and are deflned as the number of mllligrams of potassium hydroxide required for the complete neutrali-zatlon of the hydrolygig product of the fully acetyla-ted derivative prepared from one gram of polyol or mixture of polyols. The hydroxyl number i8 also de-fined by the following equation whcih indicates its relationship with the molecular weight snd functi-onality of the polyol:
OH- 56.1 x 1,000 x f .
wherein OH equals hydroxyl number of the polyol, f equals sverage functionality, that is, the average number of hytroxyl group8 per molecule of polyol, and M.W. equals average molecular weight of polyol.
The alk.ylene oxlde usually employed in the polyether polyol reactants are the lower alkylene ox-ides, that is, compound~ having from 2 to 4 carbon toms including ethylene oxide, proW lene oxide, butylene oxides ~1,2' or 2,3') in combination thereof. .:
When more than one type of oxyalkylene unit i8 desired in.the polyol product, the alkylene oxide reactants may be fed to the reaction system sequentially to provide polyoxyalkylene chains containing respective bloc~- of different oxyalkylene units or they may be fed simult~neously to provide substantially random .:
dlstribution of the units. ~lternatively, ;.
12.
:, ~585 ~0~3682 the polyoxyalkylene chains may con~i~t e3sentially of one type of oxyalkylene unit, such as, oxypropylene c~pped with oxyethylene units.
The second class of polyether polyols whlch i9 suitable for use in preparin8 the flexible polyurethsne foams of the pre~ent invention are grat polymer poly-ether polycl~. Such reactants are producet by poly-merizlng one or more ethylenically unsaturated monomers dissolved or disper~et in a polyether polyol in the presence of a free r~ticsl catalyst. Suitable poly-ether polyols for protucing ~uch composition include, for example, any of the ~bove describet polyols.
Illustrative of ~uitable ethylenically unsaturated monomer~ are those encompas6ed by the general formula Rl whereln Rl i~ hydrogen, ~etihyl or any of the halogens (l.e., fluorine, chlorlne, bromine, or iodine); and R2 i8 Rl, cyano, phepyl, m~thyl-substituted methyl, or alkenyl radicals having from 2 to 6 carbon atoms such as vinyl, allyl ant isopropenyL groups. Typical examples of ~uch polymerizable mon~mers are the following which may be employed $ndividually or in combination: ethylene, propylene, acrylonitrile, methacrylonitrile, vlnyl chlorlde, vinylidene :. .
13~

. : . - . .. . . ~ . . . -- ` -1~3Uj~ ~ 9585 chloxite, ~tyrene, ~lph~-m~thyl styrene, ~nd buta-tiene. The~e ~nd other polymer polyol compositions which ~re ouitably employed either lndiv~dually or in combinatfon with polyether polyole d~scr~bed above are those described in Brltish Patent 1,063,222 and U.S. Patent No. 3,383,351. Such compositions . _ . . .. . . . . ... .. ..
are prepared by polymerizing the monomers in the polyol at a temperature between about 40C. and about 150C. employing any free radical-generating initiator including peroxides, per6ulfates, percArbonates, per-borates, or azo compounds, such a~, for example, hy-trogen peroxide,dibenzoyl peroxide, benzoyl hydro-perox$de, lauroyl peroxide, and azobis (isobutyroni-trile).
When u~ed in the pFactice of thi~ ~nvention, the polymer polyol compo~ition usually contains from about 5 to about 50, and more u6ually from about 10 to about 40 weight percent of the ethylenically un-~aturated monomer polymerized ln a polyether polyol.
E~peclally sui~able polymer/polyols are those con-taining:
h) from about 10 to about 30 weight per cent of a copolymer of (1) acrylonitrile or methacryloni-trile, and (2) ~tyrene or ~lpha-methyl styrene, the 14.

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said copolymer cont~ining from abou~ 50 to 75 and from about 50 to 25 weight per cent of (1) and (2~, re-spectively;
(B) from sbout 90 to about 70 weight per cent of the polyether polyol and particularily tri-functi-onal polyol8 such as alkyl~ne oxite ~dducts of glycerine.
The urethane-forming reac~ion i9 effectet in the presence o~ a minor amount of a catslyst com-prising an amine cataly~t ant 8 metal catalyst useful in promoting gelation of the fosming mixture. The amine component of the polyurethane-forming reaction mixture i8 usually a tertiary amine. 8ultable amine catalysts include one or more of the followlng: N-methyl-morpholine; N-ethylmorpholine, N-octotecylmor-pholine; N,N,N'N', tetramethylethylenedi~mine; N,N,N' N', tetramethyl-1,3-butanet~amine; hexadecyldimethylamine;
N,N-timethylbenzylamine; and tha like. The amine cata-lyst may be introduced to the polyurethane-producing reaction mixture as ~uch or a~ a 601ution in a suit-able solvent.
The amine cataly~t i8 pre~ent in ~he inal poly-urethane-protucing renctlon mixture in an smount of ~-fram about 0.05 to about 3 part~ by weight of active catal~st, that i8, the amine (exclusive of other com-ponents present in solutions thereof) per 100 parts --by weight o~ the polyether polyol react-nt.

15.

10~3~B;~

Metal cataly8t8 which ~re also used in con-junction with the amine cataly~t in producing poly-urethAnes from polyether polyol8 include organic deriv-atives of tin, particularly the tin compounds of car-boxylic acids such as stannous octoate, stannous oleate, stannous acetate, stannous laurate, dlbutyl tin dilaurate, ant other such tin salts. Additional metal catalysts are organic derivatives of other polyvalent metals such as zinc and nickel (e.g., nickel acetyl-8cetonate). In general, the amount of such metal co-catalysts which can be pre~ent in the polyurethsne-protucing reaction mixture is within the range from about 0.05 to about 2 psrt~ by weight per 100 parts by weight of the polyether polyol reactant.
Foaming is accGmplished by the presence in the reaction mixture of vsrying amounts of a polyurethane blowing agent, such a8, water which upon reaction with isocyanate generate~ carbon dioxide in situ, or through the u~e of blowing agents which are vaporized by the exothermic reaction, or by a combination of the two methods. These various methots are known in the art.
Thus in addition to or ln place of wster, blowing agents which csn be employet in the presence of this inventlon include methylene chloride, liquified gases which have boiling points below 80F (27C) and above -60F (-52C), or other inert gases such as nitrogen, 16.

10~

carbon dioxide added as such, methaneJ helium and argon Suitable liquifying 8s~es include aliphatic and cyclofluorocarbon8 which vaporize st or below the temperature of the foaming mass. Such gases are at least partially fluorinated ant m~y also be other-wise halogenated. Fluorocarbon blowing agent~ suit-able for use in foaming the formulations of this in-vention include trichloromono~luoromethane, dichloro-difluoromethane, l,l-dichloro-l-flùoroeth~neJ 1,~-1-trifluoro-2-fluoro-3,3-difluoro-4,4,4-trifluoro- ~-butane, hexafluorocyclobutane and octsfluoro- ~-cyclobutane. Another u~eful class of blowing agents include thermally-uw table compounds which liberate ~ ~-. .
gases upon heating, such ~8 N,N'-dimethyl-N,N'-dinitro-Q~oterephthalamide, and the llke. The generally pre-erred method of foamlng for producing flexible foams is the U9- of water or a combinatlon of water plus a fluorocarbon blowlng agent such as trichloromono-fluoromeehane.
The smount o blowing agent employed ln the~foaming reaction will vary with fsctors such -s tensity that is de~ired in the foam product.
Usually, however, fro- about 1 to sbout 30 partY by . .
w ight of the blowing agent per 100 parts by weight -~
of the polyether polyol rea¢tant i8 preferred.
- ::
The polyurethane foam of this invention msy be formed in sccordsnce with any of the processinK

~- 17-10~3682 techniques known to the arts such as ~ in p~rticular, the one-shot technique. In accordance with this method, foamed products are provlded by carrying out the reaction of the polyisocyan~te and polyether poly-ol simultaneously with the foaming operation. It is to be understood that the relative amounts of the various components of the conventional foam formu-lations are not narrowly critic~l. The polyether polyol and polyisocy~n~te are present in the foam-producing formul~tion in a ma~or amoùnt. The relativeamounts of these two components i8 the amount required to produce the urethane structure of the foam and such relatlve amounts re well known in the art.
The source of the blowlng agent such as water, auxill-ary blowlng agents, amin catalyst and metal catalyst of the present inventlon Jre each present in J minor amount necessary to achleve the function of the in-divldual component. Thus the blowing ~8ent is pre-ent Ln an amount sufficient to foam the reaction mixtur-, tho amine cat-ly~t ~nd metal cJtalyst are each presene ln a catalytic amount ~l.e., an ~mount uffict~nt to catalyze th- reaction to produce the .
urethane at a reasona~le rate) and the surfactant is present io a foam~9tabilizingamount. The preferred amounts of these various components are as given herein.
~-.

18.

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1 O~ ~6 ~ Z 9585 Suitable surfactants include a ~oaming sta-bilizer, as for example, a pluronic hydrolyzable poly-siloxane-polyoxyalkylene block copolymer such as block copolymers described in U.S. Patents Nos. 3,834,748 and 2,917,480. Another useful class of emulsifying agents or surfactants is the non-hydrolyzable polysiloxanes or polyoxyalkylene block copolymers such as those described in U.S. Patent No. 3,505,377.
The preferred substrates are polyurethanes, paper, kraft paper, leather, hides, cotton, linen, silk, hemp, jute, wool, flax, nylons, polyesters, Orlon, Dacron, rayon, rayon acetates, styrene polymers, vinyl chloride polymers and the like. The invention is not limited to any substrate and hence includes not only the above-enumerat-ed substrates but also both ferrous and non-ferrous metals, vitreous materials including glass, ceramics, clays, china, porcelain, and the like: cellulosic sub~trates :
including wood, ply-wood, cane, bamboo, rattan, and . .
the like; proteinaceous materials including gelatin, ~ ;
and the like; natural fibers; as well as, building materials, including brick, granite, sandstone, plaster, tile, wall board, cement blocks, and the like; thermo~
setting polymers such as phenol-aldehyde condensation polymers, phenol urea~ resins, epoxy resins, coumarone-indene polymers and the like; and thermoplastic poly-mers such as acrylonitrile polymers, polycarbonates, . , . ., : .... . . . ...... . .: . ~ , ,, . . . . ,... .. ..., ,. ~ , . ...
:, ,: ~ . .

1(~361~3Z
polyacetals, polyamides, synthetic rubber, polyethylene, polypropylene, ~nd the like, The laminated structure~ of the invention can be used for various purposes such 8S insulation or padding of clothing where the substrste would be cloth, the sound desdening and insulation of building materials e.g preformed panels and the like. Blocks of poly-urethane foam can be heat sealed to e~ch other (butt-welded) to form l~rger sections from smaller sections.
10. Single-ply or multi-ply lsmin~tes can be fabrlcated with this invention.
Other uses for the laminates of thi~ invent-ion include the preparation of preformed cushioning ~or furniture, automobile seflts, crash pads and the like.
The laminatel of the invention are produced by heating part or 811 of the surface of the urethane foam described above to a temperature above the fusion tempera~ure of the foam :to form a tacKy liquid or seml-liquid layer, and thereafter or concurrently with the heating operation, applying the substrate to the ~acky surface of the foam and holding in contact ~herewith while cooling until the surface c0019 and resolidifies, thereby forming an adhesive bond between ~he foam and the substrate, The fusion temperature of the foam will vary depending upon the nature snd proport~on o~ the components therein, but in general i8 in the range 20, - . .

~585 ~ 4 3 ~ ~ ~
of from about 204C. to about 315C. It i9 in general desirable not to heat the surface of the foam to a temperature higher than about 38 C~ above the fuYion temperature of the particulsr foam.
Preferred methods include flame treatment of the surface or a heat sealing means with the polyurethane foam passing continuously over the heating source and then p~ssing directly into contact with the desired substrste. Dielectric heating, heating lamps, e.g. in-frared lamps, hot plates, hot air guns and the like canalso be used.
Although not neces~ary, it i8 preferred to employ a moderate amount of pressure in contacting the substrate with the polyurethan- foam whose surface has been brought above its melting or fusion point. The pressure can be a9 low a~ that re~ulting from the weight ~-of the-foam or the sub~trate but i8 preferably in the range of about 0.1 to about 100 or more pounds per square inch.

The invention is further described in the Examples which follow. All parts and perc-ntages are by weight unless otherwi~e specified.
FoaminR Proce,dure I - Bench Scale The general proeedure used for the preparation -of the 1exible polyureth~ne foams used in this invent-ion is a~ follows.
Polyether polyol was dispensed into a con-: : .. . ~ . . . , ~ .
i: .-. -. . . . . . - .
... .: ; .. .. .: ~

10~36~Z

~ainer along with the polyol to be evaluated by stir-ring with ~ spetula until a homogeneous olution was obtained. Optional additives ~uch as flame retardants can be Added at this point if desired to prepare a flame retardant polyurethane fo~m. Surfactant, water, amine catalyst, and fluorocarbon blowing agent were then added to the mixture followed by mixing with a spatula.
The contents of the container were agitated for 15 seconds at 2000 revolutions per minute. ~tan-nous octoate co-catalyst was then added by mean~ of a hypodermic syringe. After agitating for an addi-tional 8 second~, the polyisocyanate reactant was added rapidly and agitation continued for a another 7 seconds. The mixture following agitation was then poured into a parchment lined box (12" x 12" x 12") supported by a wooden mold. The foam was allowed to rest in the mold for at least 3 minutes and then cured for 5 minutes (unless otherwise noted in the examples) at 125C. The foams were then allowed to cure for 24 hours at ambient temperature before evaluation. After cutting, the following properties were determined:
Height of rise Breathebility Density Foam-to-foam bond strength 22.

... , . ~ -104~6~Z :

Burning extent (flame retardant foams only) During foam preparation, cream time, rise time and top collapse are measured.
Breathability denotes the porosity of a foam and is roughly proportional to the number of open cells in a foam. In accordance with the NOPCO test procedure described by R. E. Jones and G. Fesman, "Journal of Cellular Pla~tics," January, 1965 breathability was measured as follows: a 2" x 2" x 1'! piece of foam was 10 cue from near the center of the test ~peciment. U~ing a ~OPCO foam breathability testeri type GP-2Mbdel 40GD10, ,- .;
air was drawn through the one inch~portion at a pressure diff rential of 0.5 inches of water~less than atmos-pheric pressure. The air flow wa~ parallel to the directLon of orlginal foam ri-e~- The degree of openness of the;~foam (or foam breath bility) is measured by air flow and~is expre-set 8 st-ndard cubic fe-t per minute (SCFM)~

Foam density, expressed in pounds per cubic foot, ~(pcf) is the;~we~ght of the fo m divided by its Foam-to-foam bond strength i8 determined by ;bonding two foam samples~cut to a size 1/8 inches by `2~inches~by~six inchés~with Vertrod Mod-l 8HTV Heat Sealing~M~chine. Dwell timei and~temperature was set t -~maximum nd foam ~ample was ~e-led. This pro-cedure was repe-ted ~-ever~al times as not-d by "nwmber of cycl-s" in the Ex~mples, infra. A bond was formed 23.

10~3~8~ 9585 which was 2 inches long by about 1/4 inches wide. The bonded foam sample was allowed to age at ambient condi-t~on9 for ~t least twenty-four hours. Bond strengths were then determined using a T~ble ~odel TM In~tron machine set at a cros~ead speed of two inches per minute and two inches per minute chart speed. The foam samples were held using pneumatic tensile jaws. Bond strengths were repor~ed in pounds per linear inch.
Cream time i8 the time in seconds that the foaming mixture takes to become heterogeneous. This condition was ascertainet by observing the time taken for the clear mixture to change to a milky white color.
Rise time i8 the time in seconds t~ken to achieve maximum height of rise in the foam.
- Top collapse is the amount in inches a foam decreases in height after maximum rise.
Examples 1-6 The enhancement of the thermal bonding properties of a conventional polyurethane foam was demonstra~ed in the following examples by the addi-tion of varying amounts of dipropylene glycol a~ the polyol modifier.
Using the procedure described supra 72 parts of polyether polyol I (the reaction product of glycerine with a mixture of 86% 1,2-propylene oxide and 14Z
ethylene oxide having a ~olecular weight of 3500) was 24.

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blended with 24 parts of polyether polyol II (the product obtained by the interaction of 80~/. of an sdduct polymer obtained by rescting glycerine with 1,2-propylene oxide having a molecular weight of 3000 interpolymerized with sbout 20Jb of a blend of styrene and acrylonitrile) and employed as the polyether polyol components of the urethane foaming composition together with 4 parts of dipropylene glycol as the polyol modifier. Four parts of water 10 was added as blowing agent together with 2 parts of amine catalyst (1) la blend of a ma~or amount of dimethyl~minopropionitrile and a minor amount of bis(2-dimethylaminoethyl) etherl,l part of L-6202 (a commercial ~ilicone-polyether copolymer foam stabilizer available from Union Carbide Corp.), 0.15 parts of stannous octoate, 2 parts of dichlorodifluoro-methane, and 53.5 parts of tolylene diisocyanate (a mixture of 80~ 2,4-tolylene tiisocyanate ant 20% 2,

6-tolylene tiisocyanate) The Isocyanate Index was 20 105 . The Isocyanate Index i8 the per cent of the stolchiometric amount of\polyisocyan-te required to resct with total active hydrogen. This index is preferably in the range of about 100 to about 115. The hydroxyl number of the total polyol blend including 25.

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the dipropylene glycol additive was 79.3. Pertinent phy~ic~l properties of the foam obtalned including foam-to-foam bond strengths are presented in Table I together with 4 additional exAmples and a Control A temon~trat-ing the lmprovement ln foam-to-foam bond ~tren8ths with increasing amounts of dlpropylene glycol motifier and the extremely low bond ~trength in the Control A in which no dipropylene glycol motifier was used. The data in Table I also 8how that based on settling and breathability data fo~ms are more dlfficult to mske, that is, the 8tannou8 octoate operating lstitude is di-minished a8 the dipropylene glycol motifier concentra-tion is increaset. This demon~trate~ that the amount of low molecular polyol motifier used ln this inventlon has a criticsl upper llmit ~8 defined supra. The~e tata pre~enting bond-to-bond strengthh values al80 establish thst the lower limit is critical as well.

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A ~ 2 7 ~:~ 5856 As the concentration of dipropylene glycol modifier is increased in these Examples, the hydroxyl number of the total polyol blend increases along with the bond-to-bond strength8. ControIs B-I show that mere ad~ustment of the hydroxyl number of the poly-ether polyol component will not give re8ults equiv-alent to the compo8itions containing,low lecular weight polyols a8 well. This i8 de n8trated in Table II where urethane foaming Control compositions comparable to those in Examples 1 to 4 were prepared and foamed with the exception that no dipropylene glycol modifier wa8 pre8ent. Polyether Polyol I
was uset a8 the polyether polyol component together with the series Polyether Polyol III, IV, V and VI.
These latter polyols are all reaction products of glycerine and propylene oxide having average molecu- , ,' lar welght of 3000, 2240, 1500 and 700 respectively.
A comparison of Table8 I ant II demonstrate clearly : ,:
~ that whereas Example 1, having an ad~u8ted hydroxyl '~
;~ 20 number of 79.3, gave excelLent f'oam to foam bond strengths the Controls D and G u8ing Polyether Polyol IV with ~, an ad~u8ted hydroxyl number of 75.3 gave markedly ~ -inerlor bond-to-bond 8trengths. Thu8, a blend of ::
conventional polyether polyol8 with a low molecular x~
weight polyol modifier 8uoh a8 dipropylene glycol ~ ' i8 surpri~ingly and unexpectedly unique in improving bond-to-bond strength8 of thermally bonded 28.

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polyuretllane foams. Thi~ unexpected finding is al80 ~:
corrobor~ted in Table II where it can be ~een that the Control H which u~ed Polyether Polyol V having an hydroxyl nunber of 112 ant an average molecular weight of 2240 afforded 8 polyurethane bond with a very low bond-to-bond strength further supporting the conclus-ion that molecular weight variations of a ba~e polyol are not the controlllng key to obtalning polyurethane foams with high bond-to-bond strength.

Exa-p1e~ 5-lO
A comparison of ethylene glycol with , : .
d1ethylene glycol as the polyo1 modifIer of thl~
invention i8 shown in Table III. In these exampleo the base polyether polyol choJen was Polyether .. . . .
~ Polyol II demonstratlng the use of~a graft polymer " .. , . . ~ ~
~; polyo1. All of~th- ex- p1e- how satlsfactory to excellent~foam-to foam bond~trëngth~.
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Ex-~D1e~ 11-14 - Example8 11-14 show the effectlvene~s of 20; ;~dLpro~ lene~ glycol -- the polyo1 motLfler of poly-; ; ureth-ne foam co~mpo~itlon in bu11tlng foam-to-fo~m bond ~trength~ A comparlson with controls J and~K ln whi¢h no~dlpropylene glycol was~used demon~trates the effectlvenes~ of this sL~p1e polyol dlfier in ~ proving foam-to-foam bond trength as demon~tra~et Ln T-ble IV. The~e data . ' '~

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Example 15 The superiority in foam-to-foam bond strength of a polyurethane foam farmulated from a composition containing the polyol modifier, dlpropylene glycol, over that of Control L contain-ing an organic polyisocyanate reaotion product of an excess of an aromatic polylsocyanate with a ., . ~ .
tLol, designated a Prepolymer I80cyanate, was deDonstrated. Control L was carried out with a Prepolymer l80cyanate prepared by reacting 9,8 grams of tipropylene glycol with lO0 part8 of the isomeric .. ,. . i: ~ ~
mixture of 2,4 and 2,6 tolylene diisocyanate (an -., :
exc~e~s) as disclo8ed in U.S. 3,497,416. The form~
ulatlons and the physical properties Sncluting foam-to-foam-bond 8trength~ ofExample 15 and Control L
are shown in Table V. At both three cycles and four cycles the foam-to-foam bond ~trength, of Example lS, i~ de~onstrated to be superior to Con-trol L.

Examples 16 18 The practical upper l~mit of molecular 32.

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Polyether Polyol II 95 100 D propylene glycol (part8) 5 --Water (parts) 3.0 3.0 Amine Cat~lyst(l) (parts) 0.15 0,30 Stannous Octoate (parts) 0.15 0.10 Silicone surfactant (part8) l.0 ~0.5 TDI 80/20 (parts) 42.1 17.1 Pr-polymer Isocyanate (part~ 30,25 .. ..
Cream Time (sec.) 12 12 . ,":: :
Rise Time (sec.) 113 187 ~;
~; H-~ight~of Rise (in.) 5.4 4.7 Bre~tk~bility (SCFM~ i.5 1.10 Den~ity (pcf) 1.95 2.26 ~Fo~m-To-Foam Bond Strength~ -~(lbs./inch) 3 c~cles 3 40 2.4 -~-4~cyclos ; 3,25 ~ 2.0 (l) Blend of a m~or a nt of N,N-dimethylethanol-amlne and a minor amount of bi8(2-dimethyl-amino~th~yl) ethor 34, .

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weight of the polyol modifier8 wa8 temon8trated by comparing the foam-to-foam bond otrength8 of poly-urethane foamo formulated from compooition8 ba8ed on Polyol I and a 8eries of polyethylene glyco10 and polypropylene glycolo of increasing molecular weights (~verage of mixtures), tetraethylene glycol, and propylene glycol. Ao can be 8een from Table VI, while satisfactory fosm-to-foam bond 8trengths are obtainet with polyether glycol~ out8ite the ocope of thi8 1nventlon one muot~u~e incroa-ingly higher and -higher amount8 in the formulation to aohieve e~uiv-alent bond 8trength8. Th10 make~ thém oommercially .
unacceptable.

Example8 19-25 The~r quire~:ment for a~polyol a8~modifier rather~th-n -~monohydric~a100hol wa8~denon~trated by ;~
ing~ever-l ExAmple~oontainlng~the~mo~dlfier8 diethylene glycol, -thylene~glycol, gI~ erine, re80rcino1~0r~triétha l -1n~ agai t Control8 wh-re 20~ but-nol,~-nd~propanol;were u8et a8~additiveo. A~
can bé~oéén from the~d-t-~in Table~VII, th- foam-to-foam bond ~trength~of f ~ latlon8 u8~1ng polyol modi- ~
fiers~wlth-~Polyo1 1~were~good but the fornulation --of mon ~ ic~alcohol8~and~the~Po~lyol I 8howed very Low fo ~-to-foam;bond ~tr ngth~ and were therefore un cc-ptable.

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Examples 26-32 FOAMING PROCEDURE II - MACHINE SCALE
A series of comparative machine scale flexi-ble polyurethane foams was prepared at a through-put rate of about 70-80 pound~ per minute. The foams were all prepared as follows:
Blends of conventional polyurethane foaming compositions were mixed with the polyol modifiers to be evaluated by weighing the proper amounts into a fifty gallon drum and tumbling several hours to effect mixing. The mixture was referred to as the polyol stream. A con-stant stream of polyol blend (21,000-22,000 grams per minute) along with an activator stream consisting of water, amine catalyst and silicone surfactant (800-1000 grams per minute), a separate stream consisting of additional silicone surfactant (150-300 grams per minute), a separate stream of auxillary blowing agent (trichlorofluoromethane;300-500 grams per minute) and a ~eparate stream of tolylene diisocyanate (10,000-11,000 grams per minute) was introduced to a hybrid foam machine under low foam pressure conditions. To prepare flame retardant foam8~ NLAX Flame Retardant 3CF, tris(2-chloroethyl) phosphate, was added via a separate stream (1300-1500 gra~ per minut2~ or a blend 38.

1043Uj8Z 9585 of QYNV-l vinyl resin (polyvinyl chloride dispersion re~in sold by ~nion Carbide Corp.) and antimony oxide was added via the polyol stream.
The mixer speed was 500~ RPM, discharge nozzle 1 inch in diameterJ conveyer angle 3.5 degrees and conveyer speed between 8 and 12 feet per minute.
At ambient temperatures, the emerg~ng foam mixture was poured onto a continuously moving conveyer belt. The foam was allowed to set ant cure in the form of ten foot long 26 inch wide, 18 inch high slabs. After twenty-four hours of aglng at am-bient temperature, the foams were cut and physical pro-perties determined. The re~ult~ along with other phy-sical propertles are reported in part in Table VIII.
The results in Table IX show excellent foam physical propertles are obtalned using either diethy-.
len glycol or dipropylene glycol as the modlfier poly-ol. The control T foam exhibits poor humid sge com-pres-ion sets. Numid age compression sets of foams made according to the present invention have good com-pr-ssion qets before and after humid aglng.
Bond strength values in all of the examples except Example 27 were superior to ehe control T.
Based~ on the totality of all of the work in this rea including both hand mixed and machine mixed foams the bond strength values of Example 27 are anomalous.

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Foams prepared in Examples 26-32 were test-ed for flame lamination properties according to the following procedure. Foam samples were cut into 1/2 inch thicknesse~ and passed into a laminator. The sub-strate used wa~ a cloth-backed vinyl automotive up-holstery material previously marketed by Union Carbide as T-9012. The wid~h of the half-inch foam and T-9012 Yinyl/cloth substrate was 36 inches. The laminating flame consisted of propane gas and air in a ratio of 58:400, The foam wa~ pa sed over the flame at a given speed and pressed to the substrate with nip rollers set 0.4 inches apart. Foam thickness after la~ination was measured and substracted from the original thick-neGs to determine the amount of foam burned off. Bond strengths were determined by tearing the laminates (cut 1" x 6") using an Instron machine as described pre-viously. Bond strengths were determined at different times after la~ination to determine the rate at-which they build. Speed of lamination was varied to make the test more critical. During each test a polyester poly-ol polyurethane foam of 1.8 pcf density prepared on a commercial machine was used as a control. During Instron te~ting ~t was recorded whether or not the bond between the foam ant the substrate W89 separating , 42, .. . . . .

la436~z (referred to as bond tear) or whether the fo~m W89 tearing (referred to as foam tear). It is well known in the art, that once the strength of the foam/~ub-strate bond exceeds A certain value, the foam will tea~. At this point, lt i~ impo~sible to determine the foam/substrate bond value. It i8 also well known in the art that samples that give foam tear are of excel-lent quality.
The foam physical properties and heat 8e81-ing results are presented in Table IX. The flame lami-nation resultQ are presented in Table X.
It may be concluded from these lAst data that:
1. Flame lamination properties of the compo-sitions used in the instant invention are excellent by commercial standard~. Thi~ can be de~on~trated by bond strength resul~s as well 88 ,the number of ExAmples glving foam tear.
2. The Control U polyester polyol polyurethane foam bond strength valu-s are higher than those in the Examples due to higher tensile/elongation values of the foam. This is well known in the art and does not de-tract from the excellent re~ults of the polyether poly-ol polyurethane foams in the Examples.
3. Humid aging dsta demonstratos foams pre-pared accordlng to this invention are superior to poly-ester fo~m (~ontrol U) as can be seen from the fact 43.

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104;~6~2 that the latter totally degraded after three 5-hour humid aging cycles resulting in zero bond strength, 4. Control T laminates took longer to de-velop bond strength than foam laminstes of the present invention. This was determined qualitatively immedi-ately after lamination by pulling samples apart. This constitutes a serious commercisl disatvantage for foams made according to the compos~tion of Control T.
ExamPles 33-38 When Examples 26-32 are repeated with the exception that the cloth-b-ck vinyl automotive up-holstery nsterial i8 replaced by paper, nylon, cotton, leather, rayon acetate, or polyvinyl chloride sheet, respectively, comparable bond strengths are obtained between these substrates and polyurethane foam.
.
Although the invention has been descrlbed in its~preferred forms with a certain tegree of partl-cularity, it is understood that the~present tisclosure of the preferred forms has been made only by way of examp~le and that numberous changes may be resorted to .: .
without departing from the spirit and ~cope of the ~ -invention.

- 48.

' ' .
~ .,

Claims (14)

WHAT IS CLAIMED IS:

1. Method of thermally bonding flexible polyether polyurethane foam to a substrate which comprises:
(A) reacting and foaming a composition consisting essentially of:
(a) a polyisocyanate reactant containing at least two isocyanate groups per molecule;
(b) at least one polyether polyol re-actant having a molecular weight of at least about 2000 and containing an average of at least two hydroxyl groups per molecule;
(c) a blowing agent;
(d) a catalyst;
(e) a surfactant; and (f) about 1 to about 7%, based on the weight of polyether glycol, of at least one polyol modifier selected from the class consisting of:
(1) alkylene glycols having 2 to about 8 carbon atoms;
(2) glycol ethers having the empirical formula:
wherein n is an integer having values of 2 to 4 and m is an integer having values of 2 to 4 when n is 2, 2 to 3 when n is 3 and 2 when n is 4;

49.

(3) triols having the empirical formula;
CxH2x-1(OH)3 wherein x is an integer having values of 3 to about 10;
(4) alkanolamines having the empirical formula:
CyH2yNz(OH)p wherein y is an integer having values of 2 to about 10, z is an integer having values of 1 to 2 and p is an integer having values of 2 to 4; and (5) polyhydric mononuclear phenols;
(B) Heating the surface of the foamed composition of (A) above its melting or fusion point;
(C) Contacting the melted or fused surface of the foamed composition of (A) with a substrate whereby a flexible polyurethane foam/substrate laminate is formed; and (D) Cooling the flexible polyurethane foam/
substrate laminate below the melting or fusion point of the flexible polyurethane foam.

2. Method claimed in claim 1 wherein the temperature of the melted or fused surface of the flexible polyurethane foam is about 204°C to about 315°C.

50.

3. Method claimed in claim 1 wherein the flexible polyurethane foam surface is melted or fused by passing over a flame at a constant rate of speed.

4. Method claimed in claim 1 wherein the flexible polyurethane foam surface is melted or fused by contact with a heat sealing means.

5. Method claimed in claim 1 wherein the substrate is maintained at ambient temperatures when contacted with the melted or fused surface of the flexible polyurethane foam.

6. Method claimed in claim 1 wherein the polyether polyol is an adduct of glycerine and a mixture of 1,2- propylene oxide ant ethylene oxide.

7. Method claimed in claim 1 wherein the polyether polyol is a graft copolymer of styrene and acryloni-trile onto a glycerine-propylene oxide adduct polymer backbone.

8. Method claimed in claim 1 wherein the polyol modifier (f) is ethylene glycol.

9. Method claimed in claim 1 wherein the polyol modifier (f) is 1,2-propylene glycol.

10. Method claimed in claim 1 wherein the polyol modifier (f) is diethylene glycol.

51.

11. Method claimed in claim 1 wherein the polyol (f) is di(1,2-propylene)glycol.

12. Method claimed in claim 1 wherein the polyol (f) is glycerine.

13. Method claimed in claim 1 wherein the polyol (f) is triethanolamine.

14. Method claimed in claim 1 wherein the polyol (f) is resorcinol.