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WO2011090627A1 - Mousse de polyuréthane résistante au feu, pour absorption des sons et des vibrations - Google Patents

Mousse de polyuréthane résistante au feu, pour absorption des sons et des vibrations Download PDF

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Publication number
WO2011090627A1
WO2011090627A1 PCT/US2010/060886 US2010060886W WO2011090627A1 WO 2011090627 A1 WO2011090627 A1 WO 2011090627A1 US 2010060886 W US2010060886 W US 2010060886W WO 2011090627 A1 WO2011090627 A1 WO 2011090627A1
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weight
mixture
polyether polyol
polyether
mdi
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Inventor
Yoshiaki Miyazaki
Gakusen Ishimoto
David J. Honkomp
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Dow Global Technologies LLC
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Dow Global Technologies LLC
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    • 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
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4072—Mixtures of compounds of group C08G18/63 with other macromolecular compounds
    • 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
    • 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
    • C08G18/4804—Two or more polyethers of different physical or chemical nature
    • C08G18/4812—Mixtures of polyetherdiols with polyetherpolyols having at least three hydroxy groups
    • 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
    • C08G18/4804—Two or more polyethers of different physical or chemical nature
    • C08G18/4816—Two or more polyethers of different physical or chemical nature mixtures of two or more polyetherpolyols having at least three hydroxy groups
    • 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
    • C08G18/4833—Polyethers containing oxyethylene units
    • C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
    • C08G18/4845—Polyethers containing oxyethylene units and other oxyalkylene units containing oxypropylene or higher oxyalkylene end groups
    • 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
    • C08G18/4833—Polyethers containing oxyethylene units
    • C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
    • C08G18/485—Polyethers containing oxyethylene units and other oxyalkylene units containing mixed oxyethylene-oxypropylene or oxyethylene-higher oxyalkylene end groups
    • 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

  • the present invention relates to methods for making fire-resistant sound and vibration-absorbing polyurethane foam.
  • Noise and vibration management is a significant issue for vehicle manufacturers, as cabin noise is a major factor in the comfort experience of automotive passengers.
  • Polyurethane foams are often used to absorb these noises.
  • the foam is installed in or around the engine compartment of the vehicle, to absorb engine and road sounds and thereby reduce noise in the passenger compartment of the vehicle.
  • These foams must not only perform well as noise and vibration absorbers, but due to the proximity to the engine and other hot components, also should be fire resistant. Because the foam often is subjected to temperatures as high as 80-100°C over extended periods of time while the engine is in operation, it is important that the foam can sustain its properties, even after it has been exposed to elevated temperatures for a long time.
  • flame retardants are added to a foam formulation in order to enable the foam to pass flammability tests.
  • flame retardants add expense and can hurt the physical properties of the foam.
  • Halogenated and/or phosphorus-containing flame retardants also can contribute to the toxicity of combustion gasses or produce a lot of smoke. Therefore, it is especially desirable to produce a foam which can pass fire tests such as the UL-94 ignition resistance test, without including halogenated and/or phosphorus-containing flame retardants into the foam formulation.
  • the invention is in one aspect a polyether polyol mixture containing dispersed polymer particles, wherein the polyether polyols are each 500 to 3000 hydroxyl equivalent weight homopolymers of propylene oxide or random or block copolymers of propylene oxide and up to 30% by weight ethylene oxide, wherein from 0 to 21% by weight of the polyether polyols are nominally difunctional, from 1 to 6% by weight of the polyether polyols have a nominal functionality of four or higher, and the balance of the polyether polyols are nominally trifunctional, and further wherein the polyether polyol mixture contains from 10 to 30 weight percent of dispersed polymer particles, based on the combined weight of the dispersed polymer particles and the polyether polyols.
  • the invention is also a process for preparing a polyurethane, comprising blending the polyether polyol mixture with a polyisocyanate and subjecting the resulting blend to conditions sufficient to cure the blend to form a polyurethane.
  • the polyol mixture of the invention is particularly suitable for preparing flexible noise and vibration-absorbing polyurethane foams. Therefore, the invention is also a process for preparing a flexible polyurethane foam comprising blending the polyether polyol mixture with a polyisocyanate in the presence of water and subjecting the resulting blend to conditions sufficient to cure the blend to form a flexible polyurethane foam.
  • foam formulations that include the polyol mixture of the invention form polyurethane foams that are efficient absorbers of noise and vibration.
  • Certain foams made using the polyol mixture have been found to meet the requirements for a V-2 rating on the UL-94 flammability test, often with immediate extinguishment of the flames once the igniting source is removed. The foams often exhibit these characteristics even after accelerated high temperature aging at 135°C for 600 hours.
  • the polyol mixture contains at least two, and preferably at least three, different polyether polyols. Each of them has a hydroxyl equivalent weight of at least 500, preferably at least 800, more preferably at least 1000, up to 3000, preferably up to 2000 and more preferably up to 1800.
  • Each of the polyether polyols is either a homopolymer of propylene oxide, or a copolymer of propylene oxide and ethylene oxide.
  • the copolymers may contain up to 30% by weight ethylene oxide, and more preferably contain up to 20% by weight ethylene oxide.
  • the ethylene oxide can be randomly polymerized with the propylene oxide, and/or can be present as an ethylene oxide cap. It is preferred that at least some of the polyether polyols contain ethylene oxide capping and have primary hydroxyl groups. It is preferred that at least 50% of the hydroxyl groups in the mixture are primary hydroxyl groups. The proportion of primary hydroxyl groups may be up to 100%, or up to 90%, or up to 85%.
  • nominally difunctional it is meant that the polyol is prepared from a difunctional starter compound. It is well-known that propylene oxides form some amount of monofunctional impurities when propylene oxide is polymerized, particularly when polymerized in an anionic polymerization process under strongly basic conditions. As a result, the actual average functionalities of propylene oxide homopolymers and copolymers tend to be somewhat lower than the nominal functionalities. For purposes of this invention, functionalities are all nominal functionalities, meaning that the functionality of a polyether polyol is considered to be the same as that as its starter compound.
  • the difunctional polyether polyol preferably constitutes from 5 to 20.5% of the total weight of the polyether polyols, more preferably from 7 to 15 % by weight thereof and still more preferably from 7 to 13% by weight thereof.
  • the functionally of these components may be 8 or even higher, with preferred functionalities being from six to eight.
  • the balance of the polyether polyols are nominally trifunctional.
  • the polyether polyols in the mixture are each initiated with polyalcohol compounds that do not contain amino groups.
  • the mixture also contains dispersed polymer particles, which constitute from 10 to 30%, preferably from 16 to 24% and still more preferably from 16 to 20% of the combined weight of the polyether polyols and the dispersed polymer particles.
  • the dispersed polymer particles preferably are prepared by an in situ polymerization of starting monomer in one or more of the polyether polyols that are contained in the mixture.
  • the dispersed polymer particles may be, for example, polyurea, polyurethane, polyurethane-urea, polystyrene, polyacrylonitrile, polystyrene-co-acrylonitrile or other types. Dispersed polystyrene, polyacrylonitrile or polystyrene-co-acrylonitrile particles are preferred types.
  • the polyol mixture can be prepared by separately manufacturing the constituent polyether polyols, blending them together and then polymerizing the dispersed polymer particles in the mixture. However, it is more typical to produce a dispersion of polymer particles in one of the polyols, and to blend that dispersion with other polyether polyols to obtain the final mixture. In that case, the starting dispersion should have a solids level higher than that of the final mixture. A typical solids level in a starting dispersion of that type is from 30 to 60%, more preferably from 35 to 50% by weight. It is also possible to form the mixture of polyether polyols (or subcombinations of the constituent polyols) by alkoxylating a mixture of starter compounds.
  • Such a mixture of starter compounds may be a mixture of a difunctional and a trifunctional starters; a mixture of a difunctional starter with a starter having a functionality of four or more; a mixture of a trifunctional initiator and a starter having a functionality of four or more; or a mixture of a difunctional starter, a trifunctional starter and a starter having a functionality of four or more.
  • High (4+) functionality starters in particular often are mixed with di- or trifunctional starters, in order to facilitate the polymerization process.
  • One way of making a polyol mixture of the invention is to blend the following four, separately manufactured polyols:
  • the continuous polyol phase in this case is nominally trifunctional polyether polyol, and the dispersed polymer particles are preferably polystyrene, polyacrylonitrile or poly(styrene-co-acrylonitrile);
  • Another way of making a polyol mixture of the invention is to blend the following three, separately manufactured polyols:
  • the continuous polyol phase in this case is nominally trifunctional polyether polyol, and the dispersed polymer particles are preferably polystyrene, polyacrylonitrile or poly(styrene-co-acrylonitrile);
  • polyether polyol From 8 to 44 parts by weight of a nominally trifunctional polyether polyol.
  • the polyether polyols in each case have the general characteristics (composition and equivalent weight) described before with respect to the components of the mixture.
  • the resulting mixture of polyether polyols is useful for preparing a variety of polyurethane polymers, through reaction with one more organic polyisocyanates.
  • Polyurethane is used herein as a shorthand term to denote polymers that have urethane groups, and optionally other groups such as urea groups.
  • the particular manufacturing process used to prepare the polyurethane is not considered to be critical to the invention. Therefore, a variety of molding, casting, bulk polymerization, dispersion or solution polymerization and like methods can be used.
  • polyurethane products can be prepared, including non-cellular elastomers, microcellular elastomers, structural foams, rigid insulating foams, viscoelastic foams, flexible foams (both molded or slabstock types), reinforced polymers of various types, and the like.
  • the organic polyisocyanate which reacts with the polyol mixture to make the polyurethane may be an aromatic, cycloaliphatic, or aliphatic isocyanate.
  • Aromatic polyisocyanates are preferred and, among these, diphenylmethane diisocyanate (MDI) and/or a polymethylene polyphenylisocyanate are preferred on the basis of generally greater reactivity, availability and cost.
  • MDI may be the 2,4'-isomer, the 4,4'-isomer, or some mixture thereof.
  • Polymeric MDI products i.e., mixtures of one or polymethylene polyphenylisocyanates and some MDI, are useful; the MDI portion of a polymeric MDI may be either or both of the 2,4'- and the 4,4'-isomers.
  • the polyisocyanate is generally used in an amount sufficient to provide an isocyanate index of from about 0.60 to 1.5, preferably from 0.75 to I, and more preferably from 0.80 to 0.90, although values outside of these ranges may be useful in specific situations.
  • the reaction between the polyol mixture and the organic polyisocyanate can be performed in the presence of various types of other materials, as may be useful in the particular manufacturing process that is used or to impart desired characteristics to the resulting polymer.
  • materials include, for example, catalysts, blowing agents, cell openers, surfactants, crosslinkers, chain extenders, fillers, colorants, fire retardants, pigments, antistatic agents, reinforcing fibers, antioxidants, preservatives, acid scavengers, and the like.
  • the polyol mixture of the invention is useful in making flexible polyurethane foam for noise abatement application. It offers particular advantages in formulations that contain water, which is typically present in amounts ranging from 1 to 2.5 parts, especially from 1.7 to 2.35 parts by weight of water per 100 parts by weight of the polyol mixture. Polyurethane foams are made from these by reacting the polyol mixture with an organic polyisocyanate in the presence of the water. This is typically done in a closed mold, although slabstock foam processes also can be used in some cases.
  • a useful polyisocyanate for noise abatement foam applications is an MDI (2,4'-, 4,4'- or mixture of isomers) or a polymeric MDI. Prepolymers made from MDI and/or a polymeric MDI are also useful.
  • the polyisocyanate may be a polymeric MDI or prepolymer made from MDI or polymeric MDI.
  • a suitable isocyanate prepolymer can contain from 90 to 100% monomeric MDI, of which up to 10% is the 2,4'-isomer, and can have an isocyanate content of from 10 to 30% by weight, preferably from 15-25% by weight.
  • a suitable prepolymer is that described in US Published Patent Application No. 2008-0041522.
  • An especially preferred polyisocyanate for noise and vibration abatement foams contains carbodiimide groups.
  • the preferred polyisocyanate may contain at least 2% by weight of a carbodiimide-modified MDI, and more preferably at least about 3.5% of a carbodiimide-modified MDI. It may contain up to 10% of a carbodiimide-modified MDI.
  • the carbodiimide-modified MDI preferably has an isocyanate equivalent weight of from 130 to 150.
  • the carbodiimide-modified MDI can be in the form of a mixture with (1) monomeric MDI, which preferably includes at least some 2,4'- isomer, (2) a polymeric MDI, and/or (3) an MDI prepolymer.
  • the MDI prepolymer may have an isocyanate equivalent weight of from about 150 to 250, and may be, for example, a reaction product of MDI, polymeric MDI and/or a carbodiimide-modified MDI with a polyether polyol and/or a polyester polyol which has a hydroxyl equivalent weight of from 250 to 2000 and a hydroxyl functionality from 2 to 3.
  • a mixture of prepolymers can be used.
  • a particularly preferred polyisocyanate product that is commercially available is sold by The Dow Chemical Company as SpecFlex NE344. It contains carbodiimide- modified MDI, polymeric MDI and MDI prepolymers. It contains about 4-8% by weight of carbodiimide-modified MDI.
  • Another suitable isocyanate includes those described in US Published Patent Application No. 2003-0096884.
  • foam formulation Various other components can be present in the foam formulation, in addition to the aforementioned polyisocyanate, polyol and water.
  • At least one catalyst normally will be present in the foam formulation.
  • One preferred type of catalyst is a tertiary amine catalyst.
  • the tertiary amine catalyst may be any compound possessing catalytic activity for the reaction between a polyol and a polyisocyanate and at least one tertiary amine group.
  • Representative tertiary amine catalysts include trimethylamine, triethylamine, dimethylethanolamine, N- methylmorpholine, N-ethylmorpholine, ⁇ , ⁇ -dimethylbenzylamine, N,N- dimethylethanolamine, N,N,N',N'-tetramethyl-l,4-butanediamine, N,N- dimethylpiperazine, l,4-diazobicyclo-2,2,2-octane, bis(dimethylaminoethyl)ether, bis(2- dimethylaminoethyl) ether, morpholine,4,4'-(oxydi-2, l-ethanediyl)bis, triethylenediamine, pentamethyl diethylene triamine, dimethyl cyclohexyl amine, N- cetyl ⁇ , ⁇ -dimethyl amine, N-coco-morpholine, ⁇ , ⁇ -dimethyl aminomethyl N-methyl ethanol amine, N,
  • Low (up to 200) hydroxyl equivalent weight polyols that are amine-initiated are also useful catalysts. These include polyols initiated with bis(3- aminopropyl)methylamine.
  • the foam formulation may contain one or more other catalysts, in addition to or instead of the tertiary amine catalyst mentioned before.
  • tin carboxylates and tetravalent tin compounds include stannous octoate, dibutyl tin diacetate, dibutyl tin dilaurate, dibutyl tin dimercaptide, dialkyl tin dialkylmercapto acids, dibutyl tin oxide, dimethyl tin dimercaptide, dimethyl tin diisooctylmercaptoacetate, and the like.
  • Catalysts are typically used in small amounts.
  • the total amount of catalyst used may be 0.0015 to 5, preferably from 0.01 to 1 part by weight per 100 parts by weight of polyol or polyol mixture.
  • Metal-containing catalysts are typically used in amounts towards the low end of these ranges.
  • the foam formulation may contain a crosslinker, which preferably is used, if at all, in small amounts, to 2 parts, up to 0.75 parts, or up to 0.5 parts by weight per 100 parts by weight of the mixture of polyether polyols).
  • the crosslinker contains at least three isocyanate-reactive groups per molecule and has an equivalent weight, per isocyanate reactive group, of from 30 to about 125 and preferably from 30 to 75.
  • Aminoalcohols such as monoethanolamine, diethanolamine and triethanolamine are preferred types, although compounds such as glycerin, trimethylolpropane and pentaerythritol also can be used.
  • a surfactant is preferably included in the foam formulation to help stabilize the foam as it expands and cures.
  • surfactants include nonionic surfactants and wetting agents such as those prepared by the sequential addition of propylene oxide and then ethylene oxide to propylene glycol, solid or liquid organosilicones, and polyethylene glycol ethers of long chain alcohols.
  • Ionic surfactants such as tertiary amine or alkanolamine salts of long chain alkyl acid sulfate esters, alkyl sulfonic esters and alkyl arylsulfonic acids can also be used.
  • the surfactants prepared by the sequential addition of propylene oxide and then ethylene oxide to propylene glycol are preferred, as are the solid or liquid organosilicones.
  • useful organosilicone surfactants include commercially available polysiloxane/polyether copolymers such as Tegostab (trademark of Goldschmidt Chemical Corp.) B-8729, and B-8719LF, and NiaxTM L2171 surfactant from OSi Specialties.
  • Non-hydrolyzable liquid organosilicones are more preferred.
  • a surfactant it is typically present in an amount of 0.0015 to 1 part by weight per 100 parts by weight polyol or polyol mixture.
  • a cell opener may be present in the foam formulation.
  • the cell opener functions during the polymerization reaction to break cell walls and therefore promote the formation of an open cell structure.
  • a high open cell content (at least 25% by number, preferably at least 50%) is usually beneficial for foams that are used in noise and vibration absorption applications.
  • a useful type of cell opener includes ethylene oxide homopolymers or random copolymers of ethylene oxide and a minor proportion of propylene oxide, which have a molecular weight of 5000 or more. These cell openers preferably have a hydroxyl functionality of at least 4, more preferably at least 6. Cell openers are preferably used in amounts from about 0.5 to about 5 parts by weight per 100 parts by weight of the mixture of ethylene oxide-capped polypropylene oxide.
  • the foam formulation preferably contains no more than 10 parts and more preferably no more than 2 parts by weight of any other polyol having an equivalent weight of 500 or greater. It is most preferred that no other polyols having an equivalent weight of 500 or greater are present in the foam formulation.
  • a chain extender by which it is meant a compound having exactly two isocyanate-reactive groups and an equivalent weight per isocyanate-reactive group of up to 499, preferably up to 250, also may be present.
  • Chain extenders if present at all, are usually used in small amounts, such as up to 10, preferably up to 5 and more preferably up to 2 parts by weight per 100 parts by weight of the mixture of ethylene oxide-capped polypropylene oxides.
  • chain extenders examples include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,4-dimethylolcyclohexane, 1,4-butane diol, 1,6-hexane diol, 1,3-propane diol, diethyltoluene diamine, amine-terminated polyethers such as Jeffamine D-400 from Huntsman Chemical Company, amino ethyl piperazine, 2-methyl piperazine, 1,5- diamino-3-methyl-pentane, isophorone diamine, ethylene diamine, hexane diamine, hydrazine, piperazine, mixtures thereof and the like.
  • amine-terminated polyethers such as Jeffamine D-400 from Huntsman Chemical Company, amino ethyl piperazine, 2-methyl piperazine, 1,5- diamino-3-methyl-pentane, isophorone diamine, ethylene diamine
  • the foaming reaction may be conducted in the presence of a filler, which reduces overall cost and may improve flame resistance, firmness and other physical properties to the product.
  • the filler may constitute up to about 50 percent of the total weight of the polyurethane foam formulation.
  • Suitable fillers include talc, mica, montmorillonite, marble, barium sulfate (barytes), milled glass granite, milled glass, calcium carbonate, aluminum trihydrate, carbon, aramid, silica, silica-alumina, zirconia, talc, bentonite, antimony trioxide, kaolin, coal based fly ash and boron nitride.
  • the amount of polyisocyanate that is used to make the foam typically is sufficient to provide an isocyanate index of from 70 to 100, although wider ranges can be used in special cases.
  • a preferred range is from 70 to 90 and a more preferred range is from 80 to 90.
  • Foam can be made in accordance with the invention in a slabstock process or in a molding process.
  • Slabstock foam is formed as a large bun which is cut into the required shape and size for use.
  • Molding processes can be either so-called hot molding process or a cold molding process.
  • An integral skin can be formed onto the surface of the foam in the mold.
  • a film, fabric, leather or other coverstock can be inserted into the mold prior to introducing the foam formulation, to produce a foam that has a desirable show surface.
  • a high open cell content (at least 25% by number, preferably at least 50%) is usually beneficial for foams that are used in noise and vibration absorption applications.
  • the foam advantageously also has a density in the range of 2.0 to 10 pounds/cubic foot (pcf) (32-160 kg/m 3 ), and, for noise and vibration dampening applications, preferably from 5.0 to 7.5 pounds/cubic foot (80-104 kg/m 3 ). Density is conveniently measured according to ASTM D 3574.
  • the polyol mixture of the invention can be processed into flexible polyurethane foam that has a V-2 rating on the UL-94 ignition test.
  • the foam often will retain that rating after exposure to elevated temperatures, as evidenced by the performance of the foam on the UL-94 test after being subjected to accelerated aging at 135°C for 600 hours.
  • Under the UL-94 test a 10 mm X 120 mm X 10 mm test sample is held vertically and ignited at the bottom for 10 seconds using a gas burner. The igniting source is then removed and the time required for the flames to extinguish is measured
  • the foams are particularly useful for noise and vibration-absorbing applications such as, for example in automotive engine compartments, or a noise and/or vibration for other motorized apparatus such as motorcycles, jet skis, trucks, busses and the like. It can also be used as noise abatement for building heating systems, in floors and walls in buildings, and for other applications.
  • the foams preferably absorb at least 10% of sound pressure over a frequency range from 1000 to 4000 Hz.
  • Formulated polyol mixtures are prepared by mixing the following ingredients:
  • This formulated polyol is reacted with an MDI prepolymer which has an isocyanate content of about 24% by weight.
  • the components are mixed for five seconds on a high speed mixer and then transferred to a 40 cm X 40 cm X 10 mm test mold heated to 50°C.
  • the isocyanate index is 80 for Example 1 and 90 for Examples 2-4.
  • Component temperatures are 22°C.
  • the foams are demolded after 90 seconds. After cooling, the foams are cut into ten, 10 mm X 120 mm X 10 mm pieces (with skin) for flammability testing on the UL-94 test. Five of the pieces are tested immediately. Another five pieces are aged at 135°C for 600 hours, and then tested. Results are as indicated in Table I, together with the post-aging tensile strength.
  • the foams exhibit excellent flammability requirements, even after aging at 135°C for 600 hours.
  • Examples 5 and 6 are prepared by reacting the same polyol mixture as is used for Examples 1 and 2 with different isocyanates, as follows:
  • Example 5 a 2: 1 by weight mixture of an MDI prepolymer having an isocyanate content of 24% and an MDI having a 2,4'-isomer content of 50% by weight.
  • Example 6 a 2: 1 by weight mixture of an MDI prepolymer having an isocyanate content of 29% and an MDI having a 2,4'-isomer content of 50% by weight.
  • Foams are made and test in the same manner as described in previous examples. Each achieves a V-2 rating both prior to and after aging.

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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

L'invention porte sur des mousses de polyuréthane qui absorbent efficacement les bruits et vibrations, et qui donnent également de bonnes performances lors d'essais d'allumage, tels que l'essai UL-94, ces mousses étant obtenues par réaction d'un mélange de polyéther-polyols avec un polyisocyanate. Le mélange de polyéther-polyols contient des particules polymères dispersées et des polyéther-polyols qui sont difonctionnels, trifonctionnels, et ont des fonctionnalités hydroxyle supérieures.
PCT/US2010/060886 2009-12-29 2010-12-16 Mousse de polyuréthane résistante au feu, pour absorption des sons et des vibrations Ceased WO2011090627A1 (fr)

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US61/290,606 2009-12-29

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106414533A (zh) * 2014-05-29 2017-02-15 陶氏化学墨西哥股份公司 于生产聚氨酯泡沫的调配物
CN108070240A (zh) * 2016-11-11 2018-05-25 天津潞易通科技有限公司 一种环保记忆棉及其制备方法
US10427391B2 (en) * 2013-05-29 2019-10-01 Dow Quimica Mexicana S.A. De C.V. Formulation for preparing a polyurethane foam
CN116874721A (zh) * 2022-11-16 2023-10-13 江苏长顺高分子材料研究院有限公司 低密度多孔材料及其制备方法和应用

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030036578A1 (en) * 2001-06-15 2003-02-20 Andreas Arlt Preparation of highly resilient polyurethane foams
US20030096884A1 (en) 2001-09-27 2003-05-22 Tokai Rubber Industries, Ltd. Flame-resistant and sound- and vibration- insulating member for vehicles, and process of manufacturing the same
EP1679327A1 (fr) * 2003-10-28 2006-07-12 Mitsui Chemicals Polyurethanes, Inc. Mousse de polyurethanne flexible et utilisation de celle-ci
US20080041522A1 (en) 2004-10-08 2008-02-21 Zhu Huide D Low volatile isocyanate monomer containing polyurethane prepolymer and adhesive system

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030036578A1 (en) * 2001-06-15 2003-02-20 Andreas Arlt Preparation of highly resilient polyurethane foams
US20030096884A1 (en) 2001-09-27 2003-05-22 Tokai Rubber Industries, Ltd. Flame-resistant and sound- and vibration- insulating member for vehicles, and process of manufacturing the same
EP1679327A1 (fr) * 2003-10-28 2006-07-12 Mitsui Chemicals Polyurethanes, Inc. Mousse de polyurethanne flexible et utilisation de celle-ci
US20080041522A1 (en) 2004-10-08 2008-02-21 Zhu Huide D Low volatile isocyanate monomer containing polyurethane prepolymer and adhesive system

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10427391B2 (en) * 2013-05-29 2019-10-01 Dow Quimica Mexicana S.A. De C.V. Formulation for preparing a polyurethane foam
CN106414533A (zh) * 2014-05-29 2017-02-15 陶氏化学墨西哥股份公司 于生产聚氨酯泡沫的调配物
CN106414533B (zh) * 2014-05-29 2020-03-13 陶氏化学墨西哥股份公司 用于生产聚氨酯泡沫的调配物
CN108070240A (zh) * 2016-11-11 2018-05-25 天津潞易通科技有限公司 一种环保记忆棉及其制备方法
CN116874721A (zh) * 2022-11-16 2023-10-13 江苏长顺高分子材料研究院有限公司 低密度多孔材料及其制备方法和应用

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