WO2010077602A1 - Mousse pistolée de polyuréthane rigide à alvéoles ouverts présentant un caractère ignifuge amélioré - Google Patents

Mousse pistolée de polyuréthane rigide à alvéoles ouverts présentant un caractère ignifuge amélioré Download PDF

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WO2010077602A1
WO2010077602A1 PCT/US2009/066976 US2009066976W WO2010077602A1 WO 2010077602 A1 WO2010077602 A1 WO 2010077602A1 US 2009066976 W US2009066976 W US 2009066976W WO 2010077602 A1 WO2010077602 A1 WO 2010077602A1
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formulation
polyol
component
parts
open cell
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Sol Mirasol
Wayne Blank
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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
    • C08G18/54—Polycondensates of aldehydes
    • C08G18/542—Polycondensates of aldehydes with phenols
    • 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
    • C08G18/54—Polycondensates of aldehydes
    • C08G18/546—Oxyalkylated polycondensates of aldehydes
    • 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
    • C08G2110/0025—Foam properties rigid
    • 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

Definitions

  • the invention relates to the field of open cell rigid polyurethane spray foams. More particularly, the invention relates to the field of open cell rigid polyurethane spray foams exhibiting reduction in flammability.
  • Rigid polyurethane foams have been used for some time in spray foam systems, particularly for roof and pipe insulation. In such applications flame retardancy is particularly desirable, in order to mitigate the effects of both residential and commercial fires.
  • a number of polyurethane foam formulations have been developed that exhibit, to varying degrees, a reduction in flammability.
  • U.S. Patent Nos. 3,297,597; 4,137,265; and 4,383,102 disclose use of nitrogen-containing polyols prepared by alkoxylation of the reaction product of a phenol, alkanolamines and formaldehyde, which are referred to as Mannich polyols. Such foams allegedly exhibit flame retardancy as well as good dimensional strength.
  • U.S. Published Application 2002/0040122 Al discloses use of an ultra low viscosity Mannich polyol (less than about 3,500 centipoise (cP) (3.5 Pa*s) at 25 0 C, to obtain improved flame retardancy.
  • cP centipoise
  • a second polyol is included, which may be a Novolac-initiated polyol.
  • Novolac resins are prepared via the acid catalyzed polymerization of phenol and formaldehyde, and these are then alkoxylated with one or more epoxides to form the polyols.
  • spray foams for these applications are relatively low density and are water-blown. They are typically prepared from a combination of high and low molecular weight polyols, and cell opening of the foam is controlled by including of rigid and/or flexible surfactants.
  • relatively high amounts of water, to reduce density tend to result in incompatibility of the polyol blends, and also may increase the viscosity of the blends, which may make spraying more difficult. Shelf-life maybe poor because of the incompatibility, leading to phase separation, Processing dynamics may be narrow because of the combinations of polyols, catalysts, and surfactants that are combined, and the system may emit an objectionable, pungent odor, which may be attributable to certain catalysts. Foams that do exhibit some flame retardancy may still fail to meet the requirements of a Class 1 flammability rating.
  • the present invention provides, in one aspect, a sprayable polyurethane foam formulation comprising an A-component, comprising a polyisocayanate, and a B- component, comprising a Novolac-initiated polyol, a brominated polyol, and water as a blowing agent, wherein the A-component and the B -component may be reacted under conditions suitable to form an open cell rigid polyurethane foam that achieves a Class I flammability rating, according to ASTM E-84*. (*The flammability test results are not intended to reflect hazards presented by the test materials or any other materials under actual fire conditions.)
  • the invention provides a method of preparing a reduced flammability construction comprising preparing a sprayable formulation comprising an A- component, comprising a polyisocayanate, and a B-component, comprising a Novolac- initiated polyol, a brominated polyol, and water as a blowing agent, and spraying the formulation onto at least one substrate under conditions such that an open cell rigid polyurethane foam having a Class I flammability rating, according to ASTM E-84, is formed on the at least one substrate.
  • the invention provides a reduced flammability construction comprising at least one substrate having contiguous thereto an open cell rigid polyurethane foam prepared according to a method comprising preparing a sprayable formulation comprising an A-component, comprising a polyisocayanate, and a B- component, comprising a Novolac-initiated polyol, a brominated polyol, and water as a blowing agent, and spraying the formulation onto the at least one substrate under conditions such that an open cell rigid polyurethane foam having a Class I flammability rating, according to ASTM E- 84, is formed on the at least one substrate.
  • the invention may provide an open cell, rigid polyurethane foam exhibiting a desirable flammability rating, wherein the formulation therefor has a wide processing window, relatively low odor, and is relatively storage stable.
  • This foam may also contribute good insulation, including as an air barrier and as a sound-dampener.
  • the formulation includes certain typical polyurethane components, and may optionally include a number of additives or other modifiers.
  • the first is a polyisocyanate component. This is referred to in the United States as the "A-component" (in Europe, as the "B-component”). Selection of the A-component may be made from a wide variety of polyisocyanates, including but not limited to those that are well known to those skilled in the art. For example, organic polyisocyanates, modified polyisocyanates, isocyanate- based prepolymers, and mixtures thereof may be employed. These can further include aliphatic and cycloaliphatic isocyanates, and in particular aromatic and, more particularly, multifunctional aromatic isocyanates. Also particularly preferred are polyphenyl polymethylene polyisocyanates (PMDI).
  • PMDI polyphenyl polymethylene polyisocyanates
  • polyisocyanates useful in the present invention also include 2,4- and 2,6-toluenediisocyanate and the corresponding isomeric mixtures; 4,4'-, 2,4'- and 2,2'-diphenyl-methanediisocyanate and the corresponding isomeric mixtures; mixtures of 4,4'-, 2,4'- and 2,2'-diphenyl-methanediisocyanates and polyphenyl polymethylene polyisocyanates (PMDI); and mixtures of PMDI and toluene diisocyanates.
  • PMDI polyphenyl polymethylene polyisocyanates
  • aliphatic and cycloaliphatic isocyanate compounds such as 1,6-hexamethylene-diisocyanate; 1-iso- cyanato-3,5,5-trimethyl-l,3-isocyanatomethyl-cyclohexane; and 2,4- and 2,6-hexahydro- toluen-diisocyanate, as well as the corresponding isomeric mixtures; 4,4'-, 2,2'- and 2,4'- dicyclohexylmethanediisocyanate, and the isomeric mixtures corresponding thereto.
  • 1,3- tetramethylene xylene diisocyanate may also be used with the present invention.
  • modified multifunctional isocyanates that is, products which are obtained through chemical reactions of the above diisocyanates and/or polyisocyanates.
  • exemplary are polyisocyanates containing esters, ureas, biurets, allophanates and preferably carbodiimides and/or uretonomines; isocyanurate and/or urethane group containing diisocyanates or polyisocyanates.
  • Liquid polyisocyanates containing carbodiimide groups, uretonomine groups and/or isocyanurate rings, having isocyanate groups (NCO) contents of from 120 to 40 weight percent, more preferably from 20 to 35 weight percent, can also be used.
  • polyisocyanates based on 4,4'-, 2,4'- and/or 2,2'-diphenylmethane diisocyanate and the corresponding isomeric mixtures 2,4- and/or 2,6-toluenediisocyanate and the corresponding isomeric mixtures
  • mixtures of diphenylmethane diisocyanates and PMDI mixtures of toluenediisocyanates and PMDI and/or diphenylmethane diisocyanates.
  • Suitable prepolymers for use as the polyisocyanate component of the formulations of the present invention are prepolymers having NCO contents of from 2 to 40 weight percent, more preferably from 4 to 30 weight percent. These prepolymers are prepared by reaction of the di- and/or poly-isocyanates with materials including lower molecular weight diols and triols, but may alternatively be prepared with multivalent active hydrogen compounds such as di- and tri-amines and di- and tri-thiols.
  • aromatic polyisocyanates containing urethane groups preferably having NCO contents of from 5 to 40 weight percent, more preferably 20 to 35 weight percent, obtained by reaction of diisocyanates and/or polyisocyanates with, for example, lower molecular weight diols.
  • diethylene glycols, dipropylene glycols, polyoxyethylene glycols, ethylene glycols, propylene glycols, butylene glycols, polyoxypropylene glycols and polyoxypropylenepolyoxyethylene glycols may be used.
  • Polyester polyols can also be used, as well as alkyl diols such as butane diol.
  • Other diols that are also useful include bishydroxyethyl- and bishydroxypropyl-bisphenol A, cyclohexane dimethanol, and bishydroxyethyl hydroquinone.
  • polyisocyanate component of prepolymer formulations are: (i) polyisocyanates having an NCO content of from 8 to 40 weight percent containing carbodiimide groups and/or urethane groups, from 4,4'-diphenylmethane diisocyanate or a mixture of 4,4'- and 2,4'-diphenylmethane diisocyanates; (ii) prepolymers containing NCO groups, having an NCO content of from 2 to 35 weight percent, based on the weight of the prepolymer, prepared by the reaction of polyols, having a functionality of preferably from 1.75 to 4 and a molecular weight of from 800 to 15,000 with 4,4'-diphenylmethane diisocyanate or with a mixture of 4,4'- and 2,4'-diphenylmethane diisocyanate; mixtures of (i) and (ii); and (iii) 2,4' and 2,6-toluene-di
  • PMDI in any of its forms is the most preferred polyisocyanate for use with the present invention, When used, it preferably has an equivalent weight between 125 and 300, more preferably from 130 to 175, and an average functionality of greater than about 1.5. More preferred is an average functionality of from 1.75 to 3.5.
  • the viscosity of the polyisocyanate component is preferably from 25 to 5,000 centipoise (cP) (0.025 to about 5 Pa*s), but values from 100 to 1,000 cP at 25 0 C (0.1 to 1 Pa*s) are preferred for ease of processing. Similar viscosities are preferred where alternative polyisocyanate components are selected.
  • the polyisocyanate component is preferably selected from the group consisting of MDI, PMDI, an MDI prepolymer, a PMDI prepolymer, a modified MDI, and combinations thereof.
  • the B-component of the formulation is the isocyanate-reactive portion, i.e., it includes a combination of a Novolac-initiated polyol and a brominated polyol in a relatively low viscosity polyol blend.
  • Novolac-initiated polyols are the alkoxylation products of a phenol formaldehyde resin, which is formed by the elimination reaction of phenol with formaldehyde in the presence of an acid catalyst, such as glacial acetic acid, followed by concentrated hydrochloric acid.
  • an acid catalyst such as glacial acetic acid
  • concentrated hydrochloric acid usually a small amount of the acid catalyst or catalysts is/are added to a miscible phenol, such as p-toluenesulfonic acid, followed by formaldehyde.
  • the formaldehyde will react between two phenols to form a methylene bridge, creating a dimer by electrophilic aromatic substitution between the ortho and para positions of phenol and the protonated formaldehyde.
  • This dimer is bisphenol F. As concentration of dimers increase, trimers, tetramers and higher oligomers may also form. However, because the molar ratio of formaldehyde to phenol is controlled at somewhat less than 1, polymerization is not completed. Thus, the Novolac may then be alkoxylated to build equivalent weight to a desired level, desirably from about 100 to about 500; in certain non-limiting embodiments, from about 200 to about 400; and in certain other non-limiting embodiments, from about 250 to about 350.
  • Phenols which may be used to prepare the Novolac initiator include: o-, m-, or p-cresols, ethylphenol, nonylphenol, p-phenylphenol, 2,2-bis(4-hydroxyphenol) propane, beta-naphthol, beta-hydroxyanthracene, p-chlorophenol, o-bromophenol, 2,6-dichloro- phenol, p-nitrophenol, 4-nitro-6-phenylphenol, 2-nitro-4-methylphenol, 3,5-dimethyl- phenol, p-isopropylphenol, 2-bromo-4-cyclohexylphenol, 4-t-butylphenol, 2-methyl-4- bromophenol, 2-(2-hydroxypropyl)phenol, 2-(4-hydroxyphenol) ethanol, 2-carb- ethoxyphenol, 4-chloro-methylphenol, and combinations thereof. It is especially preferred that the phenols used to prepare the Novolacs useful in the present invention be unsubsti
  • Alkoxylation of the Novolac initiator, to prepare the final Novolac -initiated polyol or a prepolymer from which the final Novolac-initiated polyol may be made may, in certain embodiments be carried out using any alkylene oxide typically used by those skilled in the art. For example, ethylene oxide, propylene oxide, butylene oxide, and combinations thereof may be selected.
  • a second required polyol of the present invention' s formulation is a brominated polyol.
  • the brominated flame retardants contribute to flame retardancy by inhibiting the ignition of combustible organic materials. They may also hinder the spread of fire, that is, the time to flashover, thereby providing valuable extra time in the early stages of a fire, during which escape may be possible.
  • the brominated polyol may have a functionality of from about 1 to about 3, and a hydroxyl number from about 150 to about 260.
  • the two polyols together may have a viscosity ranging from about 20,000 cP to about 60,000 cP, and preferably from about 20,000 cP to about 40,000 cP.
  • any brominated polyol may be selected herein, useful and easily obtained polyols of this type may include decabromodiphenyl ether (decaBDE) and other polybrominated diphenyl ethers (PBDEs), including, for example, pentabromodiphenyl ether (pentaBDE), octabromodiphenyl ether (octaBDE), tetrabromobisphenol A (TBBPA or TBBP-A), hexabromocyclododecane (HBCD), and combinations thereof.
  • decaBDE decabromodiphenyl ether
  • PBDEs polybrominated diphenyl ethers
  • pentabromodiphenyl ether pentaBDE
  • octabromodiphenyl ether octaBDE
  • TBBPA or TBBP-A tetrabromobisphenol A
  • HBCD hexabrom
  • the formulation of the present invention may optionally include further additives or modifiers such as are well-known in the art.
  • surfactants, catalysts, other flame retardants, and/or fillers may be employed.
  • amine catalysts including any organic compound which contains at least one tertiary nitrogen atom and is capable of catalyzing the hydroxyl/isocyanate reaction between the A-component(s) and B-component(s).
  • Typical classes of amines include the N-alkylmorpholines, N- alkylalkanolamines, I ⁇ N-dialkylcyclohexylamines, alkylamines where the alkyl groups are methyl, ethyl, propyl, butyl and isomeric forms thereof, and heterocyclic amines.
  • Typical but non-limiting specific examples thereof are tnethylenediamine, tetramethyl- ethylenediamine, bis(2-dimethylaminoethyl)ether, triethylamine, tripropylamine, tributylamine, triamylamine, pyridine, quinoline, dimethylpiperazine, piperazine, N,N- dimethylcyclohexylamine, N-ethylmorpholine, 2-methylpropanediamine, methyltriethyl- enediamine, 2,4,6-tri-dimethylaminomethyl)phenol, N,N' ,N"-tris(dimethylaminopropyl)- sym-hexahydrotriazine, and combinations thereof.
  • a preferred group of tertiary amines comprises bis(2-dimethyl-aminoethyl)ether, dimethylcyclohexylamine, N,N-dimethyl- ethanolamine, triethylenediamine, triethylamine, 2,4,6-tri(dimethylaminomethyl)phenol, N,N', N-ethylmorpholine, and combinations thereof.
  • Non-amine catalyst may also be used in the present invention.
  • Typical of such catalysts are organometallic compounds of bismuth, lead, tin, titanium, iron, antimony, uranium, cadmium, cobalt, thorium, aluminum, mercury, zinc, nickel, cerium, molybdenum, vanadium, copper, manganese, zirconium, and combinations thereof. Included as illustrative examples only are bismuth nitrate, lead 2-ethylhexoate, lead benzoate, lead naphthenate, ferric chloride, antimony trichloride, and antimony glycolate.
  • a preferred group of organo-tin catalysts is the stannous salts of carboxylic acids, such as stannous acetate, stannous octoate, stannous 2-ethylhexoate, 1-methylimidazole, and stannous laurate, as well as the dialkyl tin salts of carboxylic acids, such as dibutyl tin diacetate, dibutyl tin dilaurate, dibutyl tin dimaleate, dioctyl tin diacetate, combinations thereof, and the like.
  • carboxylic acids such as stannous acetate, stannous octoate, stannous 2-ethylhexoate, 1-methylimidazole, and stannous laurate
  • dialkyl tin salts of carboxylic acids such as dibutyl tin diacetate, dibutyl tin dilaurate, dibutyl tin dimaleate, dioctyl
  • trimerization catalysts may be used with the present invention.
  • the trimerization catalyst employed may be any known to those skilled in the art which will catalyze the trimerization of an organic isocyanate compound to form the isocyanurate moiety.
  • isocyanate trimerization catalysts see The Journal of Cellular Plastics, November/December 1975, page 329: U.S. Patents 3,745,133; 3,896,052; 3,899,443; 3,903,018; 3,954,684 and 4,101,465; the disclosures of which are incorporated herein in their entireties by reference.
  • Typical trimerization catalysts include the glycine salts and tertiary amine trimerization catalysts, as well as the alkali metal carboxylic acid salts and combinations thereof.
  • Preferred species within the classes are sodium N-2- hydroxy-5-nonylphenyl) methyl-N-methylglycinate, and N,N-dimethyl-cyclohexylamine, and mixtures thereof.
  • Also included in the preferred catalyst components are the epoxides disclosed in U.S. Patent 3,745,133, the disclosure of which is incorporated herein in its entirety by reference.
  • additives useful with the present invention are one or more non- brominated flame retardants.
  • non- brominated flame retardants such as triethylphosphate, tris(2-chloroethyl) phosphate, tris(2-chloropropyl)phosphate, tris(l ,3-dichloropropyl)phosphate, diammonium phosphate, halogenated aromatic compounds, antimony oxide, alumina tnhydrate, polyvinyl chloride, and combinations thereof.
  • Dispersing agents, cell stabilizers, and surfactants may also be incorporated into the formulations.
  • Surfactants including organic surfactants and silicone based surfactants, may also be added to serve as cell stabilizers.
  • Some representative materials are sold under the designations SF-1109, L-520, L-521 and DC-193, which are, generally, polysiloxane polyoxylalkylene block copolymers, such as those disclosed in U.S. Patents 2,834,748; 2,917,480; and 2,846,458, for example, the disclosures of which are incorporated herein in their entireties by reference.
  • organic surfactants containing polyoxyethylene-polyoxybutylene block copolymers as described in U.S. Patent 5,600,019, the disclosure of which is incorporated herein in its entirety by reference.
  • Other additives such as carbon black and colorants may be added.
  • fillers such as barium sulfate and other inert inorganic particulates, including both natural and synthetic minerals, clays, and the like, may also be included in the rigid spray foams of the present invention.
  • the last component of the formulation is the blowing agent. While it may be included in the B-component, prior to combination with the A-component, it may also be a separate component in itself, combining simultaneously with the A-component and B-component in, for example, conventional spray equipment, In the present invention water is preferred. While other known blowing agents may be used, water offers the advantages of low cost, ease of use, and effectiveness in preparing specifically open cell, rigid polyurethane foams. Water and minor amounts of other blowing agents may also be used. For example, some of these other blowing agents may include hydrocarbons, chlorinated hydrocarbons, fluorinated hydrocarbons, combinations thereof, and the like.
  • the blowing agent used with water is selected from HCFC-141b, HCFC-22, HFC- 134a, n-pentane, isopentane, cyclopentane, HCFC-124, HFC-245f, HFC-365 mfc, combinations thereof, and the like.
  • Some halocarbon blowing agents may be effective in reducing viscosity to a desirable level to optimize sprayability.
  • the A-component and the B-component be admixed at any suitable volume or weight ratio as desired for the particular composition, formulation method or equipment.
  • the Novolac-initiated polyol may be included in the B-component in an amount ranging from about 1 to about 99 parts by weight, based on 100 parts of total polyol, i.e., all polyols combined in the formulation.
  • the brominated polyol may be included in any amount ranging from about 1 to about 60 parts by weight, and in certain particular and non-limiting embodiments, ranging from about 10 to about 40 parts by weight, on the same basis, Additional polyols, if desired, may be included in any amount ranging from 0 to about 60 parts by weight, on the same basis.
  • Non-brominated phosphate additives such as tris-chloro-isopropyl phosphate (TCPP) and/or triethylphosphate (TEP), may be included in any amount ranging from 0 to about 20 parts by weight, on the same basis.
  • Surfactants such as TEGOSTAB* B-8404, may be included in any amount ranging from O to about 6 parts by weight, on the same basis.
  • TEGOSTAB* B-8404 is available from Evonik.
  • Catalysts such as NIAX* A-I, POLYCAT* 9 and/or POLYCAT* 77, may be included in amounts from about 1 to about 15 parts by weight, on the same basis.
  • NIAX* A-I is available from General Electric.
  • POLYCAT* 9 and POLYCAT* 77 are available from Air Products.) Additional catalysts, such as TOYOCAT* DM 70 or other gelling catalysts, may be included in amounts ranging from O to about 2 parts by weight, on the same basis. (TOYOCAT* DM 70 is available from Tosoh Corporation.) Finally, water may be included in amounts ranging from about 5 to about 40 parts by weight, on the same basis.
  • the Novolac-initiated polyol may, in some non-limiting embodiments, be present in the B-component in an amount ranging from about 1 to about 99 parts by weight, based on 100 parts of total polyol, and the brominated polyol is in a range of from about 1 to about 60 parts by weight, on the same basis.
  • the Novolac-initiated polyol is present in an amount from about 30 to about 90 parts by weight, with the brominated polyol representing from about 10 to about 40 parts by weight, on the same basis.
  • the Novolac- initiated polyol is present in an amount from about 40 to about 80 parts by weight, based on 100 parts of total polyol, with the brominated polyol representing from about 20 to about 30 parts by weight, on the same basis.
  • the amount of Novolac-initiated polyol, brominated polyol, and if selected, other polyols known in the art as useful for making rigid polyurethane foams equals 100 parts by weight. In calculating these amounts, additional materials, such as surfactants, catalysts, other flame retardants, and/or fillers, are excluded.
  • the water is desirably present in an amount of from about 0.5 to about 40 parts by weight, based on 100 parts of total polyol.
  • water may be used in an amount of from about 10 to about 35 parts by weight, on the same basis, and in still more preferred but non-limiting embodiments, water may be employed in an amount of from about 20 to about 30 parts by weight, again, on the same basis.
  • any methods and means known or contemplated by those skilled in the art as useful for preparing open cell, rigid polyurethane spray foams may be employed.
  • Final foam density may, in certain non-limiting embodiments, range from about 0.2 to about 10 pounds per cubic foot (pcf), and in other non-limiting embodiments, from about 0.4 to about 1.0 pcf. Such density range may be particularly desirable in preparing a reduced flammability construction wherein the foam is contiguous to surfaces of a substrate, such as a ceiling or wall, such that the foam provides both good flammability performance as well as a desirable level of insulation.
  • pcf pounds per cubic foot
  • Such other embodiments may include selections of specific polyols and isocyanates; mixing and reaction conditions; vessels and deployment apparatuses; protocols; performance and selectivity; identifi-cation of products and by-products; subsequent processing and use thereof; and the like; and those skilled in the art will recognize that such may be varied within the scope of the claims appended hereto.
  • a spray formulation is prepared using the following materials.
  • IP* 585 manufactured by The Dow Chemical Company.
  • Triethylphosphate a flame suppressant.
  • TEGOSTAB* B-8404 manufactured by Degussa.
  • a silicone surfactant comprising bis(2- dimethylaminoethyl)ether in dipropylene glycol, OH # of 250.
  • POLYCAT* 9 manufactured by Air Products.
  • a gelling catalyst TOYOCAT* DM 70, manufactured by Tosoh Corporation.
  • a curing catalyst comprising
  • the formulation is fed through a Gusmer H20/35 Series Proportioning Machine and a GX 7 spray gun.
  • One (volume) part of PAPI* 27 is matched with one (volume) part of B-component, which results in an isocyanate index of 0.38.
  • the formulation is shown in Table 1, expressed in weight. TABLE 1
  • A-COMPONENT Parts by Percent by weight, per 100 weight (of the parts of total specified polyol component)
  • PAPP 27 isocyanate 166.2 100
  • B-component viscosity is at 320 cP at 25 0 C (0.32 Pa*s), and the specific gravity of the B-component is 1.16 at 25 0 C.
  • Hand-mixing tests of a 50 g sample at 75 0 F show a cream time of 2 seconds, a gel time of 6 seconds, and a core density of the final foam of 0.50 pounds per cubic foot (pcf).
  • the final spray applied foam exhibits a density of 0.58 pcf, and a k-Factor of 0.235 Btu.in/ft 2 .hr.°F.
  • Flame test screening under American Society for Testing Materials (ASTM) E-84 showed a flame spread, at a 4-inch thickness, of 25, and smoke development of 250. This qualifies as a Class I flammability rating.

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Abstract

L'invention porte sur une mousse de polyuréthane rigide à alvéoles ouverts, particulièrement appropriée pour des applications au pistolet, préparée à partir d'une formulation renfermant au moins un polyol initié par novolac, un polyol bromé, un polyisocyanate et de l'eau en tant qu'agent gonflant. La mousse doit être apte à obtenir un classement d'inflammabilité de classe I conformément à la norme ASTM E-84.
PCT/US2009/066976 2008-12-08 2009-12-07 Mousse pistolée de polyuréthane rigide à alvéoles ouverts présentant un caractère ignifuge amélioré Ceased WO2010077602A1 (fr)

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US12071208P 2008-12-08 2008-12-08
US61/120,712 2008-12-08

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Cited By (8)

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WO2012004229A1 (fr) * 2010-07-08 2012-01-12 Basf Se Mousse de polyuréthane rigide
CN103756292A (zh) * 2014-01-08 2014-04-30 合肥杰事杰新材料股份有限公司 一种线性酚醛树脂改性的聚氨酯复合阻燃泡沫及其制备方法
US9538867B2 (en) 2012-01-20 2017-01-10 Basf Se Composite body and method of making the same
WO2017127462A1 (fr) * 2016-01-18 2017-07-27 Honeywell International Inc. Mousses thermodurcies souples à alvéoles ouverts, agents d'expansion et leurs procédés de fabrication
WO2017204782A1 (fr) * 2016-05-23 2017-11-30 Boral Ip Holdings (Australia) Pty Limited Mousse de polyuréthane chargée à microstructures adaptées
EP3280764A1 (fr) * 2015-04-10 2018-02-14 Dap Products Inc. Compositions stables de mousse à pulvériser à deux composants contenant un propulseur ou un agent d'expansion de type oléfine hydrohalogénée
CN113891903A (zh) * 2019-05-24 2022-01-04 陶氏环球技术有限责任公司 用于制备阻燃硬质聚氨酯泡沫的储存稳定的含hfo或hcfo的多元醇组合物
CN114555669A (zh) * 2019-10-08 2022-05-27 赢创运营有限公司 硬质聚氨酯泡沫的生产

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US20020040122A1 (en) * 2000-06-19 2002-04-04 Mirasol Sol M. Water blown rigid polyurethane foam with improved fire retardancy

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US3943077A (en) * 1973-05-14 1976-03-09 Owens-Corning Fiberglas Corporation Fire retardant polyurethane foams
US4579876A (en) * 1984-02-21 1986-04-01 Mobay Chemical Corporation Polyols for the production of rigid polyurethane foams
DE19736574A1 (de) * 1997-08-22 1999-02-25 Basf Ag Verfahren zur Herstellung von gegenüber Isocyanaten reaktiven Verbindungen
US20020040122A1 (en) * 2000-06-19 2002-04-04 Mirasol Sol M. Water blown rigid polyurethane foam with improved fire retardancy

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012004229A1 (fr) * 2010-07-08 2012-01-12 Basf Se Mousse de polyuréthane rigide
CN103119076A (zh) * 2010-07-08 2013-05-22 巴斯夫欧洲公司 刚性聚氨酯泡沫体
US9538867B2 (en) 2012-01-20 2017-01-10 Basf Se Composite body and method of making the same
CN103756292A (zh) * 2014-01-08 2014-04-30 合肥杰事杰新材料股份有限公司 一种线性酚醛树脂改性的聚氨酯复合阻燃泡沫及其制备方法
EP3280764A1 (fr) * 2015-04-10 2018-02-14 Dap Products Inc. Compositions stables de mousse à pulvériser à deux composants contenant un propulseur ou un agent d'expansion de type oléfine hydrohalogénée
WO2017127462A1 (fr) * 2016-01-18 2017-07-27 Honeywell International Inc. Mousses thermodurcies souples à alvéoles ouverts, agents d'expansion et leurs procédés de fabrication
WO2017204782A1 (fr) * 2016-05-23 2017-11-30 Boral Ip Holdings (Australia) Pty Limited Mousse de polyuréthane chargée à microstructures adaptées
CN113891903A (zh) * 2019-05-24 2022-01-04 陶氏环球技术有限责任公司 用于制备阻燃硬质聚氨酯泡沫的储存稳定的含hfo或hcfo的多元醇组合物
CN114555669A (zh) * 2019-10-08 2022-05-27 赢创运营有限公司 硬质聚氨酯泡沫的生产

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