WO1988008009A1 - Mousses flexibles de polyuree ou polyuree-polyurethane preparees a partir de composes a terminaison amine de poids equivalent eleve et leur procede de preparation - Google Patents

Mousses flexibles de polyuree ou polyuree-polyurethane preparees a partir de composes a terminaison amine de poids equivalent eleve et leur procede de preparation Download PDF

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Publication number
WO1988008009A1
WO1988008009A1 PCT/US1988/000935 US8800935W WO8808009A1 WO 1988008009 A1 WO1988008009 A1 WO 1988008009A1 US 8800935 W US8800935 W US 8800935W WO 8808009 A1 WO8808009 A1 WO 8808009A1
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Prior art keywords
foam
amine
parts
weight
component
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PCT/US1988/000935
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English (en)
Inventor
Ralph D. Priester, Jr.
Ronald M. Herrington
Richard D. Peffley
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The Dow Chemical Company
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Publication date
Application filed by The Dow Chemical Company filed Critical The Dow Chemical Company
Priority to BR888807445A priority Critical patent/BR8807445A/pt
Priority to JP63503240A priority patent/JPH06102710B2/ja
Publication of WO1988008009A1 publication Critical patent/WO1988008009A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/50—Polyethers having heteroatoms other than oxygen
    • C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
    • C08G18/5024—Polyethers having heteroatoms other than oxygen having nitrogen containing primary and/or secondary amino groups
    • C08G18/503—Polyethers having heteroatoms other than oxygen having nitrogen containing primary and/or secondary amino groups being in latent form
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0008—Foam properties flexible
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0041—Foam properties having specified density
    • C08G2110/005—< 50kg/m3
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0041—Foam properties having specified density
    • C08G2110/0058—≥50 and <150kg/m3
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2120/00—Compositions for reaction injection moulding processes

Definitions

  • 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.
  • a high equivalent weight 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.
  • the polyol is mixed with the blowing agent and all the other components except the polyisocyanate to form a "B-side" composition which is then reacted with the polyisocyanate to form the foam-
  • 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-linker in preparing flexible foams.
  • polymer polyols and “polymer isocyanates” provide reinforcement through the presence of colloicallv sized polymer 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.
  • SAN styrene-acrylonitrile
  • PIPA polyisocyanate polyaddition
  • a further consideration is the preparation of low density foams by the use of increasing amounts of water in the foam formulation.
  • Foams are conventionally prepared using from 2-4 parts of water per 100 parts by weight polyol to provide a cellular structure.
  • this invention is an open-celled flexible 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) 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 secondary aliphatic or aromatic amine groups
  • component (C) less than 5 parts by weight of a cross-linker or chain extender per 100 parts of component (a), and
  • this invention is a process for preparing a polyurethane foam, comprising reacting a reaction mixture as described herein in a one-step process under conditions such that a flexible polyurea or polyurea-polyurethane foam is obtained.
  • 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 (a), 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 improvement 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.
  • this invention is an active hydrogen-containing composition comprising
  • (A) 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.
  • Active hydrogen-containing groups at least 30 percent are primary aromatic.
  • component (B) from 3-5 to 10 parts by weight of water per 100 parts by weight of component (A), and (C) from 0.1 to 4.5 parts by weight of a cross-linker or chain extender per 100 parts by weight component (a).
  • amine-terminated compound 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
  • the foams have particularly good load-bearing properties, even in the absence of a cross-linker.
  • 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, at a similar level of cross-linker use.
  • 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 excellent 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 higher amounts of water than was commercially possible using conventional processes.
  • an amine-terminated compound is used to prepare a flexible polyurea or polyurea-polyurethane foam.
  • An amine-terminated compound as that term is employed in this invention, means a relatively high equivalent weight compound or polymer, or mixture 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 aliphatic 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 1.5 to 4, preferably from 1.8 to 3, active hydrogen-containing groups per molecule.
  • the amine-terminated compound can be of any convenient structure as long as it contains no substituents which undesirably interfere with its ability to react with the polyisocyanate to form a polyurea or polyurea-polyurethane foam.
  • Especially suitable amine-terminated compounds are polyethers or polyesters having a plurality of active hydrogen-containing groups of which at least 30 percent are primary aromatic, Lewis acid-blocked primary aliphatic and/or secondary aliphatic or aromatic amine groups.
  • Suitable secondary aliphatic amine-terminated compounds include polyols, especially polyether and polyester polyols which have been modified to contain a proportion of secondary amine groups of from 30 to 100 percent, preferably from 50 to 100 percent, more preferably from 60 to 90 percent.
  • Such secondary aliphatic amine-terminated compounds are conveniently prepared by reacting the corresponding polyol with a primary amine, and reducing the resulting intermediate with hydrogen, as described in U.S. Patent 4, 153, 381.
  • the primary amine is advan tageous l y an inertly -substituted alkyl-, cycloalkyl- or benzylamine.
  • 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 polyisocyanate, 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; 3,347,9206; and 4,014,933.
  • Suitable aromatic amine-terminated compounds include polyols, especially polyether and polyester polyols, which have been modified to contain a proportion of aromatic amine groups.
  • Such compounds can be prepared, for example, by capping the corresponding polyether or polyester polyol with a diisocyanate to form a pr ⁇ polymer, and then reacting the prepolymer with water to hydrolyze the free isocyanate groups to the corresponding primary amine.
  • These types are less preferred due to their relatively high viscosity, which makes their processing more difficult.
  • such compounds can be prepared by reacting the corresponding polyether or pol3/ester polyol with a halogenated nitrobenzene compound such as o- or p-nitrochlorobenzene, or dinitrochlorobenzene, followed by the reduction of the nltro group(s) to the amine.
  • a halogenated nitrobenzene compound such as o- or p-nitrochlorobenzene, or dinitrochlorobenzene
  • the products are produced by the catalytic hydrogenation method.
  • 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 comprised of the platinum group metals which includes ruthenium, rhodium, palladium, osmium, iridium, and platinum.
  • the catalyst is supported on a carrier such as activated carbon, silica gel, alumina, diatomaceous earth, pumice, and the like.
  • a carrier such as activated carbon, silica gel, alumina, diatomaceous earth, pumice, and the like.
  • the exact proportions in which the elemental metal is present on the carrier is not a critical factor.
  • 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.
  • 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 1.0 mole percent.
  • the term "equivalent of nitro group” means 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 liquid phase in the presence of the hydrogen and the catalyst 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 (I) and (II) may be employed
  • the follow 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.
  • liquid amm ⁇ ttia is also contemplated.
  • the amount of solvent is not critical per se and any amount found to be efficacious can be employed.
  • the nitroaromatic compound (II) is employed in at least 10 prercent by weight in the solvent, preferably, from 20 to 70 percent by weight, and most preferably, from 25 to 50 percent by weight.
  • temperature in any given hydrogenation is a function of, for example, the specific catalyst activity and hydrogen pressure.
  • it can fall within a range of from 0°C to 200°C, preferably from 15°C to 100°C, most preferably from 20°C to 50°C.
  • 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) to 200 psig (1400 kPa gauge), preferably from 30 (100) to 60 psig (300 kPa gauge).
  • 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.
  • a material such as nitroanisole or a lower alkyl ester of p-aminobenzoic acid, particularly the methyl ester
  • Secondary amine-terminated compounds can be prepared in 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 are suitable herein are advantageously prepared in the reductive amination of the corresponding hydroxyl-terminated 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 carboxylate.
  • the Lewis acid is advantageously used in amounts of from 0.2 to 5, preferably 0.9 to 1.5, equivalents per equivalent of primary amine groups.
  • 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, i.e., at least 30 percent of the total amount of active hydrogen-containing groups contributed by the relatively high, equivalent weight compounds.
  • a polymer polyol such as a polyurea polyol dispersion (PHD polyol), a polyaddition polyisocyanate polyol dispersion (PIPA polyol), or an addition polymer 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.
  • PLD polyol polyurea polyol dispersion
  • PIPA polyaddition polyisocyanate polyol dispersion PIPA polyol
  • an addition polymer dispersion such as a styrene-acrylonitrile copolymer polyol
  • the preferred equivalent weight of the amine-terminated compound depends somewhat on the type of foam being made, and the method of its manufacture.
  • 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.
  • the most preferred equivalent weight is from 500 to 1800.
  • Either aliphatic or aromatic polyisocyanates can be used in this invention to make foam.
  • Suitable aliphatic polyisocyanates include, for example, ethylene diisocyanate, 1 , 4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,12-dodecane diisocyanate, cyciobutane-1,3-diisocyanate, cyclohexane- 1 , 3- and -1,4-diisocyanate, 1,5- -diisocyanato-3,3,5-trimethylcyclohexane, 2,4- and/or 2,6-hexahydrotoluene diisocyanate, perhydro-2,4'- and/or -4,4'-diphenylmethanediisocyanate (H 12 MDI) 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-phenylene 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 polyphenyl-polymethylene polyisocyanates.
  • TDI 2,4- and/or 2,6-toluene diisocyanate
  • 2,4'-diphenylmethanediisocyanate 1,3- and 1,4-phenylene diisocyanate
  • 4,4'-diphenylmethane diisocyanate including mixtures thereof with minor quantities of the 2,4'-isomer
  • derivatives and prepolymers of the foregoing polyisocyanates such as those containing urethane, carbodiimide, allophanate, isocyanurate, acylated urea, biuret, ester and similar groups are useful herein.
  • 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.
  • TDI 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 95 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.
  • preferred isocyanate indices are from 60 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 and a polyol. Such materials include air, carbon dioxide, nitrogen. 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.
  • 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.
  • 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.
  • this invention in excess of 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.
  • water provides a desirable density when used in an amount of from 0.5. preferably 3.5, more preferably 4 to 10, preferably 3, more preferably 6, parts per 100 parts amine-terminated compound.
  • ultra-low density foam less than 1.5 pounds per cubic foot density (10 kg/m 3 )
  • 5 to 10 parts of water are used for making ultra-low density foam.
  • a catalyst for the reaction of the amine-terminated compound and the polyisocyanate is also used in making foam according to this invention.
  • the most widely used and preferred catalysts are the tertiary amine catalysts and the organometallic catalysts.
  • Exemplary tertiary amine catalysts include, for example, triethylenediamine, N-methyl morpholine, N-ethyl morpholine, diethyl ethanolamine, N-coco morpholine, 1-methyl-4-dlmethylaminoethyl piperazine, 3-methoxy-N-dimethylpropylamine, N,N-diethyl-3-diethylaminopropylamlne, 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.
  • organometallic catalysts include organic salts of metals such as, for example, tin, bismuth, iron, mercury, zinc and lead, with the organotin compounds being preferred.
  • organotin catalysts include, for example, dimethyltindilaurate, dibutyltindilaurate and stannous octoate.
  • an organometallic catalyst 0.5 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 condi tion such that the components react to form a cellular polymer.
  • 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 lower 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.
  • 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.
  • diethanolamine 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 foams made without the amine-terminated compound.
  • cross-linker compound When used, however, less than 5 parts, preferably 0.1 to 4 parts of the cross-linker are advantageously employed per 100parts of the amine-terminated compound. It is most 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 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), NaCl blocked methylene bis(aniline), toluene diamine, 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, i.e., less than 5 parts by weight per 100 parts by weight amine-terminated compound. Most preferably, the combined weight of chain extender and cross-linker is less than 5 parts by weight per 100 parts by weight amine-terminated compound. It Is usually preferable, however, to prepare the foam in the absence of a chain extender.
  • a surfactant which stabilizes the foaming reaction mixture against collapse until the mixture is sufficiently cured to maintain its configuration
  • Suitable surfactants include siloxane poly(al kylene 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.
  • 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 surfactant in an amount of less than 0.5, preferably less than 0.25 part per 100 parts of amine-terminated compound.
  • the foam is prepared in the substantial absence of a surfactant.
  • 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.
  • all components except the polyisocyanate are advantageously blended together and injected as a single stream into a mixing head.
  • certain components such as catalysts or halogenated methane blowing agents are sometimes blended with the polyisocyanate.
  • the 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 the mold.
  • conventional, low pressure apparatus can be used, or high pressure impingement mixing processes, such as a reaction injection molding process, can be used.
  • high pressure impingement mixing processes such as a reaction injection molding process.
  • the components are mixed at approximately room temperature, although components such as pure MDI which are solid at room temperature may be heated above their melting points.
  • 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.
  • a second technique cold molding process
  • the reactants are placed into a mold which is preheated to a temperature of from 30°C to 75°C. After the mold is filled, it is placed in a 70°C to 150°C oven to effect cure.
  • the filled mold is maintained at ambient temperature during the curing process. In this third technique, the mold may or may not be preheated.
  • the reaction mixture Sufficient of the reaction mixture is placed into the mold so that, after expansion, the mixture completely fills the mold.
  • a small excess of material is added over that minimally required to fill 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.
  • an in-mold cure time of from 2 to 30 minutes is adequate for this purpose.
  • the foam can be postcured by heating to a temperatuere of from 50oC to 120oC for a period of from 10 minutes to 24 hours, preferably from 20 minutes to 2 hours.
  • the reaction mixture also advantageously contains a surfactant and catalyst as described before.
  • Cross-linkers although they may be used, are often omitted from slabstock formulations.
  • the components can be and typically are introduced individually to a mixing head where they are thoroughly blended and metered onto a bed where foaming takes place.
  • 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 useful in applications wherein good load-bearing characteristics are desired, or where a low density, high water formulation is desired.
  • a difunctional primary aromatic amine-terminated polyether was reacted with polymeric MDI to form molded foam.
  • Polyol A 1 0 100 0 100 diethanolamine 0 0.5 0 0.5
  • Silicone Surfactant A 3 0 0.75 0 0.75
  • Polyol A is a difunctional, 1000 equivalent weight poly(propylene oxide) which contains 18% by weight of a terminal poly (ethylene oxide) block.
  • Amine- terminated 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.
  • 2 A proprietary tertiary amine catalyst sold by Union Carbide Corporation as C225 catalyst.
  • Polyol B is a 165 0 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, 2 A 25% solids SAN copolymer polyol, using Polyol B as the base polyo 3 A 33 wt.-% solution in dipropylene glycol. 4 As a 10% solution in Amine-terminated Polyether B. 5 DC-5043, sold by Dow Corning Corporation. 6 A silicone oil soId by Dow Corning Corporation as DCF 11630. 7 A mixture of 80 weight percent of the 2,4- isomer and 20 weight percent of the 2,6- isomer.
  • Foam Sample Nos. 3-7 were prepared according to the general procedure described in Example 1, with results as indicated in Table IV following.
  • a nominally trifunctional secondary aliphatic amine-terminated polyether was reacted with an isomeric mixture of TDI to form a molded foam.
  • Silicone Surfactant B 4 2.0 1.65 1.65 dibutyltindilaurate 0.0042 0.0042 0.0042
  • Foams were made from each of these formulations by mixing all components except the TDI, and with all components at 78°F (25°C), blending in the TDI and pouring 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 (60°C). After filling the mold, it was closed and immediately placed into a 250°F (121°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.
  • foams had good properties. Of particular interest are the IFD and modulus values.
  • the IFD values provided by the foam of this invention were substantially higher.
  • 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 25 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.
  • the modulus values of this foam are very high, as is desired and difficult to achieve with the use of copolymer polyol.
  • Example No. 11 a molded polyurethane foam (Sample No. 11) was made using the general procedure described in Example 1.
  • the resulting foam had properties as set out in Table VIII.
  • TABLE VIII Density, lb/ft3 (kg/m 3 ) 2.20 ( 35 ) Tensile Str., psi (MPa) 1 18 .0 ( 0. 12 ) Elongation, % 1 83 Tear Str., lb/in 2 (N/m) 1 .37 ( 240 ) Resiliency, % 3 36 .6 Compression Set,% 4 80 IFD 5
  • ASTM D-3574-81 Test E. 2 ASTM D-3574-81 Test F. 3 ASTM D-3574-81 Test H. 4 ASTM D-3574-81 Test D. 5 ASTM D-3574-81 Test B. IFD is indentation force deflection. 6 Modulus 65%IFD/25%IFD. 7 ASTM D-3574-81.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

Des mousses flexibles de polyuréthane sont préparées en faisant réagir un polyisocyanate avec certains composés à terminaison amine. Les composés à terminaison amine se caractérisent en ce qu'au moins 30% de leurs groupes actifs contenant de l'hydrogène se présentent sous la forme de groupes amine primaires aromatiques, de groupes amine aliphatiques primaires bloqués par un acide de Lewis et/ou de groupes amine aliphatiques ou aromatiques secondaires. Les mousses obtenues présentent d'excellentes propriétés physiques, même en l'absence d'un composé de réticulation.
PCT/US1988/000935 1987-04-07 1988-03-24 Mousses flexibles de polyuree ou polyuree-polyurethane preparees a partir de composes a terminaison amine de poids equivalent eleve et leur procede de preparation WO1988008009A1 (fr)

Priority Applications (2)

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BR888807445A BR8807445A (pt) 1987-04-07 1988-03-24 Espumas flexiveis de poliureia ou poliureia-poliuretana,preparadas a partir de compostos terminados em amina de peso equivalente elevado,e processo para preparacao das mesma
JP63503240A JPH06102710B2 (ja) 1987-04-07 1988-03-24 高当量アミン末端化合物より製造された軟質ポリウレアもしくはポリウレア‐ポリウレタンフォームおよびその製造方法

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US3568187A 1987-04-07 1987-04-07
US035,681 1987-04-07

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WO (1) WO1988008009A1 (fr)

Cited By (2)

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US6278180B1 (en) 1997-06-04 2001-08-21 Nikko Company Ball-grid-array-type semiconductor device and its fabrication method and electronic device
CN117946479A (zh) * 2024-03-27 2024-04-30 广州仕天材料科技有限公司 一种抗冲击耐热的聚丙烯复合材料和制备方法

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NZ231430A (en) * 1988-11-25 1991-08-27 Ici Plc Preparation of polyurethane foams which includes the use of an amino chain extender and a mixture of at least two other chain extenders
JP2010515811A (ja) * 2007-01-10 2010-05-13 アルベマール・コーポレーシヨン 反応射出成形および噴霧システムのための組成物
AU2010330056B2 (en) * 2009-12-11 2015-03-26 Basf Se Improved porous materials based on aromatic amines
CN101905505A (zh) * 2010-07-06 2010-12-08 杭州长命乳胶海绵有限公司 慢反弹海绵的生产方法
CN105418881B (zh) * 2015-12-29 2018-09-07 哈尔滨工业大学 一种聚脲泡沫材料及其制备方法
CN110643009A (zh) * 2018-06-27 2020-01-03 科思创德国股份有限公司 聚氨酯软质泡沫
CN112566954B (zh) * 2018-08-22 2022-09-09 三洋化成工业株式会社 多元醇组合物和聚氨酯泡沫
CN112409560B (zh) * 2019-08-21 2022-09-20 万华化学（北京）有限公司 一种高回弹聚氨酯泡沫及其制备方法

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EP0081701A1 (fr) * 1981-12-02 1983-06-22 Bayer Ag Procédé pour la production d'articles moulés élastiques
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US6278180B1 (en) 1997-06-04 2001-08-21 Nikko Company Ball-grid-array-type semiconductor device and its fabrication method and electronic device
CN117946479A (zh) * 2024-03-27 2024-04-30 广州仕天材料科技有限公司 一种抗冲击耐热的聚丙烯复合材料和制备方法
CN117946479B (zh) * 2024-03-27 2024-06-11 广州仕天材料科技有限公司 一种抗冲击耐热的聚丙烯复合材料和制备方法

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AU605860B2 (en) 1991-01-24
CN1027815C (zh) 1995-03-08
AU1548588A (en) 1988-11-04
JPH06102710B2 (ja) 1994-12-14
CN1030086A (zh) 1989-01-04
BR8807445A (pt) 1990-05-15

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