AU605860B2 - Flexible polyurea or polyurea-polyurethane foams prepared from high equivalent weight amine-terminated compounds and process for preparing the same - Google Patents

Description

i AU-AI-15485/88 PCT WORLD INTELLECTUAL PROPERTY ORGANIZATION INTERNATIONAL APPLICATION PUBL E~ NI T PA TUOPERATION TREATY (PCT) (51) International Patent Classification 4 (11) International Publication Number: WO 88/ 08009 C08G 18/14, 18/48, 18/32 Al (43) International Publication Date: 20 October 1988 (20.10.88) (21) International Application Number: PCT/US88/00935 (74) Agent: DAMOCLES, Nemia, The Dow Chemical Company, P.O. Box 1967, Midland, MI 48641-1967 (22) International Filing Date: 24 March 1988 (24.03.88) (US).

(31) Priority Application Number: 035,681 (81) Designated States: AU, BR, DK, JP, KR, NO.

(32) Priority Date: 7 April 1987 (07.04.87) Published (33) Priority Country: US With international search report.

(71) Applicant: THE DOW CHEMICAL COMPANY [US/ US]; 2030 Dow Center Abbott Road, Midland, MI 48640 (US).

A.O.J.p. g DEC WK (72) Inventors: PRIESTER, Ralph, Jr. 108 Daffodil, Lake Jackson, TX 77566 HERRINGTON, Ronald, M. Route 5, Box 5509, Brazoria, TX 77422 PEFFLEY, Richard, D. 108 Spanish Moss, Lake Jackson, TX 77566

AUSTRALIAN

4 NOV 1988 PATENT OFFI F (54)Title: FLEXIBLE POLYUREA OR POLYUREA-POLYURETHANE FOAMS PREPARED FROM HIGH EQUIVALENT WEIGHT AMINE-TERMINATED COMPOUNDS AND PROCESS FOR PREPARING THE SAME (57) Abstract Flexible polyurethane foams are prepared by reacting a polyisocyanate with certain amine-terminated compounds.

The amine-terminated compounds are characterized in having at least 30 percent of their active hydrogen-containing groups in the form of primary aromatic, Lewis acid-blocked primary aliphatic and/or secondary aromatic or aliphatic amine groups. The resulting foams exhibit excellent physical properties, even in the absence of a cross-linker compound.

1 Ic -ci 'WO 88/08009 PCT/US88/00935 -1- FLEXIBLE POLYUREA OR POLYUREA-POLYURETHANE FOAMS PREPARED FROM HIGH EQUIVALENT WEIGHT AMINE-TERMINATED COMPOUNDS AND PROCESS FOR PREPARING THE SAME This invention relates to flexible foams prepared in the reaction of a polyisocyanate and a high equivalent weight compound having a plurality of active hydrogen-containing groups.

Flexible polyurethane foams have been in commercial use for many years. Their most common uses are in cushioning, as in furniture and automobiles, bedding, carpet underlayment, and other padding or cushioning applications.

Flexible polyurethane foams have been conventionally prepared by reacting components comprising a high equivalent weight polyol, a polyisocyanate and a blowing agent. Several methods of reacting these have been used. In one method, the high equivalent weigh: polyol is reacted with a stoichiometric excess of the polyisocyanate to form a prepolymer which is then reacted with water and optionally other polyols and blowing agents to form the foam. In another method, the polyol is mixed with the blowing agent and all the r WO 88/08009 PCT/US88/00935 i S-2other components except the polyisocyanate to form a "B-side" composition which is then reacted with the polyisocyanate to form the foam.

In recent years it has become desirable to form higher load-bearing foam, particularly for seating materials. Several approaches to producing higher load-bearing foams have been used. One approach involves the use of cross-linkers, low equivalent weight highly reactive polyols or polyamines. Using this method, higher load-bearing foams can be prepared.

Unfortunately, the use of the cross-linkers tends to upset the balance between the so-called blowing and gelling reactions which occur as the foam is produced.

In order to get an open-celled foam having good physical properties, it is necessary that the reaction of the polyol with the isocyanate and the generation of gases by the blowing agent be properly sequenced. If 2 the foam gels too quickly the foam will shrink after cooling. If the foam gels too slowly, large, uneven cells are formed, or worse, the gases produced by the blowing agent escape altogether, producing an "air bag". For this reason, the use of cross-linkers has proved difficult in commercial practice. In addition, the cross-linkers add significantly to the cost of the foam, as not only is the cost of the cross-linker added, but additional polyisocyanate must be used to compensate for the presence of the cross-linker.

Accordingly, it would be desirable to use a minimal level of cross-linxer in preparing flexible foams.

Another approach is to use microdispersions of polymeric filler materials. These so-called "polymer polyols" and "polymer isocyanates" provide reinforcement through the presence of colloidally sized Pol.mer

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'WO 88/08009 PCT/US88/00935 particles which are dispersed in either or both of the polyol and the polyisocyanate. A wide variety of polymer particles have been dispersed in polyols and polyisocyanates in this manner, including vinyl polymers such as styrene-acrylonitrile (SAN) copolymers, polyisocyanate polyaddition (PIPA) polymers, polyurea particles, and more recently, epoxy particles.

Several problems remain with the use of these polymer dispersions. Although they do provide improved load-bearing, as well as aiding in cell opening, it is desirable in some cases to increase the load-bearing even further. In addition, they are somewhat more difficult to handle, transport and process due to a tendency of the dispersed particles to agglomerate and settle out of the continuous phase. The polymer polyols and polymer isocyanates are expensive relative to the polyols and polyisocyanates themselves. Moreover.

even with the use of these dispersions, it is usually required to use a cross-linker as well, further adding to the cost of the foam. Additionally, the problem of shrinkage of molded foams made from polymer dispersions in applications in which crushing is impossible is a further disadvantage.

A further consideration is the oreparation of low density foams by the use of increasing amounts of water in the foam formulation. Foams are conventionally prepared using from 2i parts of water per parts by weight polyol to provide a cellular structure.

Recently, lower density foams using up to 4.6 parts water have been made. Until now, these high water foams have been difficult to make and process. The water has tended to react much more quickly than the I WO 88/08009 PCT/US88/00935 I'i -4i polyol, causing premature blowing and collapse of the foam.

It would be desirable to provide a flexible foam which has good load-bearing, in which the use of cross-linkers and polymer dispersions can be minimized or even eliminated, and which can, if desired, be prepared at a low density using high amounts of water in Sthe formulation.

In one aspect, this invention is an open-celled Sflexible polyurea or polyurea-polyurethane foam having a density of 6 pounds per cubic foot (100 kilogram per cubic meter) or less, which is the reaction product of a reaction mixture comprising a relatively high equivalent weight compound or mixture thereof having an average of 1.5 to 4 active hydrogen-containing groups per molecule, of which active hydrogen-containing groups at least 30 percent are primary aromatic.

Lewis acid-blocked primary aliphatic and/or 0 secondary aliphatic or aromatic amine groups, a blowing agent, in amount sufficient to provide a cellular structure to the foam, less than 5 parts by weight of a cross- -linker or chain extender oer 100 parts of component and a polyisocyanate.

In another aspect, this invention is a process for preparing a polyurethane foam, comprising reacting a reaction mixture as described herein in a one-steo I SWO 88/08009 PCT/US88/00935 process under conditions such that a flexible polyurea or polyurea-polyurzthane foam is obtained.

In yet another aspect, this invention is an improvement in a process for preparing an open-celled flexible polymer foam by reacting components comprising a relatively high equivalent weight compound having a plurality of active hydrogen-containing groups, less than 5 parts by weight of a cross-linker or chain extender per 100 parts of component and a polyisocyanate in the presence of a sufficient amount of a blowing agent to provide the foam with a density of six pounds per cubic foot or less (100 kg/m 3 the imorovement comprising using as the relatively high equivalent weight compound a relatively high equivalent weight compound or mixture thereof having from 1.5 to 4 active hydrogen-containing groups per molecule, of which groups at least 30 percent are primary aromatic, Lewis acid-blocked primary aliphatic and/or secondary aromatic or aliphatic amine groups.

In still another aspect, this invention is an active hydrogen-containing comoosition comprising a relatively high equivalent weight compound or mixture thereof having an average of from 1.5 to active hydrogen-containing groups per molecule, of which active hydrogen-containing groups, at least 30 -ercent are primary aromatic.

Lewis acid-blocked primary aliphatic and.cr secondary aliphatic or aromatic amine groups, from 3.5 to 10 parts by weight of water per 100 parts by weight of component and

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JWO 88/08009 PCT/US88/00935 i; j -6- S(C) from 0.1 to 4.5 parts by weight of a cross-linker or chain extender per 100 parts by weight component The use of a relatively high equivalent weight compound containing at least 30 percent primary aromatic, Lewis acid-blocked primary aliphatic and/or secondary aromatic or aliphatic amine groups (hereinafter "amine-terminated compound) has been found to provide several unexpected benefits. The foams have particularly good load-bearing properties, even in the absence of a cross-linker. When a cross-linker is used, the foam of this invention generally has better load-bearing than an otherwise similar foam which is prepared using only hydroxyl-terminated high equivalent weight compounds. The foam of this invention typically has load-bearing characteristics which approach or even exceed those of foams made from a polymer dispersion.

7' at a similar level of cross-linker use. In addition, the foam of this invention is open-celled and often exhibits low shrinkage, which enables it to be used to make parts containing internal wires or other structures which prevent post foaming crushing. The foam formulation used in this invention further has excel- Slent ability to flow and fill a complex mold. It has also been found that this invention in some instances permits the manufacture of foam using much hLiner amounts of water than was commercially possible using 4O 0conventional orocesses.

In this invention, an amine-terminated compound is used to prepare a flexible polyurea or polyurea- -polyurethane foam. An amine-terminated compound, as that term is emploved in this invention, means a relatively hign equivalent weight compound or :olyer. cr i- -s WO 88/08009 PCT/US88/00935 -7mixture of such compounds or polymers, which has a plurality of active hydrogen-containing groups, of which at least 30 percent are primary aromatic, Lewis acid-blocked primary aliphatic and/or secondary alichatic or aromatic amine groups. The equivalent weight of the amine-terminated compound used herein depends somewhat on the particular type of foam being manufactured, but is advantageously from 400 to 5000 .and preferably from 500 to 2500. The amine-terminated compound or mixture thereof has an average of from to 4, preferably from 8 to 3, active hydrogen- -containing groups per molecule.

The amine-terminated compound Can be of any convenient structure as long as it conta is no substituents which undesirably interfere with i:s ability to react with the polyisocyanate to form a poliurea or polyurea-poiyurethane foam. Especially suitable amineterminated comounds are olyethers or polyesters having a plurality of active hydrogen-containing groups of which at least 30 percent are primary aroma:ic, Lewis acid-blocked primary aliphatic and/or secondary aliphatic or aromatic amine groups.

Suitable secondary aliphatic amine-terminated compounds include polyols, especially poliether and polyester polyols which have been modified to contain a proportion of secondary amine groups of from 30 :o 100 percent, preferably from 50 to '00 percent, more preferably from 63 to 90 percent. Such secondary aliohatic amine-termin-ted compounds are conveniently prepared by reacting the corresponding polyol with a primary amine, and reducing tne resulting intermediate with hydrogen, as describec in U.S. Patent 4.!53.381.

The crimary amine is advanzageously an inertlyr i i. 4 1 I -YI WO 88/08009 PCT/US88/00935 -8- -substituted alkyl-, cycloalkyl- or benzylamine.

Alternatively, secondary aliphatic amine-terminated compounds can be prepared in a Michael addition reaction of the corresponding primary aliphatic amine with an ethylenically unsaturated compound. Acrylonitrile is an especially suitable ethylenically unsaturated compound, although any compound which undergoes a Michael addition reaction with the primary amine to form a secondary amine, and which does not contain a substituent group which adversely interferes with the ability of the resultant product to react with a poly- 1 isocyanate, can be used. The primary aliphatic amine itself can be prepared in the reductive amination of the corresponding polyol with ammonia, as taught. for example, in U.S. Patents 3,128,311; 3,152;998; 3,654,370; 3,347,926; and 4,014,933.

Suitable aromatic amine-terminated compounds 2; include polyols, especially polyether and polyester polyols, which have been modified to contain a proportion of aromatic amine groups. Such compounde can be prepared, for example, by capping the corresponding polyether or polyester polyol with a diisocyanate to form a prepolymer, and then reacting the prepolymer Swith water to hydrolyze the free isocyanate groups to the corresponding primary amine. These types are less preferred due to their relatively high viscosity, whic.

makes their processing more difficult. Alternatively.

such compounds can be prepared by reacting =he corresponding polyether or polyester polyol witn a halogenated nitrobenzene compound such as o- or p-nitrochlorobenzene, or dinitrochlorobenzene, followed by the reduction of the nitro group(s) to the amine.

WO 88/08009 PCT/US88/00935 -9- Preferably, the products are produced by the catalytic hydrogenation method. For typical methods see "Catalytic Hydrogenation over Platinum Metals" by Paul N. Rylander, 1967, Academic Press, New York, N.Y.

Any of the catalysts known to be useful for the reduction of aromatic nitro groups can be employed inclusive of Raney nickel. A preferred group of catalysts is 1 comprised of the platinum group metals which includes ruthenium, rhodium, palladium, osmium, iridium, and platinum. Preferably, the catalyst is supported on a carrier such as activated carbon, silica gel, alumina, 1 diatomaceous earth, pumice, and the like. The exact proportions in which the elemental metal is present on the carrier is not a critical factor. Generally speaking, the metal can vary from 0.05 to 40 percent by weight, preferably from 0.5 to 20, and, most preferably, from 5 to 10 percent by weight.

5 The proportions of catalyst employed expressed as the pure metal in respect of the nitro group to be reduced will advantageously fall within the range of from 0.05 to 10 mole percent of metal per equivalent of nitro group. Preferably, the range is from 0.1 to mole percent. The term "equivalent of nitro group" Smeans the nitro equivalent weight which is obtained by dividing the molecular weight of the nitroaromatic compound (II) by the number of nitro groups per mole.

The hydrogenation is conducted in the licuid ohase in the presence cf the hydrogen and the ca als y component which, generally speaking, calls for the use of a solvent but the latter is not absolutely necessary. Any solvent known to be useful for catalytic hydrogenation methods but inert to the compounds and (II) may be employed. Illustratively. the follow- L_ e 1 4 -1 WO 88/0800 PCT/US88/00935 ing solvents can be used solely or as mixtures thereof: aromatic hydrocarbons such as benzene, toluene and xylene; alcohols such as methanol, ethanol, propanol and isopropanol; esters such as ethyl acetate, ethyl propionate and ethyl butyrate; ethers such as dioxane and tetrahydrofuran; and water, either alone or in combination with the above solvents. The use of liquid ammonia is also contemplated. The amount of solvent is not critical perse and any amount found to be efficacious can be employed. Advantageously, the nitroaromatic compound (II) is employed in at least percent by weight in the solvent, preferably, from to 70 percent by weight, and most preferably, from to 50 percent by weight.

The exact choice of temperature in any given hydrogenation is a function of, for example, the specific catalyst activity and hydrogen pressure.

SAdvantageously, it can fall within a range of from 0 0

C

to 2000C, preferably from 15°C to 100°C, most preferably from 20°C to 500C.

Similarly, as with temperature noted above, the hydrogen pressure employed can cover any effective range such as from 15 psig (100 kPa gauge) up to any reasonable working pressure. Generally speaking, the pressure will be from 15 psig (100 kPa gauge) -o 200 psig (1400 kPa gauge), preferably from 30 (10C0 to psig (300 kPa gauge).

Progression of the reduction is readi_7 followed by monitoring the hydrogen uptake. Accordingly, the reduction is terminated at the point at which the theoretical quantity of hydrogen has seen aosorbed.

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nlrac;-~EioEls*l-~- l~u3 rrl,-l- L WO 88/08009 PCT/US88/00935 'WVO 88/08009 PCT/US88/00935 -11- Alternatively, the reduction is continued until no further hydrogen can be consumed.

In another suitable process, the corresponding hydroxyl- or primary amine-terminated polyether or polyester can be reacted with a material such as nitroanisole or a lower alkyl ester of p-aminobenzoic acid, particularly the methyl ester, followed by reduction of the nitro group, to generate an aromatic amine-terminated compound.

Secondary amine-terminated compounds can be prepared ii a Michael reaction of the corresponding primary aromatic amine compound and an ethylenically unsaturated compound such as acrylonitrile as described before. Aromatic amine terminated compounds, either primary or secondary amine-terminated, advantageously contain a proportion of primary and/or secondary amine groups from 30 to 100, preferably from 50 to 100, more preferably from 70 to 100 percent of the total number of active hydrogen-containing groups supplied by the relatively high equivalent weight compound.

Blocked primary aliphatic amine compounds which arc suitable herein are advantageously prepared in the reductive amination of the corresponding hydroxyl-terminaced compound with ammonia, followed by the complexation thereof with a Lewis acid such as benzoyl Chloride, carbon dioxide and a metal carboxylate such as a tin, zinc. titanium or aluminum carooxylate. The Lew.s acid is advantageously used in amounts of from 0.2 :o preferably 0.9 to 1.5, equivalents per equivalent of primary amine groups.

I WO 88/08009 PCT/US88/00935 ii -12- With any of the foregoing amine-terminated compounds, mixtures thereof with a polyol of suitable equivalent weight are also useful, as long as the proportion of amine groups is within the ranges indicted before, at least 30 percent of the total amount Sof active hydrogen-containing groups contributed by the Srelatively high equivalent weight compounds. Of particular interest are mixtures of the amine-terminated compound with a polymer polyol such as a polyurea polyol dispersion (PHD polyol), a polyaddition polyisocyanate polyol dispersion (PIPA polyol), or an addition Spolymer dispersion such as a styrene-acrylonitrile copolymer polyol, containing up to 50 percent by weight of the polymer polyol based on the weight of the relatively high equivalent weight materials employed.

As mentioned before, the preferred equivalent weight of the amine-terminated compound depends somewhat on the type of foam being made, and the method of its manufacture. For making a molded polyurethane foam in a hot cure process, the amine-terminated compound preferably has an equivalent weight of from 500 to 2500, more preferably from 700 to 2000, and most preferably from 800 to 1500. For making slabstock foam Sor a molded polyurethane foam in a cold cure process.

the most preferred ecuivalent weight is from 50 to 1800.

Either aliphatic or aromatic polyisocyanates can be used in this invention to maze foam. Suitable aliphatic polyisocyanates include, for example, ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethyl ne diisocyanate, ',12-dodecane diisocyanate, cyclobutane-1,3-diisocyanate, cvclohexane-' and diisocvanate. Itl ~L C WO 88/08009 PCT/US88/00935 -diisocyanato-3,3,5-trimethylcyclohexane, 2,4- and/or 2,6-hexahydrotoluene diisocyanate, perhydro-2,4'and/or -4,4'-diphenylmethanediisocyanate (H12MDI) and isophorone diisocyanate.

Suitable aromatic polyisocyanates include, for example, 2,4- and/or 2,6-toluene diisocyanate (TDI), 2,4'-diphenylmethanediisocyanate, 1,3- and 1,4-phenyl- 1 ene diisocyanate, 4,4'-diphenylmethane diisocyanate (including mixtures thereof with minor quantities of the 2,4'-isomer), 1,5-naphthylene diisocyanate, triphenylmethane-4,4',4''-triisocyanate and polyphenylpolymethylene polyisocyanates. When the polyisocyanate is MDI or a derivative of MDI, especially a mixture including a polymeric MDI, it is preferred that the amine-terminated compound be substantially difunctional, have an average functionality of to 2.2, preferably 1.8 to 2.1. more preferably from 1.9 to 2.05. It has been found that the use of substantially difunctional amine-terminated compounds.

as opposed to the higher functionality polyols conventionally used in making flexible foam, delays the gelling of the reaction mixture and thereby further promotes the formation of good quality foam. Mixtures Sof a relatively high equivalent weight compound having an actual functionality of from 1.5 to 1.95 and another relatively high equivalen; weight compound having an actual functionality of 2.2 or higher wherein the average functionality of the mix:ure is from 1.5 to 2.2 can be used.

In addition, derivatives and prepolymers of the foregoing polyisocyanates such as those containing urethane, carbodiimide, allophanate. isocyanurate, acylated urea. biuret, ester and similar groups are WO 88/08009 PCT/US88/00935, -14useful herein. Of these, prepolymers of TDI and MDI, and the so-called "liquid MDI" products which contain carbodiimide groups and have an equivalent weight of from 130 to 150 are of particular significance.

Of the foregoing polyisocyanates. TDI, MDI, isophorone diisocyanate, H 12 MDI, hexamethylene diisocyanate, cyclohexane diisocyanate and derivatives thereof are preferred due to their cost, commercial availability and performance. TDI, MDI and derivatives of MDI are most preferred. TDI, particularly mixtures of the 2,4- and 2,6- isomers, is especially preferred.

The polyisocyanate is used in an amount sufficient to provide an isocyanate index of from 60 to 200, preferably from 90 to 125, more preferably from to 110. .At higher indices, trimerization of the polyisocyanate occurs, causing the foam to lose flexibility. At lower indices, insufficient curing occurs, causing the foam to have poor properties. When MDI or derivative thereof is used as the polyisocyanate, preferred isocyanate indices are from to 110, with from 70 to 103 being more preferred, as MDI tends to provide a board-like foam at indices greater than 110, but provides a highly resilient foam at indices as low as 60. The "isocyanate index" is 100 times the ratio of isocyanate groups to active hydrogen-containing groups contained in the mixture which reacts to form the foam.

A blowing agent is another critical component of the invention. The blowing agent is any material which is capable of generating a gas under the conditions of the reaction of a polyisocyanate ant a polyol.

Such materials include air. carbon dioxide, nitrogen.

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the polyol is mixed with the blowing agent and all the WO 88/08009 PCT/US88/00935 water, formic acid, low-boiling halogenated alkanes, finely divided solids and the so-called "azo" blowing agents such as azobis(formamide). Preferred are water, the low-boiling halogenated alkanes, or mixtures thereof. Blowing agents are advantageously employed in a quantity sufficient to provide the foam with a bulk density of from 0.5, preferably 0.9, more preferably 1.1 to 6 or less, preferably 4, more preferably 3 pounds per cubic foot. The halogenated alkanes, including methylene chloride, dichlorodi-fluoromethane and monochlorodifluoromethane and monochlorotrifluoromethane, generally provide the desired density when employed in amounts of from 5 to 50 parts per 100 parts relatively high equivalent weight compound. Lesser amounts are useful when employed in conjunction with another blowing agent, such as water.

One particular advantage of this invention is that it permits the production of very low density foam using water as the blowing agent. Previously, the use of water as the blowing agent was limited to 4.6 parts or less per 100 parts relatively high equivalent weight polyol, since the use of greater quantities tended to provide inferior foam. With this invention, in excess 7.5 parts of water can be used per 100 parts of amine-terminated compound to provide an ultra-low density foam having useful physical properties.

Accordingly, water provides a desirable density when Sused in an amount of from 0.5. oreferably 3.5. more preferably 4 to 10, preferably 3, more preferably 6, parts per 100 parts amine-terminated compound. For making ultra-low density foam (less than 1.5 pounds per cubi foot density (10 kg/m3)), 5 to 10 oarts of water are used.

men;z nrougn cne presence o- co- ioca.- sizec po-vmer WO 88/08009 PCT/US88/00935 -16- A catalyst for the reaction of the amine- -terminated compound and the polyisocyanate is also used in making foam according to this invention.

Although a wide variety of materials are known to be useful for this purpose, the most widely used and preferred catalysts are the tertiary amine catalysts and the organometallic catalysts.

I Exemplary tertiary amine catalysts, include, for example, triethylenediamine, N-methyl morpholine, N-ethyl morpholine, diethyl ethanolamine, N-coco morpholine, 1-methyl-4-dimethylaminoethyl piperazine, 3-methoxy-N-dimethylpropylamine, N,N-diethyl-3-dIethylaminopropylamine, dimethylbenzyl amine and bis(2- -dimethylaminoethyl)ether. Tertiary amine catalysts are advantageously employed, in an amount of from 0.01 to 5, preferably from 0.05 to 2 parts per 100 parts by weight of the amine-terminated compound.

Exemplary organometallic catalysts include organic salts of metals such as, for example, tin, bismuth, iron, mercury, zinc and lead, with the organotin compounds being preferred. Suitable organotin catalysts include, for example, dimethyltindilaurate, dibutyltindilaurate and stannous octoate.

Other suitable catalysts are taught, for example, in U.S. Patent 2,846.408. Advantageously, from 0.001 to part by weight of an organometallic catalyst is used per 100 parts of amine-terminated compound.

Polyurea or polyurea-polyurethane foam is prepared according to this invention by contacting the amine-terminated compound, blowing agent, polyisocyanate and catalyst together under conditions such that the components react to form a cellular ool mer. Gen- I~ r i. I WO 88/08009 PCT/US88/00935 -17erally, the reaction mixture may contain additional components such as cross-linkers, catalysts, surfactants, colorants, cell openers, flame retardants, antioxidants, mold release agents and the like, which may vary according to the desired attributes of the foam, and whether the foam is a molded or slabstock foam.

Cross-linkers may be used, particularly in making molded foam or high resiliency slabstock foam, in order to- improve load-bearing and processing.

Suitable such cross-linkers include alkanolamines and other compounds of 200 or low:r equivalent weight having from 3 to 8, preferably from 3 to 4 active hydrogen-containing groups per molecule. Exemplary such compounds are glycerine and trimethylolpropane, as well as other alkylene triols. Preferred, however, are alkanolamines such as diethanolamine, triisopropanolamine, triethanolamine, diisopropanolamine, adducts of from 4 to 8 moles of ethylene oxide and/or propylene oxide with ethylene diamine, and polyamines such as, for example, methylene bis(o-chloroaniline), ethylenediamine and ammonia. Most preferred, on the basis of its optimum reactivity, is diethanolamine.

One advantage of the foam of this invention is that, at an equivalent level of cross-linker, the foam exhibits better load-bearing characteristics than similar foas made without the amine-terminated comoound.

Accordingly, to achieve equivalent load-oearing, i is possible with this invention :o reduce or even eliminate the cross-linker compound. When used, however, less than 5 parts, preferably 0.1 to 4 parts of the cross-linker are advantageously employed per 100 carts of the amine-terminated compound. _t is most

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L- 1- WO 88/08009 PCT/US88/00 9 3 -18i 1 i preferred that the combined weight of cross-linker and chain extender, when used, is less than 5 parts per 100 parts by weight of the amine-terminated compound.

Chain extenders may also be used to further improve the load-bearing of the foam. "Chain extenders", for the purposes of this invention, include compounds having two active hydrogen-containing groups per molecule and an equivalent weight of from 31 to 300, preferably from 31 to 150. Hydroxyl-containing chain extenders include the alkylene glycols and glycol ethers such as ethylene glycol, 1,3-propylene glycol, -1,4-butylene glycol, 1,6-hexamethylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol and 1,4-cyclohexanedimethanol. Amine chain extenders include diethyltoluene diamine, phenylene diamine, methylene biS(o-chloroaniline), NaCI blocked methylene bis(aniline), toluene Sdiamine, aromatic diamines which are alkyl substituted on at least one of the carbon atoms adjacent to each amine groups. Such chain extenders, when used, are advantageously employed in a minor amount, less than 5 parts by weight per 100 parts by weight amine- -terminated compound. Most preferably, the combined Sweight of chain extender and cross-linker is less than parts by weight per 100 parts by weight amine-terminated compound. It is usually preferable, however. :o prepare the foam in the absence of a chain extender.

In order to make a stable foam, one which does not collapse or contain significant quantities of large pores, a surfactant which stabilizes the foaming reaction mixture against collapse until the mixture is sufficiently cured to maintain its configuration may De used. Suitable surfactants include siloxane :clvyalr, i n -Y I I- WO 88/08009 PCT/US88/00935 -19kylene oxide) copolymers as described, for example, in U.S. Patents 3,887,500 and 3,957,842. The selection and use of such surfactants in preparing foams is well- -known in the art. However, one advantage of this invention is that reduced levels of surfactant can be used, and sometimes the surfactant can be eliminated altogether. Accordingly, it is preferred to use a Ssurfactant in an amount of less than 0.5, preferably less than 0.25 part per 100 parts of amine-terminated compound. In an especially preferred embodiment, the foam is prepared in the substantial absence of a surfactant, According to this invention, foam is prepared in a one-shot process by mixing all reactive components, catalysts, and optional ingredients and permitting same to react. The benefits of this invention are particularly seen in the preparation of molded foam.

In preparing molded polyurea-polyurethane foam, all components except the polyisocyanate are advantageously blended together and injected as a single stream into a mixing head. However, certain components such as catalysts or halogenated methane blowing agents are sometimes blended with the polyisocyanace. In addition, Sthe water and surfactant. when used, can be introduced as a separate stream, if desired. The polyisocyanate is added to the mixing head as a separate stream where it is mixed with the polyol mixture and injected into U0 the mold. In performing the mixing and mold filling steps, conventional, low pressure apparatus can be used, or high pressure impingement mixing processes, such as a reaction injection molding process, can be used. Generally, the components are mixed at approximately room temperature, although components such as J. .l C'-j i* 'Ju il J I WO 88/08009 PCT/US88/00935 i I pure MDI which are solid at room temperature may be heated above their melting points.

In one molding technique (hot molding process), the reactants are placed into a mold which is at ambient temperature. After filling, the mold is placed into an oven at a temperature of from 150°C to 275'C to effect curing. In a second technique (cold molding process), the reactants are placed into a mold which is preheated to a temperature of from 30°C to 750C. After the mold is filled, it is placed in a 70°C to 150°C oven to effect cure. In a third technique, the filled mold is maintained at ambient temperature during the curing process. In this third technique, the mold may or may not be preheated.

Sufficient of the reaction mixture is placed into the mold so that, after expansion, the mixture completely fills the mold. Advantageously, a small excess of material is added over that minimally required to fill the mold. After filling the mold, the reaction mixture is permitted to cure in the mold at least to a state which permits the molded foam to be removed from the mold without permanent undesired distortion. In typical commercial procedures. an in-mold 35 i cure time of from 2 to 30 minutes is adequate for this purpose. If required, the foam can be posccured by heating to a temperatuere of from 5CC to 120zC for a period of from 10 minutes to 24 hours, preferabl from minutes to 2 hours.

It may be necessary or desirable to meehanically open the cells of the foam during or after cure.

This can be done by crushing the foam, puncturing the foam. vacuum crushing the foam, or by releasing the The orimary amine is advanageous1-:- an inert- WO 88/08009 PCT/US88/00935 -21pressure in the mold at a proper stage of cure as taught in U.S. Patent 4,579,700. An advantage of this invention is that the postcure shrinkage associated with inadequate cell opening is usually substantially reduced, thereby reducing or eliminating the need to mechanically open the cells.

In making the less preferred slabstock foam, the reaction mixture also advantageously contains a i surfactant and catalyst as described before. Crossi -linkers, although they may be used, are often omitted i 15 from slabstock formulations. In the commercial production of slabstock foam, the components can be and typically are introduced individually to a mixing head I0 where they are thoroughly blended and metered onto a 'I 20 bed where foaming takes place. However, preblending of the components, except for the polyisocyanate, can be done if desired. The components are advantageously at room temperature or a slightly elevated temperature when blended in the mixing head, although preheating may be necessary in some instances to melt components which are solid at room temperature.

The foam of this invention is useful, for example, as bedding, furniture cushioning, padding, carpet underlayment, attached cushion carpet backing, automobile head rests, crash pads, door handles, head liners and seating. This invention is particularly 40 useful in applications wherein good load-bearing characteristics are desired, or where a low density, high water formulation is desi-ed.

The following examples are provided to illustrate the invention but are not intended to limit the I' h i i i- II~IVYOY-IL*----rruurr-r- WO 88/08009 PCT/US88/00935 -22scope thereof. All parts and percentages are by weight unless otherwise indicated.

Examole 1 In this example, a difunctional primary aromatic amine-terminated polyether was reacted with polymeric MDI to form molded foam.

Flexible foam Sample Nos. 1 and 2, and Comparative Samples A and B were prepared from the formulations indicated in Table I.

-~ilCI"~ILI^6 SWO 88/08009 PCT/US88/00935 -23- TABLE I Parts by Weight Comp.

Sample Sample No. 1 A* Comp Sample Sample No. 2 B* Comoonent Amine-terminated Polyether A® Polyol A® diethanolamine 100 0 0 4.5 0 100 0 0.5 Water Amine Catalyst® Silicone Surfactant A' Silicone Surfactant BO Silicone Surfactant CO Silicone Surfactant DO Polymeric MDI A Polymeric MDI B Not an examole of this 4.5 4.5 0 0.75 0 0.75 0.75 0 0.75 0 0.3 0 0.3 0.3 0 0.3 80.3 80.3 0 0 0 0 80.3 80.3 invention.

Polyol A is a difunctional, 1000 equivalent weight poly(propylene oxide) which contains 18% by weight of a terminal poly(ethylene oxide) block. Amineterminated Polyether A is prepared by reacting Polyol A with p-nitrochlorobenzene and subsequently reducing the nitro groups to primary amine groups.

About 83% of the hydroxyl groups are converted to primary aromatic amine groups.

®A proprietary tertiary amine catalyst sold v- Union Carbide Corooration as C225 catalyst.

®Y-10148 surfactant, sold by Union Carbide Corp.

DC-5043 surfactant. sold by Dow Corning Corp.

surfactant. sold by Union Carbid oro.

DC-0140 surfactant. sold by Dow Corning Corp.

SA 135 equivalent weight polymeric MDI (2.2-2.4 functional) prepared from 12 weight percent of the 2,4'-isomer.

®A 135 equivalent weight polymer MDI functional) prepared from 2.5 weight percen: of the isomer.

L I I SII I

I

WO 88/08009 PCT/US88/00935 -24-.

Molded foam was made from each of Sample Nos.

1 and 2 and Comparative Samples A and B by mixing the components, transferring same to an 8" X 8" X 3" (200 mm x 200 mm x 76 mm) mold which was preheated to,145°F (63 0 and after the foam had risen, placing the mold in a 175 0 F (80°C) oven for 3 minutes, at which time the foam was demolded. The foams had properties as indicated in Table II following.

i d_ 0 ©o TABLE II Sample or Comparative Sample No.

Property DenusiLy, lb/ft 3 (kg/nii 3 Tensile Str., psi'" (HPa) ElonqaLion, Tedar lb/in (N/III) Resiliency, Complession Set,%" I FDI) iet. to 25% '6 lysteresis Return Modu i lus Ai Flow, FL3/miin (mi 3/s) 1 2.02 (32) 22.7 (0.16)' 70 2.14 (375) 28 81

A*

1.91 (31) 12.9 (0.09) 50 1.25 (220) 30 56 2 2.13 (31) 35.1 (0.24) 82 2.19 (385) 33 72 54 158 28 52 2.93 0.14 (6.6 x 10 5

B*

2.11 (34) 14.0 (0.10) 74 1.22 (215) 68 159 37 54 2.34 0.43 (2 x 10- 4 46 140 22 47 3.04 0.41 65 131 35 54 2.11 0.18 (1.9 x 10 4 (8.5 x 10 5 SHNot an example of this invention.

ASTM D-3574-81 Test E. I ASTM D-3574-81 Test F.

AS'I'M D-3574-81 Test II.

U)

ASTM 1 3574-81 Te D. 00 ASTM D1-3574-81 Test B. IFD is indentation force deflection.

Mthdulius 65%1FD/25 I1"ID.

A.;TM 1) 3574 81.

UI

WO 88/08009 PCT/US88/00935 -26- As can be seen from the data in Table II, major improvements in modulus, tensile strength, and tear strength were obtained with this invention. The modulus values are particularly significant, since moduli such as obtained with this invention indicate that the foam will provide particularly comfortable seating. These values are particularly surprising because Sample Nos. 1 and 2 were made without a cross- -linker.

Examole 2 Flexible foam Sample Nos. 3-7 were prepared from formulations as described in Table III following.

L0 j.

WO 88/08009 WO 8808009PCT/US88/00935 -27- TABLE III Parts by Weight Samp. Sarno. Samp. Samp. Sarnp.

No. 3 No. 4 No. 5 No. 6 No. 7 Corneanen t Amine-terminated Polyether BO Polyol BO Polyol C® diethanolamine 50 40 60 100 60 40 0 0 1 .7 3.8 1 .7 3.8 1 .7 3.8 Water 3.8 triethylene diamine solution~ bis(2-dimethyl aminoe thy].)ethero Silicone Surfactant B Cell Opener@ 80/20 TDID 0.25 0.25 0.25 0.25 0.25 0.05 0.05 0.05 0.05 0.05 1 .6 0.0~4 1 .6 0 1 .6 0 48.4 48.4. L18.4 489.' 51.-- Polyol B i~s a 1650 equivalent weight, nominally trifunctional poly(propylene oxide) containing about 18 weight percent ethylene oxide end-capping.

Amine-Terminated Polyether B is prepared by reacting Polyol B with p-nitrochlorobenzene and reducing the nitro groups to primary amine groups.

1A 25%/ solids SAN cooolymer polyol us ing Polyol B as the base polyol SA 33 wt.-7 0 solutEion in dioropylene glycol.

SAs a 10%,1 solution in Amine-terminated Pol-yether B.

4 C-5043, sold by Dow Corning Corporation.

'A silicone oil so!-d Dow Corning Corpora-_icn a=s DCF' 11630.

®A mixture of 80 weight percent of the 2,4- isomer and 20 weight percent, of the 2,6- isomer.

jr-~ WO 88/08009 PCT/US88/00935, -28- Foam Sample Nos. 3-7 were prepared according to the general procedure des2ribed in Example 1, with results as indicated in Table IV following.

i k I TABLE IV Sample Number Densi Ly, 1b/ ft0 kq/u 3 1Tensi le Sir., psi (Mlla) LEnLfJ. ionl, V" Teat Str., lb/in Res ii licy Comn1pti.:Ssi On Set,%'" ict. Lo) 2!A Ilystuiesis Return"' Modmi I LS Ait Flow, FL 3/in (11 3 1.98 (32) 15.0 (0.10) 109 1.18 (207) 50 41 .0 66 21 73 2.36 2,0 (9.4 x 10-4) 1.92 20.9 104 1.40 49 23.1 11 (31) (0.14) (245) 5 1.95 (31) 15.8 (0.11) 125 1.17 (205) 60 16.7 19 47, 16 83 2.47 3.1 (1.5 x 10-3) 1.84 15.6 121 1.23 55 14 8 6 (30) (0.11) (215) 7 1.19 (19) 19.1 (0.13) 91 1.76 (308) 46 66.5 31 78 23 75 2.52 1.2 (5.6 x 10-4) 19 46 15 80 2.42 2,8 (1.3 x 10-3) 26 59 2.12 1.1 (5.2 x 10-4) 'ASTM D 35-14 81 Test E.

ASTH 1) 3574-81 Te st F'.

SASTM 1) 3574-81 Test 11.

ASTM 1P 3514--81 Test D SASIM1. '15'14-81 Te st B. 1FD is indentation force deflection.C 0 Modtlus 65'[FD/ 5%JP 0 ASTM D-354-81 L _i YC WO 88/08009 PCT/US88/00935 3 All foams had good physical properties. Of particular interest is Sample No. 7, in which 7.5 parts of water were used per 100 parts amine-terminated compound. A very low density foam having particularly good physical properties, especially tensile and load- -bearing properties, was obtained.

Examole 3 In this example, a nominally trifunctional secondary aliphatic amine-terminated polyether was reacted with an isomeric mixture of TDI to form a molded foam.

Flexible foam Sample Nos. 8-10 were prepared from the formulations, indicated in Table V.

-I

4 WO 88/08009 PCT/US88/00935 -31- TABLE V Parts by Weight Samp. Samp. Samp.

No. 8 No. 9 No. Comoonent 1 Amine-terminated Polyether

C®

Diethanolamine Water triethylene diamine solution® bis(2-dimethyl aminoethyl)ether® Silicone Surfactant B® dibutyltindilaurate N-[3-(dimethylamino)propyl]- N,N',N'-trimethyl-l,3propanediamineo 80/20 Toluene diisocyanate 9 100 1.5 3.8 0.25 0.05 100 1.7 3.8 0.12 100 1.7 3.8 0.12 0.075 0.075 2.0 1.65 1.65 0.0042 0.15 0.0042 0.0042 0.24 0.24 101 101 105 index index index Prepared by reacting a primary amine-terminated, 5000 molecular weight, nominally trifunctional polyether with acrylonitrile until essentially all primary amine groups are converted to secondary amine groups.

A 33% solution in dipropylene glycol (DPG).

As a 10% solution in Amine-terminated Polyether C.

SDC-5043 surfactant. sold by Dow Corning Corooration.

Sold by Abbott Laboratories as Polycat 77.

See footnote of Table III.

Foams were made from each of these formulations by mixing all components except the TDI, and with all comoonents at 78? blending in the TD: and -e

U

WO 88/08009 PCT/US88/00935 -32pouring the mixture into a 15" X 15" X 4.5" (381 mm x 381 mm x 114 mm) mold which was preheated to 140°F (600C). After filling the mold, it was closed and immediately placed into a 250°F (121 0 C)oven for four minutes, after which the resulting foam was demolded.

After cooling, the physical properties of the foam were determined to be as indicated in Table VI.

TABLE V1 Sample No.

P-1 operty D~ensity, lb/ft 3 k/id 3 Tenrsile Str., psi (MPa) Elongation, 'I'La SL lb/in (N/in)' Comnpiession Set,% I FD I 8 2.02 (33) 20.5 (0.14) 184 1.75 (306) 48 15.5 9 2.17 (35) 19.0 (0.13) 168 1.55 (271) 43 19.7 18 56 15 80 3.11 1.9 8.9 x 10-4 3.4 (1.6 x 10-3 2.20 18.6 10.13) 147 1.42 (249) 51 21.3 16 79 3.25 1.75 (8.2 x 10- 4 3.7 (1.7 x 103) 6 Y6 eL. to 25% 'A lhysteresis Return'' Muin Flw fL mn(s13/) Air Flow, crushed, ft 3 /ni (11n 11ISce notes 0) of Table IV.

22 65 17 79 2.95 1.75 (8.2 x 10-4 4.0 (1.9 x 10-3) ruerrr~mr~Ml~a~ar~ WO 88/08009 PCT/US88/00935 J -34- All foams had good properties. Of particular interest are the IFD and modulus values. A foam similarly made, except usirg a hydroxyl-terminated polyether instead of the amine-terminated polyether, normally has a 25 percent IFD of 16 and a 65 percent IFD of 44. The IFD values provided by the foam of t"'s invention were substantially higher. Likewise, a foam made using a mixture of a SAN copolymer polyol at an effective solids level of 12.5 percent by weight, based on the weight of the polyol, demonstrated typical percent IFD values of 17 to 21 and 65 percent IFD values of 52 to 59. The use of amine-terminated polyethers is seen to provide load-bearing properties equal or superior to foam made with microscopic reinforcement. In addition, the modulus values of this foam are very high, as is desired and difficult to achieve with the use of copolymer polyol.

Examole 4 0 Using the formulation set out in Table VII below, a molded polyurethane foam (Sample No. 11) was made using the general procedure described in Exampie 1.

WO 88/08009 PCT/US88/00935 TABLE VII Parts by Weight Component Amine-terminated Polyether B® Copolymer Polyol A® Diethanolamine Water triethylene diamine solution® bis(2-dimethylaminoethyl)ether® dibutyltindilaurate N-[3-(dimethylamino)propyl]-N,N',N'trimethyl-1,3-propanediamine® Cell Opener® 80/20 Toluene diisocyanatee 1.7 3.8 0.12 0.075 0.0042 0.24 0.05 105 index Prepared by reacting a primary amine-terminated, 5000 molecular weight, nominally trifunctional polyether with p-nitrochlorobenzene, followed by reduction of the nitro group to the primary amine.

®A 40% solids SAN-type copolymer polyol having Polyol B as the base polyol.

®A 33% solution in dipropylene glycol (DPG).

As a 10% solution in Amine-terminated Polyether C.

®Sold by Abbott Laboratories as Polycat 77.

A silicone oil sold by Dow Corning Corporation as DCF 11630.

See note O of Table III.

The resulting foam had properties as set out in Table VIII.

WO 88/08009 PCT/US88/009 3 -36- TABLE VIII Density, lb/ft3 (kg/m 3 Tensile Str., psi (MPa)® Elongation, %O Tear Str., Ib/in® (N/m) Resiliency, Compression Set,%®

IFD®

Hysteresis Return® Modulus® Air Flow, ft 3 /min (m 3 2.20 18.0 (0.12) 83 1.37 (240) 36.6 61 148 66 2.43 6.0 (2.8 x 10- 3 ASTM D-3574-81 Test E.

®ASTM D-3574-81 Test F.

®ASTM D-3574-81 Test H.

ASTM D-3574-81 Test D.

ASTM D-3574-81 Test B. IFD is indentation force deflection.

Modulus 65%IFD/25%IFD.

ASTM D-3574-81.

The combination of amine-terminated compound and copolymer polyol here provided dramatic improvement in load bearing, as indicated by the IFD values reported in Table VIII. A similar, but less pronounced effect was also seen in Sample No. 4, which also employed a blend of amine-terminated compound and copolymer polyol.

Claims (4)

1. An open-celled flexible polyurea or poly- urea-polyurethane foam having a density of 6 pounds per cubic foot (100 kilograms per cubic meter) or less, which is the rdaction product of a reaction mixture comprising a relatively high equivalent weight compound or mixture thereof having an average of from 1.5 to 4 active hydrogen-containing groups per molecule, of which active hydrogen-containing groups, at least 30 percent are primary aromatic, Lewis acid-blocked primary aliphatic and/or secondary aliphatic or aromatic amine groups, a blowing agent, in amount sufficient to provide -a cellular structure to the foam, less than 5 parts by weight of a cross- -linker or chain extender per 100 parts of component and a polyisocyanate. L SWO 88/08009 PCT/US88/00935 1 -38-

2. The foam of Claim 1 wherein the i polyisocyanate is present in an amount sufficient to provide an isocyanate index of from 90 to 125. Sf -Focrr-f cs r

53. The foam ofClaim 2 wherein the blowing agent comprises water, which is present in an amount of at least 3.5 parts by weight per 100 parts of Component and Component and Component has an equivalent weight of from 500 to 2500. 4. fcs>rr- I.S Ce\n\ e-(m \C\ 4. The foam of any one of the preceding claims wherein the polyisocyanate comprises; an isomeric mixture of 2;4- and 2,6-toluene diisocyanate, or an isomeric mixture of and 4,4'-diphenylmethanediisocyanate or derivative thereof and component has an average functionality of from 1.9 to 2.05. T4e-f-cm--o£, any one of Caims 1 to 3 wherein Component comprises an aromatic amine-terminated polyether or a secondary aliphatic amine-terminated polyether. 6. The foam ofCClaim 5 wherein the aromatic amine-terminated polyether comprises a reaction product of a polyether polyol and a halogenated nitrobenzene compound in which the nitro groups are subsequently reduced to primary amine groups. 7. The fanm nf laim 5 wherein the secondary aliphatic amine-terminated polyether comprises a Q -TCc 9 i I~nY I WO 88/08009 PCT/US88/00935 -39- Michael addition product of a primary amine-terminated polyether and an ethylenically unsaturated compound. foc-v-% r\ 8. The foam of jlaim 7 wherein the secondary aliphatic amine-terminated polyether is prepared in a reductive amination of a polyether polyol with a primary amine. 9. A process for preparing an open-celled polyurethane foam, comprising reacting a reaction mixture in a one-step process under conditions such that a flexible polyurea or polyurea-polyurethane foam is obtained', wherein the reaction mixture comorises a relatively high equivalent weight compound or mixture thereof having an average of from 1.5 to 4 active hydrogen-containing groups per molecule, of which active hydrogen-containing groups, at least 30 percent are primary aromatic, Lewis acid-blocked primary aliphatic and/or secondary aromatic or aliphatic amine groups, a blowing agent, in amount sufficient to provide the foam with a density of less than 6 pounds per cubic foot (10 kilograms per cubic meter), less than 5 parts by weight of a cross- -linker or chain extender per 100 parts of component and a poiyisocyanate. pnj L .I _I S WO 88/08009 PCT/US88/00935 The process of Claim 9 wherein component has an average equivalent weight of from 500 to 2500, component comprises an isomeric mixture of toluene diisocyanate, MDI or a derivative of MDI, and the reaction mixture further comprises effective amounts of a catalyst and a surfactant. 11. An open-celled polyurea or polyurea-poly- urethane foam having a density of 6 pounds per cubic foot (100 kilograms per cubic meter) or less prepared by reacting a reaction mixture comprising a polyether having an equivalent weight of from 500 to 2500, an average func- tionality of from 1.8 to 3, and having from 50 to 100 percent of its active hydrogen-containing groups in the form of 25 (1)aromatic amine groups or secondary aliphatic amine groups; from 3.5 to 8 parts of water per 100 parts by weight of component an effective amount of a tertiary amine catalyst; from 0.1 to 4 parts, per 100 parts by weight of component of an Salkanolamine cross-linker: and a sufficient amount of an aromatic polyisocyanate to provide an isocyanate index of from 95 to 120. 1 -41- 12. An active hydrogen-containing composition comprising a relatively high equivalent weight compound or mixture thereof having an averaqe of from 1.5 to 4 active hydrogen-containing groups per molecule, of which active hydrogen-containing groups, at least 30 percent are primary aromatic, Lewis acid-blocked primary aliphatic and/or secondary aliphaticf or aromatic amine groups, from 3.5 to 10 parts by weight of water per 100 parts by weight of component and from 0.1 to 4.5 parts by weight of a cross-linker or chain extender per 100 parts by 0* weight of component 13. A foam as claimed in claim 1 or claim 11 substantially as hereinbefore described with reference to any one of the examples. 14. A process as claimed in claim 9 substantially as hereinbefore described with reference to any one of the examples. 15. A composition as claimed in claim 12 substantially as hereinbefore described with reference to any one of the examples. DATED: 28 August, 1990 PHILLIPS ORMONDE FITZPATRICK Attorneys for: THE DOW CHEMICAL COMPANY WDP 5043N U L INTERNATIONAL SEARCH REPORT International Application No. PCm/US88/00935 1. CLASSIFICATION OF SUBJECT MATTER (if several classification symbols apply, indicate all) e According to International Patent Classification (IPC) or to both National Classification and IPC IPC(4) C08G 18/14, 18/48, 18/32 U.S. CL. 521/160, 167, 163; 252/182 II. FIELDS SEARCHED Minimum Documentation Searched 7 Classification System Classification Symbols US 521/125, 126, 160, 163, 167; 252/182 Documentation Searched other than Minimum Documentation to the Extent that such Documents are Included in the Fields Searched 8 Ill. DOCUMENTS CONSIDERED TO BE RELEVANT 9 Category Citation of Document, ii with indica' n, where appropriate, of the relevant passages 12 Relevant to Claim No, 13 Y US, A, 4,569,951 (NELSON) 11 FEBRUARY 1986 1-11 SEE THE FNTIRE DOCUMENT. Y US, A, 4,444,910 (RICE ET AT,) 24 APRIL 1984 1-12 SEE THE ENTIRE DOCUMENT. Y JA, B, 58-152014 (MITSUI NISSO URETHA) 1-12 09 SEPTEMBER 1983. X US, A, 4,442,236 (RASSHOFFR FE AL) 10 APRIL 1-12 1984, SEE COLUMN 3, LINES 33-41. A US, A, 4,642,320 (TURNER ET AL) 10 FEBRUARY 1 1987, SEE THE ENTIRE DOCUMENT. A US, A, 3,838,076 (MOSS ET AL) 24 SEPTFMBER 1 1974, qEE ENTIRE DOCUMENT. A US, A, 4,530,941 (TURNER FT AL) 23 JULY 1-12 1985, SEE ENTIRE DOCUMENT. X EP, A, 0,081,701 (BAYER) 22 JUNE 1983, SEE 1-12 PAGE 6. SSpecial categories of cited documents: to later document published alter the international filing date document defining the general state of the art hih i not or pririity date and not in conflict with the application but considered to be of particular relevance cited to understand the principle or theory underlying the invention earlier document but published on or after the international "X document of particular relevance; the claimed invention Scannot be considered novel or cannot be considered to document which may throw doubts on priority claim(s) or involve an inventive step which is cited to establish the publication date of another document of particular relevance; the claimed invention citation or other special reason (as specified) document of particular relevance; the claimed invention citation or othr pecial reason (as specified) cannot be considered to involve an inventive step when the document referring to an oral disclosure, use, exhibition or document is combined with one or more other such docu- other means ments, such combination being obvious to a person skilled document published prior to the international filing date but in the art. later than the priority date claimed document member of the same patent family IV. CERTIFICATION Date of the Actual Completion of the International Search Date of Mailing of this International Search Report 26 MAY 1988 2 8 JUN 1988 International Searching Authority Signature of Authorized Officer ISA/US DENNIS R. DALEY Form PCTISA'210 (second sheel) (Rev.11-87) International Application No. P T U 8 0 3

111. DOCUMENTS CONSIDERED TO BE RELEVANT (CONTINUED FROM THE SECOND SHEET) Category Citoilion of Document, with indication, where appropriate, of the relevant passages Relevant to Claim No A US, A, 4,474,901 (DOMINGUFZ 1-12 02 OCTOBER 1984, SEE ENTIRE D)OCUMENT. A us, zk,'4,555,531 (CHRISTMAN) 26 NOVEDPARPR 1-12 1985, SEE ENTIRE DOCUMENT. Y US, A, 4,569,952 (RADOVICH ET AL)ll"FEBRUARYV 1-12 1986, SEE ENTIRE DOCUMAENT. Form PCTIISNt2IO (eera sheet) (Rev.1 1.87) International Application No. pCrn/US 8 8/0 0 93 FURTHER INFORMATION CONTINUED FROM THE SECOND SHEET OBSERVATIONS WHERE CERTAIN CLAIMS WERE FOUND UNSEARCHABLE1 This international search report has not been established in respect of certain claims under Article 17(2) for the following reasons: Claim numbers because they relate to subject matter ti not required to be searched by this Authority, namely: Claim numbers ,because they relate to parts of the international application that do not comply with the prescribed require- ments to such an extent that no meaningful international search can be carried out speciically: 3. E Claim numbers because they are dependent claims not drafted in accordance with the second and third sentences of PCT Rule 6.4(a). Vl.] OBSERVATIONSWHERE UNITY OF INVENTION IS LACKING 2 This International Searching Authority found multiple inventions in this international application as follows: GROUP I, CLAIMS 1-11, DRAWN TO AN OPEN-CELLED FLEXIBLF POLYUREA OR POLTUREA-POLYURETHANE FOPM: CLASS 521, SUBCLASS 167. GROUP II, CLAIM 12, DRAWN TO AN ACTIVE HYDROGEN-CONTAINING COMPOSITION: CLASS 252, SUBCLASS 182. 1.[X As all required additional search fees were timely paid by the applicant, this international search report covers all searchable claims of the international application. Tele p ho t FrAC e.. As only some of the required additional search fees were timel, paid by the applicant, this international search report covers only those claims of the International application for which fees were paid, specifically claims: No required additional search fees were timely paid by the applicant. Consequently, this international search report is restricted to the invention first mentioned in the claims; it is covered by claim numbers: As all searchableclaims could be searched without effort lustilying an additional fee, the International Searching Authority did not invite payment of any additional lee. Remark on Protest E The additional search tees were accompanied by applicant's protest. S No protest accompanied the payment of additional search fees. Form PCT/ISA/210 (supplemental sheet (Rev. 11-87)