WO1997015606A1 - Formulation pour mousse de polyurethane a fluidite amelioree et mousses de polyurethane flexibles produites avec lesdites formulations - Google Patents

Formulation pour mousse de polyurethane a fluidite amelioree et mousses de polyurethane flexibles produites avec lesdites formulations Download PDF

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Publication number
WO1997015606A1
WO1997015606A1 PCT/US1996/016467 US9616467W WO9715606A1 WO 1997015606 A1 WO1997015606 A1 WO 1997015606A1 US 9616467 W US9616467 W US 9616467W WO 9715606 A1 WO9715606 A1 WO 9715606A1
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viscosity
polyol
less
copolymer
cps
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PCT/US1996/016467
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English (en)
Inventor
Oomman P. Thomas
Dana R. Gier
David E. Laycock
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The Dow Chemical Company
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Priority to AU74311/96A priority Critical patent/AU7431196A/en
Publication of WO1997015606A1 publication Critical patent/WO1997015606A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
    • 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
    • C08G18/63—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers
    • C08G18/632—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers onto polyethers
    • 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
    • C08G18/63—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers
    • C08G18/636—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers characterised by the presence of a dispersion-stabiliser
    • 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

Definitions

  • This invention relates to polyurethane foam formulations and a method for preparing polyurethane foams.
  • This invention particularly relates to low viscosity, high solids copolymer polyols for use in polyurethane foam formulations.
  • foams are useful in a variety of applications.
  • foams are used in seat cushions, automobile head rests, ca ⁇ et pads, and other applications where flexible support is desirable.
  • flexible foams include both molded foams and slabstock foams. It is important that polyurethane foams are prepared by processes that do not detrimentally affect the performance ofthe foams in the various applications in which they are used. At the same time it is important that polyurethane foams are produced by rapid and efficient processes.
  • Polyurethane foams are sometimes prepared under conditions designed to promote rapid curing of the foam, and high catalyst levels are usually necessary for this result. Using high levels of catalyst where rapid curing is desirable may present difficulties, since a high catalyst level can cause a decrease in the flowability of a polyurethane foam formulation (hereinafter foam formulation). Decreased flowability of the foam formulation might be observed, for example, while pouring the foam formulation into a mold or after the foam formulation is poured into the mold.
  • foam formulation is a mixture that contains all of the ingredients required to prepare a polyurethane foam.
  • a typical foam formulation can include base polyols, copolymer polyols, isocyanates, catalysts, cell openers, blowing agents, mold release agents, water and surfactants.
  • Low initial viscosity is important in a foam formulation since low initial viscosity will promote efficient flow ofthe foam formulation. Efficient flow ofthe foam formulation is obtained, for example, when the foam formulation flows freely into a mold. Efficient flow during pouring is important to allow the foam formulation to adequately fill the mold or cover the slab and prevent the formation of void spaces (voids) in the foam during the pouring step. Voids are considered defects which diminish the properties ofa flexible foam, and high void volume is an undesirable characteristic of a foam.
  • the foam formulation may not fill a mold or cover the slab area properly.
  • Various factors can contribute to high viscosity in foam formulations.
  • One such factor is premature gelation caused by the presence of high catalyst levels in the foam formulation.
  • Another factor is that the copolymers in copolymer polyols can increase the viscosity of the polyol formulation.
  • Still another factor is that high molecular weight polyols used in typical copolymer polyols can also contribute to an increase in the viscosity of a foam formulation.
  • High molecular weight polyols in addition to contributing to high viscosity in copolymer polyols, can have unsaturated monols present as an impurity. Unsaturated monols are formed, for example, when a diol is dehydrated. The presence of unsaturated monols in a foam formulation can detrimentally affect the physical properties of a molded foam. For example, the load bearing and resiliency properties of a molded foam can be detrimentally affected by the presence of unsaturated monols. Attempts have been made in the art to prepare compositions for use in polyurethane processes having low initial viscosity or low unsaturated monol content. U.S.
  • the present invention is copolymer polyol composition
  • the present invention is a method of preparing a low viscosity, high solids copolymer polyol composition
  • a method of preparing a low viscosity, high solids copolymer polyol composition comprising the steps dispersing polymerizable ethylenically unsaturated monomers in a polyol solvent matrix, the solvent matrix including a low molecular weight diol component, a low molecular weight triol component, and a stabilizer; polymerizing the monomers in the solvent matrix, wherein the copolymer polyol composition has an unsaturation level of less than 0.03 meq/g, a solids content of at least 40 percent by weight, and a viscosity of less than 4500 cps.
  • the present invention is a method for lowering the viscosity of polyurethane foam formulations comprising preparing a polyurethane foam formulation wherein the formulation includes a copolymer polyol composition having as part ofthe composition a low molecular weight diol having a molecular weight of 200 to 3000, a low molecular weight triol having a molecular weight from 300 to 4000, and a copolymer of copolymerizable ethylenically unsaturated monomers, wherein the copolymer polyol composition has an unsaturated monol level of less than 0.03 meq/g, a solids content of at least 40 percent by weight, and a viscosity of less than 4500 cps.
  • the formulation includes a copolymer polyol composition having as part ofthe composition a low molecular weight diol having a molecular weight of 200 to 3000, a low molecular weight triol having a molecular weight from 300 to 4000, and
  • this invention is a low viscosity polyurethane foam formulation comprising a low viscosity polyol formulation and an isocyanate formulation
  • the polyol formulation includes a copolymer polyol composition having as part of the composition a polymer formed from a dispersion of polymerizable ethylenically unsaturated monomers in a polyol solvent matrix, the solvent matrix having a low molecular weight diol component, a low molecular weight triol component, and a stabilizer; and wherein the copolymer polyol composition has an unsaturation level of less than 0.03 meq/g, a solids content of at least 40 percent by weight, and a viscosity of less than 4500 cps.
  • polyurethane foam made by a process wherein a polyurethane foam formulation is prepared by combining a low viscosity polyol composition with an isocyanate composition, wherein the polyol formulation includes a copolymer polyol composition having as part ofthe composition a polymer formed from a dispersion of polymerizable ethylenically unsaturated monomers in a polyol solvent matrix, the solvent matrix having a low molecular weight diol component, a low molecular weight triol component, and a stabilizer; and wherein the copolymer polyol composition has an unsaturation level of less than 0.03 meq/g, a solids content of at least 40 percent by weight, and a viscosity of less than about 4500 cps.
  • the present invention is a low viscosity, high solids copolymer polyol formulation which includes a copolymer that is derived from ethylenically unsaturated monomers, and a method making the same.
  • the copolymer is dispersed in a solvent matrix consisting of a mixture of low molecular weight diols and low molecular weight triols.
  • the copolymer polyol dispersion can be combined with a base polyol to make a polyol composition which has low viscosity, and is suitable for reaction with an isocyanate compound in a process for preparing polyurethane molded foams.
  • the diol and triol components ofthe present invention can be derived from alkylene oxides.
  • Representative diols and triols suitable for use in this invention are generally known and are described in such publications as High Copolymers. Vol. XVI, "Polyurethanes, Chemistry and Technology” by Saunders and Frisch, Interscience Publishers, New York, Vol. I, pp. 32-42, 44-54 (1962) and Vol. II, pp. 5-6,198-199 (1964); Organic Copolymer Chemistry by K. J. Saunders, Chapman and Hall, London, pp. 323-325 (1973); and Developments in Polyurethanes. Vol. I, J. M. Burst, ed., Applied Science Publishers, pp.
  • Examples of such materials include those selected from the following classes of compositions, alone or in admixture: (a) alkylene oxide adducts of poly hydroxy alkanes; (b) alkylene oxide adducts of non- reducing sugars and sugar derivatives; (c) alkylene oxide adducts of phosphorus and polyphosphorus acids; and (d) alkylene oxide adducts of polyphenols.
  • alkylene oxide adducts of polyhydroxyalkanes useful herein are adducts of ethylene glycol, propylene glycol, 1 ,3-dihydroxypropane, 1 ,4-dihydroxybutane, and 1 ,6- dihydroxyhexane, glycerol, 1 ,2,4-trihydroxybutane, 1 ,2,6-trihydroxyhexane, 1,1,1- trimethylolethane, 1 , 1 , 1 -trimethylolpropane, and similar compounds.
  • Preferred herein as alkylene oxide adducts of polyhydroxyalkanes are the ethylene and propylene oxide adducts of trihydroxyalkanes and dihydroxyalkanes.
  • the molecular weight ofthe diol component ofthe copolymer polyol is in the range from 200 to 3000.
  • the molecular weight ofthe diol component is from 500 to 3000. More preferably the molecular weight ofthe diol component is from 500 to 2500. Most preferably the molecular weight of the diol component is from 600 to 2500.
  • molecular weight can also be expressed in terms of an equivalent weight, which is the molecular weight divided by the functionality ofthe molecule or polymer.
  • the molecular weight of the triol component ofthe copolymer polyol is in the range from 300 to 4000.
  • the triol component has a molecular weight of from 400 to 4000. More preferably the triol component has a molecular weight of from 500 to 3500. Most preferably, the triol component has a molecular weight of from 750 to 3500.
  • molecular weight can also be expressed in terms of an equivalent weight, which is the molecular weight divided by the functionality ofthe molecule or polymer.
  • alkylene oxide adducts ofthe type described previously can be prepared by combining an alkylene oxide, such as propylene oxide or butylene oxide, with an initiator such as ethylene glycol or propylene glycol, in the presence of an alkaline catalyst such as potassium hydroxide.
  • the ratio of initiator to alkylene oxide can be any ratio that is effective in making a polyol that has the desirable functionality and molecular weight.
  • a ratio of oxide to initiator of from 2 to 1 to 70 to 1 , preferably from 4 to 1 to 60 to 1 , more preferably from 6 to 1 to 60 to 1 may be used to make the diols and triols of this invention.
  • the catalyst may be present in an amount from 1 percent to 10 percent, preferably from 2 percent to 8 percent, more preferably from 2 percent to 6 percent based on the weight ofthe initiator.
  • Elevated temperature may advantageously be employed to effect the polymerization.
  • a suitable temperature may be any temperature above 20 °C.
  • the temperature range is from 20 to 200 °C. More preferably the temperature range is from 50 to 180 °C. Most preferably the temperature range is from 100 to 150 °C.
  • the copolymer component of the copolymer polyol is derived from monomers having polymerizable ethylenic unsaturation.
  • the copolymer component ofthe copolymer polyol is the sometimes referred to herein as the "solids" component and, for the purposes of this invention, is equal to the amount of monomer added to the solvent matrix. Suitable monomers are disclosed in U.S. Patent No. 4,581 ,418, incorporated herein by reference.
  • Such monomers include aliphatic conjugated dienes such as butadiene; monovinylidine aromatics such as styrene, ⁇ -methylstyrene and vinylnapthalene, including other inertly substituted styrenes; ⁇ , ⁇ -ethylenically unsaturated carboxylic acids and esters such as acrylic acid, methacrylic acid, 2- hydroxyethacrylic acid and other similar compounds; ⁇ , ⁇ -ethylenically unsaturated nitriles such as acrylonitrile; acrylamide; vinyl esters such as vinyl acetate; vinyl ethers; vinyl ketones; vinyl and vinylidene halides and similar compounds.
  • aliphatic conjugated dienes such as butadiene
  • monovinylidine aromatics such as styrene, ⁇ -methylstyrene and vinylnapthalene, including other inertly substituted styrenes
  • the hydroxyl number ofthe copolymer can range from 20 to 40. Preferably the hydroxyl number of the copolymer can range from 22 to 37. More preferably the hydroxyl number ofthe copolymer can range from 25 to 35.
  • a high solids, low viscosity copolymer polyol dispersion ofthe present invention is advantageously prepared by polymerizing ethylenically unsaturated monomers in the presence of a free radical initiator and a stabilizer, typically employing heat and agitation to obtain a suitable dispersion.
  • the term "high solids” is herein defined as solids content of at least 40 percent by weight of the total dispersion.
  • a suitable copolymer polyol is advantageously prepared by dispersing the ethylenically unsaturated monomers in a heated matrix of low molecular weight diol, low molecular weight triol, or a mixture of low molecular weight diol and low molecular weight triol in the presence of a free radical initiator and a stabilizer.
  • the temperature at which the process is carried out can vary from 20 to 150 °C, preferably from 80 to 130 °C, more preferably from 105 to 125 °C. The temperature that is used can depend somewhat on the monomers and free radical initiator used.
  • the monomers may be inco ⁇ orated such that a solids level of greater than 40 percent by weight ofthe total dispersion is obtained. Preferably the solids level is at least 40 percent and not greater than 60 percent, more preferably at least 40 and not greater than 50 percent.
  • a free radical initiator is usually added to the monomer dispersion to facilitate the polymerization of the ethylenically unsaturated monomers.
  • Sufficient free radical initiator is added to provide a commercially acceptable polymerization rate.
  • the free radical initiator is used in an amount from 0.1 to 1.75, preferably from 0.2 to 1, more preferably from 0.25 to 0.8 percent based on the weight ofthe monomers.
  • Initiators suitable for use in this invention include peroxyesters, peroxides, persulfates, percarbonates and perborates and similar such compounds. Azo compounds are also useful.
  • Examples of useful initiator compounds include hydrogen peroxide, t-butylperoctoate, di(t-butyl)peroxide, lauroyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, 2,2'-azobis (2,4-diethyl)pentanenitrile, 2-(t-butylazo)-2,4-dimethylpentenitrile, azobis(isobutyronitrile), azobis(methylbutyronitrile) as well as mixtures of such compounds.
  • the azo compounds particularly azobis(isobutyronitrile) and azobis(methylbutyronitrile), are preferred.
  • chain transfer agents such as are described, for example, in U.S. 4,689,354, inco ⁇ orated herein by reference.
  • Preferred chain transfer agents include various mercaptans such as tertiary dodecyl mercaptan, ⁇ -toluenethiol, 1 -tetradecanethiol, 2-octanethiol, 1- octanethiol, 1-heptanethiol, 1-hexanethiol, 2-napthalenethiol, 1-napthalenthiol, ethanethioi, 1 -dodecanethiol, benzyl sulfide, iodoform, iodine and similar such compounds.
  • mercaptans such as tertiary dodecyl mercaptan, ⁇ -toluenethiol, 1 -tetradecanethiol, 2-octanethiol, 1- octanethiol, 1-heptanethiol, 1-hexanethiol, 2-napthalenethi
  • the use of chain transfer agents has been found in some cases to improve the stability and filterability of the product copolymer polyol, particularly when used in an amount from 0.1 to 5, preferably from 0.25 to 2.5, most preferably from 0.5 to 1 percent based on the weight of the vinyl monomers.
  • the copolymer polyol is prepared in the presence of a seed polymer, which is a copolymer polyol that is present in an amount sufficient to promote copolymer growth on the surface ofthe seed polymer.
  • the polymerization ofthe unsaturated monomers is carried out in a polyol solvent matrix in the presence of a stabilizer.
  • the stabilizer is a molecule having polymerizable ethylenic unsaturation and active hydrogen functionality.
  • stabilizer is not critical to the practice of this invention. Examples and methods of preparing stabilizers are described in U.S. Patent No. 4,883,832, U.S. Patent No. 4,390,645 and Serial No. 08/291,786 to Moore, et al. filed August 17, 1994 (allowed August, 1995), each inco ⁇ orated herein by reference.
  • stabilizers suitable for use in this invention include vinyltrialkoxysilanes, alkyl vinyldialkoxysilanes, and dialkyl vinylalkoxysilanes, linear macromers, and unsaturated polyether polyols obtained by reaction ofa polyether polyol with the anhydride of an unsaturated acid.
  • Copolymer polyols that are suitable for the practice of the present invention can be obtained by mixing low molecular weight diols, low molecular weight triols, or mixtures thereof, with low molecular weight diol based copolymer polyols, low molecular weight triol based copolymer polyols, or mixtures thereof.
  • a copolymer polyol ofthe present invention can be prepared by mixing a diol based copolymer polyol with a triol based copolymer polyol. The copolymer polyol mixture produced is within the scope ofthe present invention.
  • a low molecular weight triol within the scope of this invention can be mixed with a diol based copolymer polyol to make a copolymer polyol that is within the scope of this invention.
  • a copolymer polyol ofthe present invention can be prepared from a triol based copolymer polyol mixed with a suitable diol.
  • Still another alternative is to polymerize suitable ethylenically unsaturated monomers in a polyol matrix which is prepared from a mixture of a low molecular weight diol and a low molecular weight triol.
  • the copolymer polyol is "diol based". If the copolymer polyol is prepared using a triol solvent matrix, the copolymer polyol is "triol based”. If the copolymer polyol is prepared using a diol/triol mixture as a solvent matrix, the copolymer polyol is "dioi/triol based". Copolymer polyols prepared by mixing diol based, triol based, or diol/triol based copolymer polyols with diols or triols that are within the scope of this invention are also within the scope of this invention.
  • Copolymer polyols ofthe present invention have viscosities of less than 4500 cps.
  • copolymer polyols ofthe present invention have viscosities of greater than 2000 cps and less than 4000 cps. More preferably, copolymer polyols ofthe present invention have viscosities greater than 2300 cps and less than 3900 cps. Most preferably, copolymer polyols ofthe present invention have viscosities of greater than 2500 cps and less than 3500 cps.
  • Low viscosity polyol compositions can be prepared by mixing the copolymer polyols ofthe present invention with any base polyol composition known in the art to be useful for preparing polyurethane foams.
  • base polyol as used herein describes an active hydrogen containing composition that is capable of reaction with an isocyanate to form polyurethanes.
  • Base polyols useful in the present invention can be derived from, but are not limited to, the materials used to prepare the diol and triol components ofthe claimed copolymer polyols.
  • Such materials include those selected from the following classes of compositions, alone or in admixture: (a) alkylene oxide adducts of polyhydroxyalkanes; (b) alkylene oxide adducts of non- reducing sugars and sugar derivatives; (c) alkylene oxide adducts of phosphorus and polyphosphorus acids; and (d) alkylene oxide adducts of polyphenols.
  • alkylene oxide adducts of polyhydroxyalkanes useful herein are adducts of ethylene glycol, propylene glycol, 1,3-dihydroxypropane, 1 ,4-dihydroxybutane, and 1,6- dihydroxyhexane, glycerol, 1,2,4-trihydroxybutane, 1 ,2,6-trihydroxyhexane, 1,1,1- trimethylolethane, 1,1,1 -trimethylolpropane, pentaerythritol, polycaprolactone, xylitol, arabitol, sorbitol, manitol,.
  • alkylene oxide adducts of polyhydroxyalkanes are the ethylene oxide adducts of trihydroxyalkanes.
  • Other useful adducts include ethylene diamine, glycerin, ammonia, 1,2,3,4-tetrahydroxy butane, fructose, and sucrose.
  • poly(oxypropylene) glycols triols, tetrols and hexols and any of these that are capped with ethylene oxide.
  • These polyols also include poly(oxypropyleneoxyethylene)polyols.
  • Ethylene oxide, when used, can be inco ⁇ orated in any way along the copolymer chain, for example, as internal blocks, terminal blocks, or randomly distributed blocks, or any combination thereof.
  • copolymer polyols ofthe present invention are mixed with a base polyol in any amount sufficient to impart to the polyol composition a percent solids level in the range from 10 percent to 40 percent.
  • a copolymer polyol having a percent solids level of 40 percent can be mixed with a base polyol at a ratio of 25 to 75 by volume of copolymer polyol to base polyol, to give a polyol composition with a percent solids level of 10 percent.
  • a copolymer polyol ofthe present invention having 40 percent solids can be mixed in a 1 to 1 ratio, by volume, with a base polyol to give a polyol formulation of 20 percent solids.
  • the polyol composition ofthe present invention may optionally include other components such as, for example, water, catalysts, fillers, crosslinkers, surfactants, cell openers, mold release agents, flame retardants, and blowing agents.
  • Blowing agents for the pu ⁇ ose of this invention, include any material which generates a gas under the conditions ofthe reaction of the polyol with an isocyanate or polyisocyanate. Examples of blowing agents are water, low-boiling hydrocarbons and halogenated hydrocarbons, azo-compounds which release nitrogen, and similar materials.
  • Suitable hydrocarbons and halogenated hydrocarbons include pentane, hexane, heptane, pentene, and heptene, dichlorodiflouromethane, trichloroflouromethane, 1,1,1 -trichloroethane and methylene chloride. Water and mixtures thereof with low boiling hydrocarbons and halogenated hydrocarbons are preferred.
  • catalysts examples include tertiary amine catalysts such as triethylene diamine, N-methyl mo ⁇ holine, N-ethyl mo ⁇ holine, diethylethanolamine, N-coco mo ⁇ holine, l-methyl-4-dimethylaminoethyl piperazine, bis(N,N-dimethylaminoethyl)ether and similar compounds.
  • Amine catalysts are usually used in an amount of from 0.1 to 5, preferably from 0.2 to 2 parts per 100 parts of polyol formulation.
  • Organometallic catalysts are also suitable, and examples include organolead, organoiron, organomercury, organobismuth, and preferably organotin compounds.
  • organotin compounds such as dibutyltin dilaurate, dimethyltin dilaurate, stannous octoate, stannous chloride and similar compounds.
  • Organometallic compounds are usually used in an amount from 0.05 to 0.2 parts per 100 parts of polyol formulation.
  • crosslinkers are diethanolamine and methylene bis(o-chloroaniline) and similar compounds.
  • surfactants are silicone surfactants, most of which are block copolymers containing at least one polyoxyalkylene segment and one poly(dimethylsiloxane) segment.
  • surfactants include polyethylene glycol ethers of long chain alcohols, tertiary amine or alkanolamine salts of long chain alkyl sulfate esters, alkyl sulfonic esters and alkylaryl sulfonic acids. When used, 0.1 to 3, preferably 0.3 to 1 part by weight of surfactant to 100 parts of polyol formulation is normally adequate.
  • cell openers, mold release agents, flame retardants, fillers, and other additives are known in the art to modify the properties and aid in the processability ofthe foam.
  • Polyol compositions that inco ⁇ orate the copolymer polyols ofthe present invention have significantly lower viscosity than conventional polyol compositions having similar solids content.
  • polyols with similar solids levels typically have viscosities greater than 3900 cps, while polyols of the present invention typically have viscosities lower than 3900 cps.
  • polyols of the present invention have viscosities of less than 3500 cps. More preferably, polyols of the present invention have viscosities of less than 3000 cps. Most preferably, polyols ofthe present invention have viscosities of less than 2500 cps.
  • Low viscosity in a polyol formulation facilitates the polyurethane forming process by lowering the viscosity of polyurethane foam formulations and decreasing the incidence of defective foams that can result from high viscosity polyurethane foam formulations.
  • the low viscosity polyol compositions of this invention have low levels of unsaturated monols (monols) present.
  • the level of monols present is less than 0.03 meq/g.
  • the monol content is less than 0.025 mq/g. More preferably, the monol content is less than 0.02 meq/g.
  • this invention is a foam prepared from polyurethane foam compositions which include the copolymer polyols of the present invention.
  • Foams ofthe present invention are advantageously prepared by combining the low viscosity polyol compositions ofthe instant invention with an isocyanate composition or polyisocyanate composition to form a low viscosity polyurethane foam composition, pouring the foam composition into a mold or on a slab maintained at a temperature effective for sustaining the polyurethane reaction, allowing the foam to rise, removing the foam, passing the foam through a foam crusher.
  • the temperature is held at 20 to 150, preferably from 40 to 125, more preferably from 50 to 100 °C.
  • the foam is typically cured within about 8 minutes.
  • the isocyanate or polyisocyanate used in this invention is not unique to this invention. Any isocyanate used in the art is suitable for the practice of this invention. Useful isocyanates are described in U.S. Patent No. 4,785,027, inco ⁇ orated herein by reference.
  • Suitable isocyanates include: the isomers of toluene diisocyanate (TDI) such as 2,4-toluene diisocyanate and 2,6- toluene diisocyanate; prepolymers of TDI; bis(4-isocyanatophenyl)methane (MDI); prepolymers of MDI; bis(isocyanatoethyl fumerate); dianisidine diisocyanate; toluidine diisocyanate; 1 ,6-hexamethylene diisocyanate; and mixtures of at least any two suitable compounds of this type.
  • TDI toluene diisocyanate
  • MDI bis(4-isocyanatophenyl)methane
  • MDI bis(isocyanatoethyl fumerate)
  • dianisidine diisocyanate toluidine diisocyanate
  • 1 ,6-hexamethylene diisocyanate and mixtures of at least
  • copolymer polyols prepared herein were analyzed for particle size and unsaturation level. Particle size distribution ofthe copolymer polyol was determined using a HORIBA Particle Size Analyzer. The sample was measured against a "blank" methanol reference. The unsaturation level was determined using ASTM Method D- 4671-87.
  • Viscosity was determined using a Brookfield Viscometer, the pivot shaft was initially set at 6. The sample was kept at a constant temperature of 25 °C prior to the viscosity measurement. The #3 spindle was carefully placed in the sample (946 mL) and air bubbles eliminated by gently swirling the spindle in the sample. The spindle was connected to the viscometer without removing it from the sample, and the sample positioned so that the spindle was centered in the sample, and the notched indicator on the spindle was level with the surface of the sample. The viscometer motor was turned on and the pivot shaft setting was adjusted until the readout was close to 50 percent of the scale. The previous step may be repeated as many times as necessary.
  • the tube in a heating block for at least two hours, the sample must be at constant temperature and have no air bubbles;
  • a slurry prepared from 571.6 g ofthe diol/triol blend, a free radical initiator (10.78 g), and a stabilizer (100 g) was fed into the reactor, together with styrene (752.5 g), acrylonitrile (322.5 g) and docecyl mercaptan (10.75 g).
  • the reactants were fed to the reactor over a period of 104 minutes, total.
  • the copolymer polyol had a viscosity of 3280 cps, with 42.7 percent solids, a median particle size of 0.49 ⁇ m, and unsaturated monol content of less than 0.02 meq/g.
  • a reactor pressurized to 50 psia held at 125 °C was charged with 6667 g of molecular weight 2000 diol , including a stabilizer (3 percent of total reactor charge).
  • To the reactor was fed 1860.3 g of a slurry made from 85.50 g of free radical initiator in 4333 g ofthe diol with stirring. The slurry was fed over a 65-minute period.
  • Example 2 The procedure of Example 2 was followed, except that 100 percent of a 19.5 percent ethylene oxide capped triol having an equivalent weight of 1000 was used in lieu of the diol.
  • a low molecular weight polyol mixture was made by combining a 510 equivalent weight diol and a 666 equivalent weight triol in a ratio of 35 parts diol to 65 parts triol.
  • a reactor pressurized to 50 psia held at 125 °C was charged with 6667 g of the diol/triol blend, including a stabilizer (2.75 percent of total reactor charge).
  • To the reactor was fed 1860.3 g of a slurry made from 85.50 g of free radical initiator in 4333 g ofthe diol/triol blend, with stirring. The slurry was fed over a 65-minute period. Acrylonitrile (2700.1 g) was fed to the reactor over a period of 65 minutes.
  • styrene (300 g) was fed to the reactor over a period of 63 minutes, along with 90.28 g of docecyl mercaptan, which was added over a period of 61 minutes.
  • the remaining slurry containing free radical initiator was added to the reactor over a 43-minute period.
  • the copolymer polyol had a particle size of 0.76 ⁇ m, solids level of 43.3 percent, and a viscosity of 2610 t ⁇ , with less than 0.02 meq/g unsaturated compounds.
  • the diol and triol based copolymer polyols listed in Table 1 were prepared using diols and triols made according to the procedures in the previous examples.
  • Low viscosity copolymer polyols ofthe present invention, listed in Table 2 were prepared by combining the diol based copolymer polyols with the triol based copolymer polyol listed in Table 1 according to the ratio given in Table 2, with one exception as noted in Table 2.
  • diol has ⁇ 0 02 meq/g unsaturated monols b
  • triol has ⁇ 0 02 meq/g unsaturated monols
  • Control is styrene-acrylonitrile copolymer polyol in a 1000 equivalent weight triol solvent matrix
  • Molded pads were prepared from 460 g of a low viscosity polyol formulation (S3) and the required amount of TDI for either a 100 or a 103 index.
  • S3 low viscosity polyol formulation
  • the mixture of the polyol formulation and TDI was poured into a 380x380x100 mm mold maintained at a temperature of 68 °C +1 °C.
  • the rising foam was extruded through four small vents located in the lid of the mold, and the time of the last extrusion was recorded as the mold fill time.
  • the demold time was six minutes, and the pad was passed through a crusher to open the cells.
  • Foams were made using the copolymer polyol blends in Table 2. The make-up of each foam formulation was given in Table 3 using sample numbers that correspond to the numbering in Table 2.
  • A COPOLYMER POLYOL
  • B BASE POLYOL
  • C WATER
  • D CROSSLINKER
  • E CATALYST 1
  • F CATALYST 2
  • G SURFACTANT
  • H CELL OPENER
  • Indention Force Deflection testing was done according to ASTM METHOD 3574 (1991). The results of the testing on the foams prepared using the formulations in Table 3 were listed in Table 4.
  • the Box Foam Procedure above, was followed except that there were two vents in the lid ofthe maze mold.
  • the maze mold contains three separate compartments with variable depth and were connected to each other through small pathways in the corners of each compartment. The flow time was recorded as foam was extruded from the last vent. The results were reported in Table 7.

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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)
  • Dispersion Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

L'invention concerne une formulation de cocolymères de polyols à faible viscosité et à haute teneur en solides, ainsi qu'un procédé pour les fabriquer. L'invention concerne également des mousses en polyuréthane préparées par moulage, en utilisant ces colymères de polyols. Les copolymères de polyols de la présente invention ont été préparés à partir de diols de faible poids moléculaire et de triols de faible poids moléculaire. Ces copolymères ont une fluidité améliorée et ils sont plus faciles à mettre en oeuvre dans les réactions de formation de polyuréthanes. Les copolymères de polyols de la présente invention sont également caractérisés par un niveau très bas d'impuretés insaturées.
PCT/US1996/016467 1995-10-23 1996-10-15 Formulation pour mousse de polyurethane a fluidite amelioree et mousses de polyurethane flexibles produites avec lesdites formulations WO1997015606A1 (fr)

Priority Applications (1)

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AU74311/96A AU7431196A (en) 1995-10-23 1996-10-15 Polyurethane foam formulations having improved flowability and flexible polyurethane foams prepared therewith

Applications Claiming Priority (2)

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US582895P 1995-10-23 1995-10-23
US60/005,828 1995-10-23

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1295266C (zh) * 2004-09-30 2007-01-17 青岛科技大学 阻燃高活性聚合物聚醚多元醇制备方法及其用于制备高回弹阻燃聚氨酯软泡材料的方法
CN1308373C (zh) * 2004-09-30 2007-04-04 青岛科技大学 阻燃聚合物聚醚多元醇制备方法及其用于制备块状阻燃聚氨酯泡沫材料的方法
WO2008005708A1 (fr) * 2006-07-05 2008-01-10 Dow Global Technologies Inc. Polyols de copolymères et leur procédé de production

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0162588A1 (fr) * 1984-04-24 1985-11-27 Polyol International B.V. Préparation d'un polymère polyol
JPS61136512A (ja) * 1984-12-07 1986-06-24 Yokohama Rubber Co Ltd:The ポリウレタンプレポリマ−組成物

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0162588A1 (fr) * 1984-04-24 1985-11-27 Polyol International B.V. Préparation d'un polymère polyol
US4883832A (en) * 1984-04-24 1989-11-28 Bp Chemicals Limited Preparation of polymer polyols
JPS61136512A (ja) * 1984-12-07 1986-06-24 Yokohama Rubber Co Ltd:The ポリウレタンプレポリマ−組成物

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 106, no. 12, 23 March 1987, Columbus, Ohio, US; abstract no. 86369u, page 91; XP000015116 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1295266C (zh) * 2004-09-30 2007-01-17 青岛科技大学 阻燃高活性聚合物聚醚多元醇制备方法及其用于制备高回弹阻燃聚氨酯软泡材料的方法
CN1308373C (zh) * 2004-09-30 2007-04-04 青岛科技大学 阻燃聚合物聚醚多元醇制备方法及其用于制备块状阻燃聚氨酯泡沫材料的方法
WO2008005708A1 (fr) * 2006-07-05 2008-01-10 Dow Global Technologies Inc. Polyols de copolymères et leur procédé de production
CN101501086B (zh) * 2006-07-05 2012-07-04 陶氏环球技术有限责任公司 共聚物多元醇及其制备方法

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